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Pub Liquid-Crystals PDF
Pub Liquid-Crystals PDF
Pub Liquid-Crystals PDF
classic book Liquid crystals, first published in 1977. In this second edition
the author has brought the subject completely up to date.
This book will be of great value to advanced students and research workers
in condensed matter physics, chemical physics, materials science and
technology with an interest in the physics, chemistry and applications of
liquid crystals.
LIQUID CRYSTALS
LIQUID CRYSTALS
Second edition
S. CHANDRASEKHAR, F.R.S.
Centre for Liquid Crystal Research, Bangalore
CAMBRIDGE
UNIVERSITY PRESS
Published by the Press Syndicate of the University of Cambridge
The Pitt Building, Trumpington Street, Cambridge CB2 1RP
40 West 20th Street, New York, NY 10011-4211, USA
10 Stamford Road, Oakleigh, Victoria 3166, Australia
A catalogue record for this book is available from the British Library
UP
Contents
vii
viii Contents
' I am at a loss to give a distinct idea of the nature of this liquid, and
cannot do so without many words.'
The Narrative of Arthur Gordon Pym of Nantucket,
Edgar Allan Poe
The foundations of the physics of liquid crystals were laid in the 1920s but,
surprisingly, interest in these substances died down almost completely
during the next three decades. The situation was summarized by F. C.
Frank in his opening remarks at a Discussion of the Faraday Society in
1958: 'After the Society's successful Discussion on liquid crystals in 1933,
too many people, perhaps, drew the conclusion that the major puzzles were
eliminated, and too few the equally valid conclusion that quantitative
experimental work on liquid crystals offers powerfully direct information
about molecular interactions in condensed phases.' In the last few years
there has been a resurgence of activity in this field, owing partly to the
realization that liquid crystals have important uses in display technology.
An exposition of the physics of liquid crystals involves many disciplines:
continuum mechanics, optics of anisotropic media, statistical physics,
crystallography etc. In covering such a wide field it is difficult to define
what precisely the reader is expected to know already. An attempt is made
to present as far as possible a self-contained treatment of each of these
different aspects of the subject. Naturally, discussion of some topics has
had to be curtailed for reasons of space. For example, we have not dealt
with lyotropic systems, whose complex structures are only just beginning
to be elucidated; or the special applications of magnetic resonance
techniques, as these have been adequately reviewed elsewhere; or the very
recent results of neutron scattering experiments. The primary aim of this
monograph is to provide an insight into the variety of new phenomena
exhibited by these intermediate states of matter.
Xlll
xiv Preface to the first edition
This book would probably never have been completed without the
unstinting cooperation of my young colleagues in Bangalore. I am
particularly indebted to N. V. Madhusudana, G. S. Ranganath, R.
Shashidhar, U. D. Kini, R. Nityananda and T. G. Ramesh, whose notes
and critical comments were of inestimable value at every stage of the
writing, and to K. A. Suresh and B. R. Ratna for their assistance in
preparing the diagrams and the list of references. Finally, it is a pleasure to
express my thanks to Michael Woolfson for his encouraging interest and
advice.
Since the publication of the first edition 15 years ago, the subject of liquid
crystals has grown enormously to become a fascinating interdisciplinary
field of study. A variety of new thermotropic phases have been discovered,
including over a dozen different smectic modifications, discotics, biaxial
nematics, etc., which have opened up a veritable treasure-house for the
theoretical condensed matter physicist. On the technological side, the
advances have been no less spectacular: portable computers and hand-held
TV sets using liquid crystal display devices are being sold in large numbers,
and high-definition LCD-TV would seem to be just round the corner. The
aim of the present edition is to bring the coverage up to date. The chapters
dealing with the classical nematic, cholesteric and smectic types of liquid
crystals have been revised substantially and a new chapter has been
included on discotics. However, mainly for reasons of space, special topics
like the applications of magnetic resonance techniques, non-linear optical
properties, etc., have not been discussed here as these have been
comprehensively reviewed elsewhere.
It is my privilege to express my thanks to my young colleagues who kept
me alive to the subject: in particular to V. N. Raja, S. Krishna Prasad,
D. S. Shankar Rao, S. M. Khened and Geetha Nair for their invaluable
help throughout the preparation of this book, and to Sriram Ramaswamy
and U. D. Kini for their advice on certain theoretical points. I am indebted
to the Council of Scientific and Industrial Research, New Delhi, for a
Bhatnagar Fellowship which made it easier for me to undertake this task.
xv
1
Introduction
1
1. Introduction
Crystal
Nematic
(a)
(b)
Fig. 1.1.2. X-ray diffraction patterns from an 'ordinary' nematic liquid crystal:
4-n-propyloxy-benzylidene-4/-n-propylaniline: (a) an unaligned (though not quite
randomly oriented) sample; (b) a well aligned sample. (De Vries.(6))
(a)
(b)
Fig. 1.1.4. The cholesteric liquid crystal: schematic representation of the helical
structure.
(a)
Illllllllllllllllll
Illlllllllllllllll
Illllllllllllllllll
Fig. 1.1.5. Schematic representation of the molecular arrangement in (a) smectic A
and (b) smectic C.
These phases exist over a small temperature range (~ 1 °C) between the
liquid crystal phase and the isotropic liquid. Their structures will be
discussed in §4.8.
Smectic liquid crystals have stratified structures but a variety of
molecular arrangements are possible within each stratification. In smectic
A the molecules are upright in each layer with their centres irregularly
spaced in a 'liquid-like' fashion (fig. I A.5 (a)). The interlayer attractions
are weak as compared with the lateral forces between molecules and in
consequence the layers are able to slide over one another relatively easily.
Hence this mesophase has fluid properties, though it is very much more
viscous than the nematic. Smectic C is a tilted form of smectic A, i.e., the
molecules are inclined with respect to the layer normal (fig. 1.1.5(6)).
Several polymorphic forms of smectics A and C exist, as we shall see later.
Over a dozen other distinct smectic modifications have been identified/ 10 ' U)
Some of them (e.g., SB, S E , SG, SH, ST and SK) have three-dimensional long-
range positional order as in a crystal, though with weak interlayer forces
(and hence energetically weak interlayer ordering), while some others,
referred to as hexatic phases, have three-dimensional long-range 'bond-
orientational' order, but without any long-range positional order. (12) The
1.1 Thermotropic liquid crystals
Fig. 1.1.6. (a) Threads in a nematic liquid crystal. Crossed polarizers. Film
thickness ~ 100 jum. (b) Schlieren texture in a nematic film of thickness ~ 10 jum.
Crossed polarizers. (Sackmann and Demus. (14))
8 1. Introduction
Fig. 1.1.7. Focal conic textures in smectic A. (a) The polygonal texture. Crossed
polarizers. (Friedel.(4)) (b) Simple fan-shaped texture. Crossed polarizers. (Sack-
mann and Demus.(14))
systems (see fig. 1.2.2), but a number of variants of this structure have been
identified: hexagonal, rectangular, tilted, etc. The nematic phase has an
orientationally ordered arrangement of the discs without any long-range
translational order (fig. 1.1.8(6)). Unlike the classical nematic of rod-like
molecules, this phase is optically negative. A cholesteric (or twisted
nematic) phase has also been identified. A smectic-like lamellar phase has
been reported(22) but the disposition of the molecules in the layers has not
yet been resolved.
10 1. Introduction
(a)
Fig. 1.1.8. The structure of (a) the columnar phase and (b) the nematic phase of
disc-like molecules.
(b)
Fig. 1.1.9. Polymers that exhibit liquid crystalline phases. The basic monomer units
are low molar mass rod-like or disc-like mesogens which may form part of the main
chain (a) or attached as side groups (b).
(a)
to
Fig. 1.1.10. Mesophases of discotic polymers: (a) the hexagonal columnar phase.
The diagram illustrates intercolumnar binding as well as intracolumnar back-
folding of the main chain (Herrmann-Schonherr, Wendorff and Ringsdorf (24) );
(b) the' sanidic' nematic phase composed of boards stacked parallel to one another
(Herrmann-Schonherr et al.{25)); (c) the columnar nematic phase (Ringsdorf
et al (26) ).
backbone, the mesogenic unit and the spacers. With rod-shaped repeating
units, mesophases similar to the nematic, cholesteric and smectic types of
rod-like molecules are observed(23) whereas with disc-shaped repeating
units, some new kinds of mesophase structures have been found. For
12 1. Introduction
example, a polyester with (disc-shaped) triphenylene as the repeating unit
in the main chain separated by flexible spacers forms a hexagonal columnar
structure (24) (fig. 1.1.10 (a)). On the other hand, rigid aromatic polyamides
and polyesters with disc-shaped units in the main chain exhibit a different
type of mesophase which has been described as a ' sanidic' (or board-like)
nematic,(25) the boards stacked parallel to one another as shown in fig.
1.1.10(6). The addition of electron acceptor molecules to discotic polymers
results in the formation of charge transfer complexes which stabilize - or in
certain non-mesomorphic materials, induce-mesophases. (26) A new type
of induced mesophase identified in such a system is the' columnar nematic'
illustrated in fig. 1.1.10(c).
4'-n-Pentyl-4-cyanobiphenyl'I (39)
(1.3.2)
111
\ / / \ / /
22.5 °C 35 °r
solid ^ • nematic -* • isotropic
17.2 kJ o.8 kJ
7?-Quinquephenylv }
4'-n-Octyl-4-cyanobiphenyl (39)
\
n C8H17- (1.3.4)
t\
24 °C +. A 34 °C . 42.6 °C
solid -* • smectic A -* • nematic -* • isotropic
25.3 kJ 0.13 kJ 0.97 kJ
16 1. Introduction
Cholesteryl nonanoate (monotropic smectic A) (41>42)
CH 3 (CH 2 ) 7 C O
78.6 °C 91 °C 91.3 ° C
solid -• • cholesteric -* • blue phase I -* • blue phase II
0.017 kJ 0.017 kJ
36 °C 38 4 °C 42.4 °C
solid -* • smectic G -*—: »• smectic F -* • smectic B
15.2 kJ 0.39 kJ 0.15 kJ
50 °C 25 kJ
17
18 2. Statistical theories ofnematic order
cJ2
where
r(q,s) = \ m
f
la
1UJV(1 - ? ) ( 1 +^)]![17V(1 -
n+s
W(\-q
2 ) KT\
B J 4
K1AA)
kBr{
To evaluate the contribution of the disorder to the various thermodynamic
quantities it is necessary to specify the dependence of PFand W on volume.
It is found(5)6) that the empirical trends in the properties, especially for
large orientational barriers which is the main region of interest in the
present discussion, are reproduced well by the model when W —
W0(V0/vy and W = WO(VO/V)Z where the suffix zero denotes the value
corresponding to the equilibrium intermolecular separation as defined by
the Lennard-Jones potential. When W = 0, the theory reduces identically
to the LJD model for spherical molecules. Applying the equilibrium
conditions,
8 In Q 8 In Q
= = 0,
dq ds
we obtain
<2U)
-(H-FWr)*
where v = z'W'JzWQ is a measure of the relative barriers for the rotation
of a molecule and for its diffusion to an interstitial site.
22 2. Statistical theories ofnematic order
7w vx v l
NkBT kBT
-0.2
-0.4
15
zW/kBT
Fig. 2.1.2. (a) Variation of the equilibrium value of the positional order parameter
q and the orientational order parameter s with zW/kB rfor v = 0.3. (b) Theoretical
isotherm for v = 0.3 showing rotational transition in the solid state followed by the
melting transition. (The isotherm is drawn for the solid rotational transition
temperature kB T/e = 0.593.)
L (b)
Fig. 2.1.3. (a) Variation of the equilibrium values of q and s with zW/kB T for
v = 0.8. (b) Theoretical isotherm for v = 0.8 showing a single transition in which
both positional and orientational orders collapse simultaneously (k B T/e = 0.625).
1.0
q, s
Fig. 2.1.4. (a) Variation of the equilibrium values of q and s with zW/kB T for
v = 1.3. (b) Theoretical isotherm for v = 1.3 showing solid-nematic and nematic-
isotropic transitions. (The isotherm is drawn for the solid-nematic transition
temperature kB T/e = 0.678.) (After reference 5.)
0.6
•0.4
0.2
a-1
3 --
\S-N
2 -
S-I '
1 -
s-s
0 -
1
0
1
0.2
1 i
0.4
i
0.6
i
0.8
i
1.0
N-I/
1.2
S" = -
ZT);
\ + 2 T ( \ ]
)/2T{ aril*
Table 2.1.2. Latent heat and volume change data for some nematogenic
compounds
Solid-nematic Nematic-isotropic
transition transition
S-N
0.2 ^—
0.1
s-s/ N-I /
n ^
1 1 i i
0.4 0.8 1.2
Fig. 2.1.7. Relative change of volume on transition versus v (see legend offig.2.1.5).
(b)
0.2 - / iNemat
(«)
0.2
Solid /
/ Isotropic
pVo Solid /Nematic/Isotropic "T^~ / /
0.1 -
0.1
/
/
/ i i
500
400
200
100 -
the slope AT/dp for the latter being greater in accordance with the
experimental data (fig. 2.1.10). Of course, such a behaviour is also to be
expected from the Clausius-Clapeyron equation.
Fig. 2.1.9(6) represents a more interesting case. Here v is just below the
critical value for the nematic phase to occur at zero pressure. As the
pressure is raised, there is initially a single transition, viz, the solid-liquid
melting transition, but at higher pressures branching takes place and
there are two transitions. The branching point represents the solid-
nematic-isotropic triple point.
Experiments were done on the first two members of the p-n-
alkoxybenzoic acid series to verify this prediction. (22) These two com-
pounds, methoxy- and ethoxybenzoic acids, do not form liquid crystals
at atmospheric pressure, whereas propoxybenzoic acid and the higher
homologues show at least one liquid crystalline phase. As the pressure is
raised, both compounds exhibit mesophases, initially a nematic phase and
2.2 Phase transition in a fluid of hard rods 29
2
e
200 -
Solid
1/
1
' Smectic / Nematic
/ /
/isotropic
7k
100 - / /
Triple point tS
^ 7
/
Triple point
/ i i
i
205 215 225
Temperature ( C)
then, at higher pressures, a smectic phase as well (fig. 2.1.11). (The smectic
phase is not included in the framework of the theory in its present form. It
would require the introduction of another order parameter, viz, a lamellar
order parameter (see chapter 5).) The transitions were detected by
differential thermal analysis and the mesophases identified by microscopic
observations using a high pressure optical cell (fig. 2.1.12). These studies
also established for the first time the existence of the solid-nematic-
isotropic and the solid-smectic-nematic triple points in single com-
ponent systems.
UN = \tuij9 (2.2.1)
where Utj is oo if the molecules / and j intersect and zero if they do not. The
intersection may occur either in a parallel or perpendicular configuration
as shown in fig. 2.2.1. Let the position vector of they'th rod be represented
by Rj and its orientation by up and let the set of all positions be abbreviated
by R and the set of all orientations by u. The configurational integral for
the system consisting of TV rods in the volume V can then be expressed as
where TV! allows for the indistinguishability of the particles and 3^ for the
total number of orientational states. The potential energy of the system
depends on the sets R and u. Since the configurational space available for
each molecule is V,
where the new function <pN depends only on the orientations. Thus
tT}.
Now for any given configuration of the system, there will be N(\) molecules
pointing in the direction u(l), N(2) in the direction u(2) and N(3) in the
direction u(3). Therefore q>N becomes a function of the occupation numbers
in the three allowed directions, i.e.,
<pN = <pN[N(l),N(2),N(3)].
The indistinguishability of the molecules requires that for any given set of
occupation numbers N(l), N(2) and N(3) there are N\/N(l)]N(2)\NQ)\
equivalent configurations, so that
= J^_ » » » N\exp(-<pN/kBT)
V* N\lN {? £
N )=a N )=o N ^ N(\)\N{2)\N{?)\ '
) Nil) M3)l ^
we have
Q»= £ £ £ t[N(l),N(2),N(3)]. (2.2.2)
iV(l)=0 A^(2)=0 iV(3)=0
N-1]nt=l-]np-]n3-txttlnxa-(<pN/NkBT), (2.2.3)
2.2 Phase transition in a fluid of hard rods 33
(2.2.4)
^(N-1lnt) = 0, a =1,2,3.
F=-kBTlnQN
and the pressure by
°' 0) =
The first volume integral is evaluated directly so that
5(2,0,0) = -4W 2 .
2.2 Phase transition in a fluid of hard rods 35
B { 1 l 0 )
ni+d)/2 r(i+d)/2 ra
d3R2 = -
J-(l+d)/2 J-(l+d)/2 J -d
2?(l,l,0)^-2/ 2 41+2(<///)],
£(2,0,0) ~-4l2d(d/l).
Thus, the virial coefficient for parallel configuration is smaller than that for
orthogonal configuration by an order d/l. Higher order virial coefficients
exhibit the same behaviour. To simplify the calculation Zwanzig neglected
all terms of order d/l, i.e., he confined himself to the limit /-> oo, d-^0,
l2d = constant, thereby reducing considerably the number of coef-
ficients to be considered. It is readily verified that only coefficients of the
type B(m,n,0), B(0,m,n) and B(m,0,n) survive, and that by symmetry
B(m, 0, n) = B(n, 0,ra)= B(0,ra,n) = B(0, n, ra).
Let us now choose the z axis (/ = 3) as a preferred direction. By
symmetry the numbers of molecules in the x and y directions are equal, so
that the mole fractions along the three directions can be expressed in terms
of a single order parameter x:
v —v
x2 = x,
x3 = 1— 2x.
VN _ sr ^r D/,^
NkBT
(2.2.6)
The mole fraction x is then determined by
— (AT1 In 0 = 0,
ax
i.e.,
x \ d / cpN
2 In
\-2x) dx\ NkBT)'
36 2. Statistical theories ofnematic order
3.0
2.0
= (31nr/ain/>). (2.2.8)
38 2. Statistical theories of nematic order
which is a measure of the relative sensitivity of the order parameter s to
changes in density versus changes in temperature, it follows that y = oo for
a system of hard particles, whereas experimentally y = 4 for PAA (see
(2.3.18)). Clearly, therefore, attractive interactions must also be included
to give a proper description of the nematic phase.
(2.3.2)
where fj = \{n1 + 2n2) and n the number of molecules per unit volume.
Similarly
Therefore
n2). (2.3.4)
r/1 and n2 can be obtained from the susceptibilities of the solid crystal if the
structure is known. Thus a measurement of xz>Xz o r t n e anisotropy xz~Xx
in the nematic phase gives the absolute value of s. In a similar manner,
s can be related to the optical anisotropy (birefringence (51) and linear
dichroism(50)) though, as is well known, there is a difficulty in this case as
there is no rigorous way of correcting for the effects of the polarization field
in the medium. Approximate methods have been proposed (50>52) which
appear to yield satisfactory results/ 53 ' 54)
Another important tool for investigating molecular order is nuclear
magnetic resonance (NMR) spectroscopy. (55) The principle of this method
is that if there is a pair of protons in a molecule, each spin is coupled to the
external magnetic field H as well as to the dipole field created by its
neighbour. The latter gives rise to a small perturbation of the eigenstates of
the Zeeman Hamiltonian so that the signal appears as a doublet. The
doublet separation is easily seen to be proportional to (3cos 2 # — l)/r 3 .
where 9 is the angle which the interproton vector rtj makes with H. In the
isotropic phase xtj can assume all possible orientations with respect to H
and <3cos 2 # —1> vanishes, but in the nematic phase there is a splitting
which is a measure of the order parameter s. The analysis is, of course, not
so straightforward for complex molecules as it requires precise knowledge
of the interproton distances and angles. The quadrupole splitting in the
magnetic resonance spectrum of 14N(56) or of deuterium(57) has also been
employed for studying molecular order. Other methods involve the use of
40 2. Statistical theories of nematic order
0.7 r
0.6
a 0.5
O
6
0.4
I
0.3
-40 -30 -20 -10
r-rNI(°Q
Fig. 2.3.1. The temperature variation of the long-range orientational order
parameter s in PAA. Open circles from NMR measurements (McColl and Shih(66)),
filled circles from diamagnetic anisotropy (Gasparoux, Regaya and Prost(67));
triangles from refractive indices.(65)
where a,/? = x9y9z refer to the space-fixed axes, ij = x\y\z' refer to the
principal axes of the molecule, /a, jp denote the projection of the unit vectors
i, j along a,/?, and 3a/3, S(j are Kronecker deltas. $"/is symmetric in /, j and in
a,/?. It is also a traceless tensor with respect to either pair, i.e.,
where repeated tensor indices imply the usual summation convention. The
generalization of (2.3.2) and (2.3.3) is
2.3 The Maier-Saupe theory and its applications 41
0 0 -(Sll + s2i.
In the uniaxial nematic case, s n = s22.
If the molecule is flexible more parameters are required to define the
degree of alignment of its different parts. (64) However, in a large part of the
discussion that follows on the theory of the nematic state we shall ignore
all these details and assume the molecules to be cylindrically symmetric
rods.
2.3.2 The mean field approximation
We assume that each molecule is subject to an average internal field which
is independent of any local variations or short-range ordering. Consistent
with the symmetry of the structure, viz, the cylindrical distribution about
the preferred axis and the absence of polarity, we may postulate that the
orientational energy of a molecule
ut oc |(3 cos2 6i—\)s,
where 0i is the angle which the long molecular axis makes with the
preferred axis and s is given by (2.3.1).
The exact nature of the intermolecular forces need not be specified for
the development of the theory. However, in their original presentation
Maier and Saupe(48) assumed that the stability of the nematic phase arises
from the dipole-dipole part of the anisotropic dispersion forces. The
second order perturbed energy of the Coulomb interaction between a pair
of molecules 1 and 2 is given by
^oo = i L 3
r>2
K
Y ( 1 ) jr < 2 )
(2.3.6)
where x$,x$ etc. are the components of the transition moments defined
as
f
_J
4? = £ f^2)*42)42Vv2)dr(2), etc.,
k J
42 2. Statistical theories ofnematic order
y/^\ y/[2) and EM,EV are respectively the eigenfunctions and eigenvalues of
the unperturbed molecules corresponding to states ju and v, EMV = EM + Ev9
^ 1) ,xj 1) ^ 1) zj 1) are the charges and their coordinates in the first molecule
measured in the space-fixed coordinate system with the origin at the centre
of mass of molecule 1, R = (X, Y,Z) is the position of the centre of mass
of molecule 2, e(*\ x^y^z™ are the charges and their coordinates in
molecule 2 measured in the coordinate system obtained by translating the
one defined above by XYZ. The second summation in (2.3.6) is over terms
with x9 y and z changed cyclically.
We assume that the rotational motions of the molecules are independent
of their translational motions. Let ^rja)C(1) and f<2y2)f<2) be the two
molecular coordinate systems with their origins at the centres of mass, £
coinciding with the long axis of each molecule. We define the Eulerian
angles as follows: 6 = the angle between z and £, 0 = angle between £ and
the normal to the z£ plane and 0 ' = angle between x and the normal to the
z£ plane. The components of the transition moments are
(237)
I K<exp(-w</fcBr)d(cos0<)
- ^ = -\NkBTBs\ (2.3.9)
exp(-ui/kBT)d(cos0J
Jo
where B = A/kB TV2 and N is the Avogadro number. The partition
function for a single molecule
k
= -NkBkBs(2s+I)-In rexp(ffecos20,)d(cos0jj. (2.3.11)
(2.3.12)
IT)
\ U l )
-o-
/V,T
or
3<cos^) + l=0.
OS
0.05 - T>TNJ
yL.
0.0
\
-0.05
-0.1
i 1 1 1
0.2 0.4 0.6 0.8
s
Fig. 2.3.2. Variation of the free energy with the order parameter calculated from the
Maier-Saupe theory for different values of A/kB TV2. The minima in the curves
occur at values of 5 which fulfil the consistency relation (2.3.13).(71)
Vl = 4.541, (2.3.14)
0.4292, (2.3.15)
0-7 (b)
2 0.6
"2
O
0.5
0.4
-40 -30 -20 -10
T-Tm C
Fig. 2.3.3. Order parameter s versus temperature predicted by the Maier-Saupe
theory, (a) ut oc V~2; (b) ut oc V\
or
2 In exp (|fts0 cos2 0) d(cos 6) - Bsc(sc + 1) , (2.3.16)
V Bs*X
from which sc can be determined if A V is known from experiment.
However, AV is usually so small (see table 2.1.2) that sc derived by this
method differs hardly by 1-2 per cent from that given by (2.3.15). In effect,
therefore, the theory predicts a universal value of sc « 0.44 for all nematic
materials. While this value is in fair agreement with the observed data for
a number of compounds, there are systematic deviations/ 53 ' 60) The
introduction of higher order terms in the Maier-Saupe potential function
to allow for contributions other than the purely dipole-dipole part of the
dispersion energy has been suggested, (71"3) which enables calculations to be
made for specific cases. Further, the long wavelength orientational
fluctuations in the medium (see §3.9) will diminish the effective order
parameter and this has to be taken into account in the theory. (62) The
assumption that the molecule is a rigid rod is also an oversimplification.
Realistic calculations of the role of the flexible end-chain in the ordering
process have been made by Marcelja (74) and by Luckhurst,(75) whose results
will be discussed presently.
Empirical data suggest that the volume dependence of ut may be
46 2. Statistical theories of nematic order
V (cm3 mole- 1 )
224 222 220 218
6.05 -
6.00 -
5.38
Fig. 2.3.4. Lines of constant order parameter s versus In Kand In T for PAA. The
slope (aIn T/ein V) = -4.0. (After McColl and Shih.(66))
(d\nT/d\nV)s = - (2.3.19)
Empirically, therefore, m = 4 for PAA. It turns out that with this value of
rn, result (ii) follows at once from the theory; on the other hand with m = 2,
2.3 The Maier-Saupe theory and its applications 47
the thermal range at constant volume is only 0.74 times the experimental
value.(78) The pressure invariance of sc is, of course, a direct consequence of
(2.3.14) or (2.3.17). Thus, the experimental data can be fitted satisfactorily
with m = 4. However, it is doubtful if this has any theoretical significance,
in view of Cotter's result,(70) referred to earlier, that m should be 1
irrespective of the nature of the intermolecular pair potential.
A drawback of the theory becomes apparent when we calculate the
latent heat of transition from the nematic to the isotropic phase. The heat
of transition is easily shown to be given by(48>72)
H = Txl[(a/P)AV-S(Ve, Tm)], (2.3.20)
where a and p are respectively the coefficients of thermal expansion and
isothermal compressibility of the isotropic liquid at Tm. (Although AFis
usually small, its contribution to H is not negligible since H itself is rather
small.) However, the theoretical values of//are found to be much too high,
usually by a factor of about 2 or 3.<72) Large discrepancies are also found in
the specific heat Cv and the isothermal compressibility /? in the nematic
phase. The failure of the theory in this respect is evidently because the
molecular field method neglects completely the effect of short-range order.
A naive way of accounting for this discrepancy is to assume that the
molecules form small clusters of 2-3 molecules each, and that the single
particle potential (2.3.8) applies to each cluster rather than to the individual
molecules/ 48 ' 72) The theory is then able to give reasonable values for //, Cv
and /?.(72) However, such a procedure cannot account for the remarkable
effects of short-range order in the isotropic phase (see §2.5).
As observed earlier, the assumption that the molecule is cylindrically
symmetric is clearly not valid for real systems, and consequently the use of
a single order parameter is not adequate. Most molecules are lath-shaped
and have a biaxial character. Therefore two order parameters are required
to describe the uniaxial nematic phase composed of biaxial molecules. (68) If
£, rj, C are the principal axes of the molecule (£ defining the molecular long
axis), it is necessary to introduce an additional order parameter
/) = f<sin 2 /9cos2^>, (2.3.21)
where y/ is the Eulerean angle made by £ with the line of intersection of the
£n plane and the xy plane (i.e., the plane normal to the director). A finite
value of D indicates that there is a difference in the tendency of the two
transverse molecular axes to project on the z axis. Theories have been
developed(79) by incorporating an additional term proportional to D in the
Maier-Saupe potential function. It emerges that molecular biaxiality
48 2. Statistical theories ofnematic order
decreases the value of s at the transition, and leads to better agreement with
experiment. Further, since different properties have, in general, different
biaxial anisotropies, the order parameters determined by different tech-
niques (optical anisotropy, diamagnetic anisotropy, etc.) need not
necessarily agree with one another if the biaxial order parameter (2.3.21) is
included in the calculations.
Until the 1970s only s — (P2(cos9)} (where P2 is the second order
Legendre polynomial) was accessible experimentally, but a technique is
now available for measuring both </>2) and <i^> (where P4 is the fourth
order Legendre polynomial). It involves polarized Raman scattering
measurements on aligned samples. Jen et al.m) who developed this
technique, made use of the C = N stretch vibration of a cyano-compound
dissolved in the nematic phase as a probe for the Raman measurements. A
number of pure nematogenic cyano-compounds have since been inves-
tigated by this method/81'82) It turns out that in every case studied so far,
<P4> is negative for at least part of the nematic range. While the observed
<P2> can be fitted quantitatively by including higher order terms in the
Maier-Saupe potential, the negative <P4> cannot be accounted for
theoretically. Using the experimental value of <P2> and <P4> one can
calculate an orientational distribution function for the molecule :(80)
truncated after the third term 1 = 4. The results show that the molecule has
a strong tendency to be tipped away from the nematic axis - very much
more than predicted by the Maier-Saupe theory (fig. 2.3.5). In the three
pure cyanobiphenyl compounds studied/81'82) it is found that the greater
the chain length, the greater is the magnitude of the negative <,P4> (fig.
2.3.6). This may possibly provide a clue to the origin of the observed
angular distribution function. However, further studies need to be carried
out before drawing any definite conclusions.
3.0 T-T=2°C
2.4
0.6
-0.3 I i I I °,OQ 6
1.0 0.6 0.8 0.4 0.2 0.0
cos 6
Fig. 2.3.5. Orientational distribution function /(cos 6) as defined by (2.3.22) in the
nematic phase of MBBA. Circles represent values from Raman measurements and
the line gives the distribution function derived from a two-term Maier-Saupe
potential in which the parameters are adjusted to give a good fit with the observed
<P2(cos#)>. The negative values of/(cos 0) at high angles arise from truncation
errors. (After Jen et al.m))
-o.i -
-0.2 -
Fig. 2.3.6. Orientational order parameter <P 4(cos#)> in three nematic liquid
crystals from Raman measurements: (a) 4 /-n-pentyl-4-cyanobiophenyl (5CB); (81)
(b) 4/-n-heptyl-4-cyanobiphenyl (7CB);(82) (c) 4/-n-octyloxy-4-cyanobiphenyl
(80CB).(82) (After reference 82.)
260 r
220
200
160
120
12
Fig. 2.3.8. The variation of the nematic-isotropic transition 7 ^ with the number of
methylene groups in the flexible spacer for a,o>bis(4,4'-cyanobiphenyloxy)alkanes,
the molecular structure of which is shown at the top of the diagram. The dashed
lines represent the theoretically calculated values. (After Luckhurst.(75))
larger contribution for the measuring field parallel to the long molecular
axis) and (ii) the dipole orientation effect. The sign of the latter contribution
is positive if the net permanent dipole moment of the molecule makes only
a small angle with its long axis and is negative if the angle is large. In the
last case the sign of the net anisotropy depends on the relative magnitudes
of the two contributions. Thus different nematic materials can exhibit
widely different dielectric properties (fig. 2.3.9).
In contrast to diamagnetism where the magnetic interactions between
molecules can be neglected, the polarization field in the medium becomes
important when discussing dielectric anisotropy (see, e.g., Bottcher(92)).
Maier and Meier(89) took this into account by applying the Onsager
theory.(93) The effective induced dipole moments per molecule along and
2.3 The Maier-Saupe theory and its applications 53
5.9 ,- (a)
tn 5.8
I
I 5.7
s
5.6
30 —
20
10
1
100 120 140
7TQ
Fig. 2.3.9. Principal dielectric constants of (a) PAA (after Maier and Meier(90)) and
(b) n(4/-ethoxybenzylidene) 4-aminobenzonitrile (after Schadt (91)). s1 and e2 refer to
the values along and perpendicular to the optic axis of the nematic medium and £is
is the isotropic value.
perpendicular to the unique axis of the nematic liquid crystal are then given
by expressions essentially similar to (2.3.2) and (2.3.3) but with appropriate
correction factors for the polarization field:
(2.3.23)
(2.3.24)
where h = 3e/(2s+ 1) is the cavity field factor, e the mean dielectric
54 2. Statistical theories ofnematic order
constant, F = 1/(1 — af) the reaction field factor, a the mean polarizability,
aa the polarizability anisotropy (the direction of maximum polarizability is
assumed to be the long molecular axis),/= 4nNp(2e — 2)/3M(2s+ 1), p the
density, M the molecular weight, s the order parameter defined by (2.3.1),
and E the applied field. Strictly speaking F and h have to be corrected for
the anisotropy of the dielectric constant but we shall ignore these
corrections.
To calculate the effective permanent dipole moment, we choose XYZ as
the space-fixed coordinate system, Z being parallel to the unique axis of the
medium, and £rj( as the molecule-fixed coordinate system, the £ axis
coinciding with the long axis of the molecule. Let v be the Eulerian angle
between the £ axis and the line of intersection of the XYand £rj planes, and
V the angle between this line and X. Suppose that the permanent dipole
moment ju is inclined at an angle ft with respect to the long molecular axis.
In dielectric measurements, low fields are usually employed so that the
potential energy of the dipoles due to the external field is small. We can
therefore write the effective dipole moments along the field directions as
,T)]juzy/(0)sin0d0dvdv/
[l+(M,hE1/kBT)]yf(ff)sin9d0dvdv'
o Jo Jo
hE2/kB T)] jux y/{0) sin 0 d6 dv dv'
> (2.3.26)
[l+(MxhE2/kBT)]¥(S)sm8dvdv'
Jo Jo
Jo Jo Jo
Jo
where
^ 1 , (2.3.27)
(2.3.29)
and similarly
Therefore
Clearly if /? is small, the two terms in the square brackets of (2.3.31) add to
give rise to a strong positive ea, whereas if /? is sufficiently large £a may be
negative. In PAA, for example, ju and /? are estimated to be 2.2 debyes and
62.5° respectively from Kerr constant measurements in dilute solutions
and dielectric measurements in the isotropic phase. Substituting for the
other known parameters for this compound and using s from theory, it
turns out that ea should be weakly negative. The absolute value of ea as well
as its temperature variation are in fair agreement with the experimental
data.(90)
The dielectric constants are, of course, frequency dependent.(94) The
dipole orientation part of the polarization parallel to the preferred
direction (1-direction) may be expected to be characterized by a relatively
long relaxation time. This arises because of the strong hindering of the
rotation of the longitudinal component of the dipole moment about a
transverse axis. On the other hand the orientational polarization along the
2-direction will have a much faster relaxation, comparable to the Debye
relaxation in normal liquids, as this involves rotation about the long axis
of the molecule. If there are additional dipoles in parts of the molecule,
with their own internal degrees of rotation, the corresponding relaxation
times will again be similar to that in a liquid. The expected form of the
dispersion curves for a compound like /7-azoxyanisole is illustrated in fig.
2.3.10. The trends in the curves have been confirmed experimentally.(95>96)
Meier and Saupe(97) have discussed the mechanism of dipole orientation in
PAA and have shown that the relaxation time for polarization parallel to
56 2. Statistical theories of nematic order
e 3
10 12
Fig. 2.3.10. Expected form of the dispersion of the principal dielectric constants of
4,4/-di-n-alkoxyazoxybenzenes. The suffix 0 refers to the static values and the suffix
oo to the optical values. ex shows the low frequency relaxation and both £x and e2
show the normal Debye high frequency relaxation. (After Maier and Meier.(95))
A \\ \l/7 ///
II. I
Splay
^
Twist
Bend
Fig. 2.3.11. The three principal types of deformation in a nematic liquid crystal.
2.3 The Maier-Saupe theory and its applications 57
the 1-direction should increase from its value in the isotropic phase by a
'retardation factor' which may amount to several orders of magnitude
depending on the strength of the nematic potential. However, the
Maier-Saupe potential yields a retardation factor smaller than the
experimental value. This is not surprising since short-range order may be
expected to play a dominant part in the relaxation process and the mean
field theory neglects this completely. No theory of the relaxation
mechanism has yet been proposed taking into account near-neighbour
correlations.
k
1
*Kik
^
juv* 00 J
1
K Y2 \
o f j f c i \ ay (fc)
J
D2 l
}XOtiXOv
+ 3—^
58 2. Statistical theories ofnematic order
The internal energy per mole due to orientational order in the mean field
approximation is then
U = \NAV~2s\
where V is the molar volume. Now let us suppose that the director at the
site of the fcth molecule is turned through an angle ak with respect to that
at /. If we define a new system of axes X Y'Z' at the site of the /:th molecule,
Z ' making an angle (xk with respect to the Z axis,
C 0 S i
*oT = ^OM <** ~ ^O
v'(fc) _ v(k)
Since we are dealing with small deformations, we assume that the director
continues to have cylindrical symmetry about the Z ' axis at the site of the
fcth molecule and that the order parameter s is unchanged in magnitude.
Substituting for x($ etc. in (2.3.33) in terms of x'0{*\ defining the Eulerian
angles between the molecular coordinate system £<fcy*>£<*> and the X'Y'Z'
system and taking appropriate averages, the extra internal energy per mole
of the system in the deformed state turns out to be
1 r/ z 2 \2 z 2 Y21
JLsin,flJ 3 ^ _ ! - 9 ^ 4 (2.3.34)
^ik L\ *^ik / ^ik J
Now for a pure bend distortion da/dX = da/d Y = 0 and we may set
sin ock « ak « 7^ifc 3a/6Z. Assuming a spherically symmetric distribution,
Xik/Rik etc. may be taken to be constant (independent of temperature),
and therefore the second sum in (2.3.34) is proportional to F~4/3. The free
energy of deformation per unit volume can then be expressed as
SF
da [ns»\2kBT
CD
3 1.2 D
'S
Q
o
% io A
0.9
0.8
290 300 310 320
T(K)
Fig. 2.3.12. The temperature dependence of the intensity (/) of light scattering from
4-methoxybenzylidene-4/-butylaniline (MBBA) in the nematic phase. The values
(plotted as kB T/I) are normalized to unity at 286 K. The squares, triangles and
circles correspond to three different experimental configurations. For one of the
configurations (squares) the data were not fully corrected for the effect of the
temperature dependence of the refractive indices on the variation of one of
the wave-vector components, which probably explains the slight increase near the
transition temperatures in this case. (After Haller and Litster.(100))
80
^ 60
g 40
20
eralized van der Waals models have also been developed(116 18) which lead
to results that are essentially the same as those predicted by the scaled
particle theory with a superposed attractive potential.
F=|^J2-|& 8
+ JCJ 4 + ..., (2.5.1)
For a' weak' first order transition, B is small and 2B2/9aC may be expected
to be a very small quantity.
In principle, a free energy expansion of this type should be valid for
nematic liquid crystals, with s denoting the usual orientational order
parameter defined by (2.3.1). The term of order ss is not precluded by
symmetry, for the states s and — s represent two entirely different kinds of
molecular arrangement which are not symmetry related and do not have
equal free energies. In the former case, the molecules are more nearly
parallel to the unique axis, while in the latter they are more nearly
perpendicular to it. However, in the nematic phase s is usually quite large
(greater than about 0.4) so that very many more terms have to be included
in the expansion in order to draw any valid conclusions. Consequently, the
2.5 Short-range order effects in the isotropic phase 63
(2.5.7)
(2.5.8)
o
I 4
0
40 44 48 52 56 60
Temperature (°C)
Fig. 2.5.2. Reciprocal of the Cotton-Mouton coefficient in the isotropic phase of
MBBA for two samples, one slightly impure and having a lower transition point
Tm. Both yield the same value of Tm- T* = 1 °C. (After Stinson and Litster.(128))
NFh2E2[ota-(Fju2/2kB T)(\-3cos2p)]
s = • (2.5.13)
3a(T- T*)
and
(2.5.14)
21nVa(T-T*)
A«E can be positive or negative depending on the sign of the quantity in the
square brackets of (2.5.14). The polarizability anisotropy aa is always
2.5 Short-range order effects in the isotropic phase 65
20
5 -
15
©
X
10
<l
-10
-15 r 0
405 Ni 415 425 435 445
Temperature (K)
Fig. 2.5.3. The electric birefringence (Tsvetkov and Ryumtsev,(122) open circles) and
the reciprocal of the magnetic birefringence (Zadoc-Kahn,(119) full circles) in the
isotropic phase of PA A versus temperature. The lines represent the theoretical
variations.(129)
positive for the long molecules under consideration, but the sign of the
dipole contribution depends on the angle /?. If /? is small, A«E will be
strongly positive, whereas if /3 is sufficiently large AnK may be negative.
Moreover, the second term in the square brackets of (2.5.14) is pro-
portional to T~x, so that, in principle, there can occur a reversal of sign of
A«E with temperature. Using the values of a and T* derived from the
magnetic birefringence of PAA and substituting for //,/?, etc. (see §2.3.4) it
is found(129) that there is in fact a reversal of sign of A«E, though it occurs
at I NI + 9 K (fig. 2.5.3). Since there is a competition between the
polarizability and the permanent dipole contributions, even a small error
in any of the parameters will cause an appreciable shift in the temperature
at which A«E = 0. Taking this into consideration, the agreement may be
regarded as satisfactory.
If p = 0, A«E given by (2.5.14) varies essentially as (T— 77*)"1. In such
materials, the electric and magnetic birefringence may be expected to
exhibit the same type of behaviour over a wide temperature range.
Measurements(130) on pure samples of hexylcyanobiphenyl, a nematogen
66 2. Statistical theories ofnematic order
3.2 - - 3.2
2.4 2.4
o
X
Magnetic
s 1.6
<l
0.8 0.8
T* Tm 30 35 40 45 50 55
Temperature (°C)
Fig. 2.5.4. Reciprocals of the magnetic and electric birefringence in the isotropic
phase of 4-hexyl-4/-cyanobiphenyl versus temperature. Both give the same value of
T*(T* = 28 °C, r N I - T* = 1.1 °C). (After reference 130.)
(2.5.17)
where
(2.5.18)
e is the mean dielectric constant and As is the dielectric anisotropy when the
2.5 Short-range order effects in the isotropic phase 67
^ 16
t 14
I
I 12
•| 10
i
I
44 48 52 56 60
Temperature (°C)
Fig. 2.5.5. Reciprocal of the intensity of light scattering in the isotropic phase of
MBBA versus temperature. (After Stinson and Litster. (128))
molecules are all exactly parallel to one another (see (2.3.2)). Both e and Ae
refer, of course, to optical frequencies. If the incident light is linearly
polarized along z and the scattered light polarized along x
(2.5.19)
so that
An2 (Ae)2kBT
(2.5.20)
dQ
(where we have made use of the condition sxx 4- syy + szz = 0) and
Thus the intensity of scattering should vary essentially as (T— T*)' 1 (fig.
2.5.5) and the ratio of the scattered light polarized along z to that polarized
along x should be 4/3. Both these predictions have been verified
quantitatively for MBBA. (131)
If the order parameter varies gradually from point to point, the free
energy expression should include gradient terms as well, which can be
written in the form
p (£J] (2.5.23)
where
{ }
a(T-T*)\
may be called the coherence length. The spatial correlation function has
the form
(2-5.25)
(2.5.26)
dF
ds,'a/?
= -AsxP from (2.5.15);
For an incompressible fluid daa = 0. All four tensors are symmetric and
traceless. Further from Onsager's relations, ju = ju'.
Now consider shear flow along x with a velocity gradient d*;/dz. The
flow induces a birefringence proportional to the velocity gradient with
the principal axes of the index ellipsoid inclined at 45° to the x, z axes. In
the steady state R^ = 0, cpxz = \pi dv/dz. Therefore
ju dv
Sxz = (2.5.27)
~2a(T-T*)~dz'
sxz 0 0
0 0 0 (2.5.28)
0 0 -sv
70 2. Statistical theories of nematic order
Therefore x'yz represent the principal axes of the order parameter tensor.
The difference between the dielectric constants (at optical frequencies) for
polarizations along the x' and z' axes is
where An is the birefringence when the molecules are all perfectly parallel.
The flow birefringence may therefore be expected to show an anomalous
increase as the temperature approaches the transition. This was observed
by Tolstoi and Fedotov(121) many years ago in PAA. The experiments of
Martinoty, Candau and Debeauvais(134) on MBBA have confirmed the
temperature dependence predicted by de Gennes's equation (2.5.29) (see
fig. 2.5.6).
2 V2
(T-T*)- 0.0762-
3 ~
45 7\
NI
47 49 51 53 55 57
Temperature (°C)
Fig. 2.5.6. Flow birefringence in the isotropic phase of MBBA. Crosses represent
the birefringence (3n) per unit shear rate (G) and circles the reciprocal of this
quantity. (After Martinoty, Candau and Debeauvais.(134))
energy expansion (2.5.1) of the Landau model. However, it does not yield
a satisfactory value of 7*. Since (A/kBTNI V2C) = 4.54, T*/Tm = 0.908.
For PAA, TNI = 408K so that 7NI - T* ~ 40 K, whereas empirically
r NI -r* - 1 K.
Clearly near-neighbour correlations have to be allowed for in the
molecular statistical approach to give a better description of the pre-
transition effects. A step in this direction was taken in 1973(135~7) which
we shall proceed to consider in the next section.
flf(00j)g(0^ (2.6.1)
3=1
where
J f• Jfl/(
J-J • (2.6.2)
while that for an outer shell molecule, say 1, to assume an orientation 015
^i is
JJ/(#oi) S(0i) d(cos 0o) d^ o J... J f l / ( ^ ) g(03) d(cos 0,) d^. (2.6.3)
If we postulate that these two probabilities are identical when 0 and 1 have
the same orientation, we obtain the following consistency relation due to
Chang :(139)
V(009tp0;Ol9q>1)=fL001)g(eei)ll
i)ll ff f/(0
f o ,)^,)d(cos0,)d^,. (2.6.5)
3=2 J JJ
2.6 Near-neighbour correlations: Bethe's method 73
Krieger and James postulated that this probability should be the same
irrespective of which molecule is regarded as the central one, i.e.,
; 0 1 5 cp^ = ^ ( 0 1 ? q>x; 00, (p0),
so that
g(00) TZI = p (constant), (2.6.6)
The assumption here is that the energy is independent of cp, i.e., that the
distribution is cylindrically symmetric. We also ignore the volume
dependence of the potential function. For a given value of z, the values of
B2, i?4, etc., can be derived in terms of B* at every temperature such that the
consistency condition (and hence the thermodynamic equilibrium of the
system) is satisfied accurately. All the properties of the system can therefore
be deduced in terms of a single parameter B*. By retaining terms up to
P4(cos0) in the mean field potential (2.6.8), it is found (137141) that the
maximum error in fulfilling Chang's relation (2.6.4) is less than 0.08 per
cent for z = 8. Further it has been verified that when terms up to P12(cos 8)
are included, the error becomes negligibly small (~ 10"9).
The long-range order parameter s is given by
... P 2 (cos 0O) y/(90, (pQ; 0j9 ^ ) d(cos 0O) dy0 d(cos 0 ; ) d ^
= r r • (2-6-9)
... y(009 (p0; 9P (p3) d(cos 0O) d(p0 d(cos 6d) dtp.
... P2(cos 60j) y/(60, <pQ; 6p ^ ) d(cos 0O) dcp0 d(cos 0^) d ^
. (2.6.11)
... y/(0o, <p0; 9p I*,) d(cos 0O) d(p0 d(cos 0§) &q>}
J J
74 2. Statistical theories ofnematic order
B*/kBT
0.60 0.62 0.64 0.66
'i i
1
i 1
—s
I
__ i
0.15 \
r
phase
" Disordered 2nd order
/ transition
0.25 -
Ordered phase
<
0.30
Fig. 2.6.1. Plot of <P2(cos 0OJ)> (= -2U/NzB*) versus B*/kB Tfor z = 8.(137) At the
first order transition temperature the shaded areas are equal so that the Helmholtz
free energy of the ordered and disordered phases are the same. At the second order
transition temperature <P2(cos6Oj)} = c2 = l/(z—1).
The plot of U versus \/T (at constant volume) shows the characteristic
sigmoid shape (fig. 2.6.1). The curves for the ordered and disordered
phases meet at the apparent second order transition point T*, which is also
the temperature at which the short-range order parameter (P 2(cos60j)) in
the isotropic phase = l/(z—1). The first order transition point 7 ^ is the
temperature at which the shaded areas are equal, i.e., when the Helmholtz
free energies of the ordered and disordered phases are the same. The
calculation gives (Tm-T*)/TNI = 0.062 for z = 8, 0.04 for z = 4 and 0.03
for z = 3. This is an improvement over the Maier-Saupe value of 0.092,
though still much higher than the experimental value of 0.003.
The curves for s, <P4(cos#)> and (P2(cos60j)} as functions of tem-
perature are shown in fig. 2.6.2. All three parameters change discon-
tinuously at Tm; the long-range order drops to zero at the transition, while
the short-range order persists even in the isotropic phase. At the transition,
s = 0.400 (for z = 8) which is slightly lower than the Maier-Saupe value of
0.4292.
Methods involving less stringent assumptions, which have the advantage
that the relevant equations are somewhat easier to solve, have since been
put forward.(142"4) These are based on approximations used earlier in
theories of magnetism. (145146) However, when higher order terms (up to
P4(cos0) or higher) are used in (2.6.8), all these methods yield results that
are practically identical to those given by the Krieger-James approxi-
2.6 Near-neighbour
correlations: Bethe's method
— - - - Nematic Isotropic
0.6
0.5 •=-—
Order parameter
0.3
0.2
<P2 (cos 60j)
0.1 -
1 1
0.90 0.95 1.0
T/Tm
Fig. 2.6.2. Short-range order parameter <P2(cos #0;.)> and the long-range order
parameters s and <P4(cos#)> versus T/T^ calculated in the Krieger-James
approximation.(137) The long-range order disappears at the transition but the
short-range order persists even in the isotropic phase.
mation. (137141) Lekkerkerker et al.a*7) and Van der Haegen et al.am have
used three-particle and four-particle cluster approximations in analogy
with a method followed in magnetism. (149) This leads to a slight
improvement in (TNI— r*)/7^ I ? the precise value depending on the type of
lattice considered. A Monte Carlo simulation study/ 150 ' 151) of a lattice
version of the Maier-Saupe theory gives (Tm-T*)/Tm « 0.01.
Nematic Isotropic
0.6 - " • . s
— — ^ ^ _
0.4
0.2
(P2 (cos 0O,)>
-
0 0
1 1
0.90 0.95 1.0
Fig. 2.6.4. Short-range order parameters (P^cos^.)), <P2(cos^0j)> and the long-
range order parameter s versus T/Tm. The negative value of (P^cos^.)) signifies
antiparallel ordering. The curves are calculated for A*/B* = 0.5.(137)
J/C B 1 KB 1 J
and
1 4nNphF\ x Fju2 , . _ o ,
M [
-j—— <cos (p0 cos q>i sin 0O sin 0^ , (2.6.14)
where the symbols F9 h, etc., have the same meanings as in §2.3.5. Using the
theoretically derived s of fig. 2.6.4, e1, e2 as well as s = l(e± + 2e2) calculated
from these equations are presented in fig. 2.6.5 for a strongly polar (nitrile)
compound of the type studied by Schadt (91) (see fig. 2.3.9(b)). The
parameters used in the calculations are: ju = 5 debyes along the major
molecular axis, a = 28 x 10~24 cm3 and aa = 15 x 10~24 cm 3 (evaluated
approximately by assuming addivity of bond polarizabilities extrapolated
78 2. Statistical theories of nematic order
25 - Nematic Isotropic
20 -
I
15 -
—-^^^_
10 -
5 -
1 1
0.85 0.90 0.95 1.0
Fig. 2.6.5. Theoretical variation of the dielectric constants e19 s2 and e = |(e1 2
with T/Tm.a31) The theory predicts that £ in the nematic phase should be slightly
lower than the extrapolated value of els, the dielectric constant in the isotropic
phase. This is found to be the case experimentally (see fig.2.6.6).
16
J4
•a
I 12
5
10
25 30 35
Temperature (°C)
Fig. 2.6.6. Principal dielectric constants of 4/-n-pentyl-4-cyanobiphenyl (5CB);
s = i(£i-f2e2) is calculated from the measured values of e1 and e2. The dashed
line denotes the extrapolated value of eis. (After reference 130.)
(5CB and 7CB), both of which are strongly polar compounds, has been
reported by Leadbetter, Richardson and Colling.(153) They have found that
the meridional reflexions correspond to a repeat distance along the
preferred axis of about 1.4 times the molecular length, which they have
interpreted as due to an overlapping head-to-tail arrangement of the
neighbouring molecules (fig. 2.6.7). In MBBA, on the other hand, the
repeat distance is approximately equal to the molecular length. These
studies appear to lend strong support to the model of antiparallel
80 2. Statistical theories ofnematic order
25.7 A
37
35
36
34
29
28
-16 -12 -S 0 4 12 16 20
r-r NI (°c)
Fig. 2.7.1. Experimental variation of the surface tension with temperature for three
nematic liquid crystals, (a) PAA,(156) (b) /?-anisaldazine(156) and (c) 5CB. (158159)
Open circles represent measurements using the pendant drop method. Filled circles
in (c) are values determined independently by Gannon and Faber(159) using the
Wilhelmy plate method.
82 2. Statistical theories ofnematic order
Fig. 2.7.2. Schematic form of the density profile p(z) and its gradient \dp{z)/dz\
across the nematic liquid crystal-vapour transition zone.
It is a well known result that the gradient of the surface tension (y) versus
temperature is directly related to the surface excess entropy per unit area as
follows:
%- = -(So-SX (2.7.1)
where the suffixes o and /? refer to the surface and bulk states. Thus if there
is surface ordering SG may be less than Sfi, and y may actually show a
positive slope.(154) Such a trend was discovered by Ferguson and Ken-
nedy(155) in PAA and some other compounds many years ago and has been
confirmed by precise measurements on a number of liquid crystals using
different techniques. (1569) Some experimental curves are shown in fig.
2.7.1. The suggestion has been made (154) that the orientational order near
the surface is determined by two competing effects: (1) the disordering
effect of the spatial delocalization across the liquid-vapour transition zone,
and (2) the ordering effect of a surface torque field. The former may be
assumed to be proportional to the density profile across the interface and
the latter to the gradient of this profile (fig. 2.7.2). The different trends
observed in the different materials (fig. 2.7.1) can then be interpreted as
arising from the relative strengths of these two opposing effects and their
variations with temperature. (160)
Light scattering and optical reflectivity studies (161) again reveal the
existence of orientational ordering at the surface. For MBBA it is found
2.7 The nematic liquid crystal free surface 83
io 4 -
101 - io1
1.0 l.i
QJQo
Fig. 2.7.3. High resolution specular reflectivity data for 80CB near the peak due to
the formation of smectic-like layers near the free surface of the nematic phase. The
open circles refer to the scale on the left and the filled circles to the scale on the right.
The temperatures T- TNA are (a) 0.10 °C, (b) 0.21 °C, (c) 0.40 °C and (d) 1.80 °C.
It is seen that the peak becomes significantly sharper as the temperature decreases,
showing that the number of surface induced layers increases on approaching the
nematic-smectic A transition point 7^A. (After Pershan et al.a62))
that the molecular long axis is inclined at about 75° with respect to the free
surface, the angle being temperature dependent, while for PAA the angle is
zero and temperature independent.
Smectic and cybotactic nematic systems may be expected to show an
oscillatory density profile near the surface. That this is the case has been
strikingly demonstrated by the very fine X-ray reflectivity measurements
of Pershan et a/.(162163) (figs. 2.7.3 and 2.7.4). Surface-induced smectic
layering is observed in the nematic or isotropic phase that extends into the
bulk, the number of layers increasing as the temperature approaches the
transition to the smectic phase.
84 2. Statistical theories ofnematic order
10" 10"
= (T-T1A)/TlA
Fig. 2.7.4. The measured X-ray reflectivity from the free surface of the isotropic
phase of 12CB at temperatures very close to the isotropic-smectic A transition
point. The step-like form of the intensity curve reveals the quantized nature of the
layer growth at the surface. (After Ocko et «/.(163))
Not much progress has yet been made in giving a quantitative molecular
statistical description of these remarkable surface phenomena.
3
Continuum theory of the nematic state
85
86 3. Continuum theory of the nematic state
Conservation of mass
— /?dF=0, (3.1.1)
Conservation of energy
d
fi i - _ f • f
2 2 X l % l
dt)v ** Jv JA
(3.1.3)
where px is a material constant having the dimensions of moment of inertia
per unit volume (ML'1), U the internal energy per unit volume, G{ the
3.1 The Ericksen-Leslie theory 87
external director body force (which has the dimensions of torque per unit
volume since nt has been chosen to be dimensionless), ti = tn Vj the surface
force per unit area acting across the plane whose unit normal is vp and
st = nn Vj the director surface force (which has the dimensions of torque
per unit area). We assume here that there are no heat sources or sinks.
jA
or in vector notation,
— [p(rxy)+Pl(nxn)]dV
dtjy
where gt is the intrinsic director body force, which has the dimensions of
torque per unit volume and whose existence is independent of Gt.
Converting surface integrals into volume integrals and simplifying,
(3-1.1)—(3.1.5) lead to the following differential equations:
p = 0, (3.1.6)
PVi=fi + hi,P (3.1-7)
U = tn dtj + nn Ntj—giNt, (3.1.8)
Pifi^Gi + gt + njij, (3.1.9)
where
hi - nkj "i, k + gj ni = hi - Xjci "j, ic + gi nP (3.1.10)
i I sdv^o,
where S is the entropy per unit volume. Defining the Helmholtz free energy
function per unit volume
F=U- TS,
we obtain for a system in isothermal equilibrium
dF dF d dF • dF d
l l 3
dnt dnt dt ' 87Vt- x ddt- dt ij
But
nt = Ni + Wyii^ Nt-wjtnj9
d
— (nt,) = Ntj - wki nk j - (dkj + wkj) nt k
and
dF d , x dF „ dF dF , dF
3.1 The Ericksen-Leslie theory
Therefore
. dF Ar dF dF „ dF . dF . dF
r V V y dtj i> k W
~ A« *^ ^ i V ^ ^ « ^ Pi AT dd " 3v
i ^ 7\rl
tj
^
dntk
J*
dF
) > a (3
^ -U3)
In view of the constitutive assumptions, it is clear that wji9 Nip Nt and dtj
can be varied arbitrarily and independently of all other quantities and
hence their coefficients must vanish, i.e.,
or
F=F(ni,niJ); (3.1.14)
dF dF dF\ ( dF dF
Wy«—hn, *.- hw*. y - — «,-—h«, fr- Yn
3 h
dn^ ' 8^>Jfc ' dnk J \ dn ^M
(3.1.15)
nji-^L = 0; (3.1.16)
Let us write the stress and the intrinsic director body force as
Since dtj and Nt can be chosen arbitrarily and independently of the static
parts fn and gf,
tf—g, (3.1.20)
t'pdv-g'tN^O. (3.1.21)
Further, using (3.1.10) and (3.1.15)
(3.1.23)
n
k,j
t j - — , (3.1.24)
nn=P}nt + ^ - , (3.1.25)
dF\ dF
— - — + ^ + ^ = 0. (3.1.27)
3.1 The Ericksen-Leslie theory 91
AT,
where A and B are functions of ni (at constant T and p). They can therefore
be expanded as
2 Sn 3
km
B
lk = 73 8^ nk + y4 J4Jfc /i^ + yb Sjk nt + y6«, /i^ wfc.
Substituting in (3.1.28) and remembering that N^ = du = 0,
i.e.,
ax nt nj dtj + (quadratic in dip Nt) ^ 0.
As di:j can be chosen arbitrarily, ax = 0. Also the coefficient of Sjf(= —p
say) in tn and that of nt ( = y say) in g[ are arbitrary since du = 0 and
ntNt = 0. Putting:
a
Ml = i4 M* = «13
//2 = a 4 /z5 = a 1 6
we obtain
t'a = Mi nk nm dkm nt H, + // 2 w, A^, + // 3 /i4 ^ + // 4rfi4+ ju5 n, nk dki + n% nt nk dkp
(3.1.32)
g't-^Nt + ^dfl, (3.1.33)
where, making use of (3.1.31),
^=^2-^3, /l2 = // 5 -// 6 . (3.1.34)
We have omitted the terms of the form/7^, in (3.1.32) and 7^ in (3.1.33) as
they do not contribute to the hydrodynamic effects and can be combined
with the corresponding terms in (3.1.23) and (3.1.24) respectively.
Substituting for t'jt and g{ it is found that the left-hand side of (3.1.21) is
a positive and definite quantity if the following inequalities are satisfied :(7)
n
PSji ^ K i + Mink nm dkm nt it,
On
k,j
+ ju2 ^ Nt + ju3 nt N, + // 4 dn
+ M5njnkdki + /i6ninkdkj9 (3.1.36)
goi+gt
yn.-p^-^ + X^ +^ n ^ . (3.1.37)
3.1 The Ericksen-Leslie theory 93
The jus represent the six coefficients of viscosity of a nematic liquid crystal.
However, the number of independent coefficients reduces to five if we
assume Onsager's reciprocal relations.
(3.1.38)
where
or
// 6 -// 5 . (3.1.39)
(11)
This is referred to as Parodfs relation. The number of independent
viscosity coefficients is therefore reduced from six to five.
It is well known that Truesdell(12) is of the view that Onsager's relations
do not apply to phenomena like heat conduction, viscosity and diffusion
since there is no unambiguous way of selecting the fluxes and forces. It
would appear therefore that there may be some doubts as to the validity of
Parodi's relation. Available data indicate that (3.1.39) is satisfied within
experimental limits,(13) but, in any case, the relation has been tacitly
assumed to be true in most discussions.
We may therefore expand the free energy per unit volume of a deformed
liquid crystal relative to that in the state of uniform orientation as
onx 9w
v
Twist:
aw,
6x'
Bend:
9z' dz
3.2 Curvature elasticity: the Oseen-Zocher-Frank equations 95
We ignore dnjdx, dnjdy and dnjdz. The three types of deformation are
shown in fig. 2.3.12. The curvature strain tensor may therefore be written
as
dx dy dz
dny driy dn^ (say).
dx dy dz 0 0
0 0 0
l_/c 31 /c 3 2 A:33J
K K (3.2.1)
K 0
-kt K 0
. 0 0 0
Additional symmetry operations reduce the number of moduli even
further:
Enantiomorphic and polar k± + 0, k2 + 0
Enantiomorphic and non-polar x = 0, k2 ==
| 0
Non-enantiomorphic and polar k2 = 0
Non-enantiomorphic and non-polar kx = 0, k2 = 0.
The tensor kijlm (or ktj in the abbreviated notation of (3.2.1)) has 81
96 3. Continuum theory of the nematic state
components in general, but as a79 a8 and a9 are zero there remain only 36.
The presence of cylindrical symmetry reduces this number to 18 with only
5 independent constants:
^22
= 0. (3-2.4)
It is seen that &24 plays no role in (3.2.4) and can be omitted as far as
equilibrium situations are concerned (Ericksen (17)). When external body
torques are absent {Gi •=0), the solutions of (3.2.4) are
n2 = sin (qz+y/\)
3.3 Summary of equations of the continuum theory 97
where
^ + ? S = 0. (3.2.6)
dx* dy*
Equation (3.2.5) describes a cholesteric structure with a twist per unit
length of kjk22. In the absence of enantiomorphy, k2 = 0 and the structure
is nematic. The solutions of (3.2.6) describe the configurations around line
singularities in the structure which we shall consider in some detail in a
later section (§3.5.1).
In vector notation the free energy density may be written in the more
compact form
$i = -P*ii-^»t.i> (3-3.4)
gi = g°i+g't, (3.3.11)
where
g°i=yni-PjniJ-dF/dnt9 (3.3.12)
g'^KNt + ^dw (3.3.13)
y and Pj are arbitrary (indeterminate) constants, and
(3.3.14)
o Jo
Transforming to a new variable X given by sin X = sin 9/sin 0
H (3A2)
'~AtV
In other words, deformation occurs only above a certain critical field Hc.
This is referred to as the Freedericksz effect. The threshold condition can be
used for a direct determination of the splay modulus klv
100 3. Continuum theory of the nematic state
z
H<H
1 1 ) 1 ) 1 }
/ / / /
(c)
H<HC »>Hc/
/ / / /
I I I I I I II
Fig. 3.4.1. The experimental Freedericksz geometries for the determination of the
(a) splay, (b) twist and (c) bend elastic constants of a nematic liquid crystal.
For H > Hc, the deformation at any arbitrary point can be computed
from the expressions*19'20*
..., (3A3)
#„ «J 0 Isin 2 ^_-sin 2 0
where q = (k^-k^/k^.
Two other important geometries are illustrated in fig. 3.4.1. For
n = (cos 0, sin 6,0), H = (0, H, 0) (fig. 3.4.1 (b)),
(3.4.5)
3.4 Distortions due to magnetic and electric fields 101
and for n = (sin 0,0, cos 0), H = (//, 0,0) (fig. 3.4.1 (c)),
/XJ- (3A6)
(21)
De Gennes introduced a parameter which he called the magnetic
coherence length to define the thickness of the transition layer near the
boundary. Consider, for example, a nematic liquid crystal occupying the
half space z > 0. Let the wall, the xy plane at z = 0, impose an orientation
along x and let the magnetic field be applied along y (analogous to the
geometry of fig. 3.4.1 (&)). If cp ( = \n — 6) is the angle made by the director
with the field, the equilibrium condition is easily shown to be
~liAAAA/\
123.2 °C
121.3 °Cu
IWIAA/W
119.6 °C
117.5 °C
—JlMAAA/\
-jmmw
115.5 °C
,,-jmm/v
106 °C
101.3 °C
0 1
Magnetic field (kG)
Fig. 3.4.2. Raw recorder traces of interference oscillations due to the change in the
sample birefringence with deformation for hexyloxyazoxybenzene at various
temperatures. Polarizer and crossed analyser are inclined at 45° to the principal
axes of the specimen. The sudden onset of oscillations occurs at the threshold field.
The increase in the threshold for the successive traces illustrates the rapid
temperature variation of the elastic constant. Sample thickness 45 /zm. 7^ =
128.5 °C. (After Gruler, Scheffer and Meier.(20))
If !•:••
f 1
— - • i!
,:i I
IS
Ill'll1
!•>:•• I
•••
'iliii!1 (a)
07/
Fig. 3.4.3. (a) The usual experimental configuration for the optical observation of
the Freedericksz effect. Light is incident normal to the film. However, for reasons
discussed in the text, this arrangement is unsuitable for observing a twist
deformation, (b)l Oblique' configuration which enables the optical detection of a
twist deformation.(22) The magnetic field is perpendicular to the plane of the paper
in both cases.
0.7
0.6
^ 0.5
J
0.4
0.3
0.2
0.1
0
i
Magnetic field (kG)
Fig. 3.4.5. Theoretical curves illustrating the relaxation of the Freedericksz
threshold as the magnetic field is tilted away from the normal to the initial
orientation of the director. The calculations have been made for PAA in the
twist geometry for a sample of thickness 12.7 jum. (a) Field normal to the director,
<p = 90°, (b) q> = 89°, (c) (p = 85° and (d) tp = 80°. 0max is the maximum deformation
in the midplane of the sample. (Kini and Ranganath, unpublished.)
(a) (b)
Fig. 3.4.6. The orienting effect of grooves. Extra elastic energy is required for the
nematic director to lie across the grooves on the solid surface as in (a) rather than
to lie parallel to them as in (b).
direction than for them to lie parallel to it (fig. 3.4.6). A simple calculation
shows that this energy difference for the material near the surface is quite
appreciable and almost impossible to overcome by means of a magnetic
field. The anchoring is therefore firm. Deposition of silicon monoxide and
certain other materials on the glass surface at oblique incidence has been
shown to have essentially the same effect as rubbing.(25)
106 3. Continuum theory of the nematic state
Electric fields
Measurements can also be made using an electric field,(20) or even an
optical field from a laser.(26) There is complete analogy between electric and
magnetic fields as far as the threshold is concerned (except when the
dielectric anisotropy is very large(191)). Above the threshold the analogy
fails in general because the distortion gives rise to a non-uniformity of the
electric field in the medium, a problem which, for all practical purposes,
does not arise in the magnetic field case. An important precaution to be
taken in electric field measurements is that the sample has to be pure to
avoid conduction-induced instabilities (see §3.10).
Capacitance measurements
The deformation at the threshold field in geometries (a) and (c) of fig. 3.4.1
may be detected conveniently by measuring the change in the capaci-
tance/ 2 ^ A slight disadvantage with this technique is that relatively
large areas have to be uniformly oriented which is not easily achieved in
practice. Non-uniform areas and edge effects tend to destroy the sharpness
of the threshold. For optical observations, on the other hand, a well
oriented area of less than 1 mm2 is adequate.
t
H < Hc
t Hc
{cos [9(z)] cos [<pO)L C O S [#( Z )1 si n [<P(z)], sin [#(z)]} where # is the angle made
by n with the xy plane. From (3.3.17) we get
and
(3.4.8)
where
f(9) = kxl co
g(9) = (k22 cos2 9 + £33 sin2 9) cos2 9.
After integration, (3.4.7) and (3.4.8) yield
(3.4.9)
and
(3.4.10)
(3.4.11)
108 3. Continuum theory of the nematic state
Substituting in (3.4.11)
or
Aw)
i//, say.
7r
Therefore
=2 (3.4.12)
JJ 00
and
(3.4.13)
,=2 r r__j
and Jo L ^ -
Jo
where
1 T 1 1
M{¥)
(si
= [fc33 - 2k22 - (kS3 - k22) (sin 2 W + sin 2 emj]/g(6) g(0m!lx).
3.4 Distortions due to magnetic and electric fields 109
6 h
Fig. 3.4.8. Computed relative capacitance change AC/C 0 and optical transmission
T between parallel polarizers (both parallel to the director at one of the boundaries)
of a twisted nematic film as functions of H/Hc. The total twist angle is n/2. Film
thicknesses 13 and 54 jum. The threshold for optical transmission increases with the
thickness of the film. (After Van Doorn.(27))
=2n I
Jo \x.H*- (4tpl/d*){k^-2k22)
or
(3.4.14)
which is the critical field for the deformation to occur. (28) Thus a
measurement of Hc in this geometry gives k22, if kxl and kZ3 are known.
However, for reasons discussed in §4.1.1, the deformation cannot be
detected optically by observation in polarized light at normal incidence
until the field is well above the threshold value Hc. A more convenient way
of detecting Hc would appear to be by measuring the change in the
capacitance (27) (fig. 3.4.8).
A noteworthy feature of the twisted nematic (TN) is that the intensity of
110 3. Continuum theory of the nematic state
the transmitted light (through a pair of polarizers) as a function of field
shows a 'bilevel' behaviour (fig. 3.4.8). It can therefore act as an electric-
ally controllable optical shutter, as was first demonstrated by Schadt
and Helfrich.(29>30) This principle is now finding extensive application
for making liquid crystal display devices (LCDs) for watches, pocket
calculators, automobile dashboards, miniature TVs, etc. A thin nematic
film of positive dielectric anisotropy is sandwiched between two glass
plates, the inside surfaces of which are coated with transparent conducting
material. By surface treatment, the director is aligned parallel to both
plates except that a 90° twist is imposed on the liquid crystal (fig. 3.4.7,
top). Linearly polarized light incident normal to the plates, say with the
vibration direction parallel to the director on the entrance side of the film,
will emerge with its vibration direction rotated through 90° (see (4.1.15)).
The emergent beam will be transmitted by a second polarizer set at the
crossed position with respect to the first one. If now an electric field is
applied, the molecules in the bulk of the sample tend to align themselves
normal to the electrodes when the voltage exceeds a threshold value,
which, by analogy with (3.4.14), is given by
for 2q>0 = n/2, where ea is the dielectric anisotropy. For voltages of the
order of 2 Vc the twist is lost over most of the sample (fig. 3.4.7, bottom), the
polarization is no longer rotated by 90° and the transmitted light is
extinguished by the second polarizer. With parallel polarizers, one can get
the opposite effect, namely bright field in the ON state and extinction in the
OFF state. LCDs are often operated in the ' reflexion' mode: this is done
by having a diffuse reflector on the rear side of the cell. Unlike the dynamic
scattering mode (see §3.10.1) in which conductivity plays a crucial role, the
TN LCD is a field effect device. Therefore, it is advantageous to have high
purity (low conductivity) materials. A major advance in the materials
development was the discovery by Gray and others(31) of highly stable
mesogens of strong positive dielectric anisotropy, like 5CB, 7CB and
related compounds. A wide nematic range, from about —10 °C to 70 °C,
that is necessary for most practical devices, is obtained by making suitable
mixtures of these compounds. With a 90° twist there is equal probability of
the medium acquiring a right-handed or left-handed twist, which results in
the formation of disclination walls. To avoid this, a small quantity of a
cholesteric dopant is added to the nematic mixture in order to favour one
sense of twist throughout the sample. Typically, with such materials, the
threshold voltage is about 1 V, the switching time (for a cell of thickness
3.4 Distortions due to magnetic and electric fields 111
8 //m) a few tens of milliseconds and the power consumption a //W cm" 2 of
display area. A disadvantage with the TN cell is that the viewing angle is
limited to about ± 45° from the normal, but the advantages far outweigh
this disadvantage. By patterning the electrodes appropriately, it is possible
to display the required information, whether it is digits or letters or any
other symbols.
For higher information content it is convenient to use the dot matrix
configuration, with electrodes as horizontal rows on one glass plate and as
vertical columns on the other. The intersection of a row and a column is a
picture element (pixel). Thus a matrix display with TV rows and M columns
has TV x M pixels but only N+M connections. When the number of pixels
becomes large one resorts to an electronic addressing technique known as
multiplexing: each row in the matrix is selected sequentially, while
appropriate data waveforms coded with the information are applied to the
columns.(32) Because of the slow response times of LCDs (~50 ms), each
pixel responds only to the rms of the resulting waveforms. As the number
of lines TV in the matrix increases, the fraction (I/TV) of the total time that
the selected pixels see the full select pulse decreases, thereby reducing the
ratio J^ ms (sel)/^ ms (unsel). Alt and Pleshko(33) showed that
For TV = 100, this ratio is just about 1.1. If the electrooptic response of the
display were very steep (like a step function), a small change in the voltage
would produce a large change in the director orientation, and it would be
possible to activate a given pixel without altering the state of the other
pixels, but since the response is rather broad (fig. 3.4.8), TV is restricted to
about 100 to get a reasonable contrast ratio. To overcome this limitation,
in the pocket TV, for example, an active addressing technique is used in
which each pixel is backed by a thin film transitor (TFT) which enables one
to apply any desired voltage to the ON pixels and zero voltage to the OFF
pixels. With each column replaced by three which are coated with different
pigments, one can get full colour display. Further, the broad electrooptic
response of the material is actually helpful for producing grey scales.
An advance that has extended the application of LCDs to full page
computer terminals and other high information content displays without
having to resort to TFTs is the supertwisted nematic device/ 34 ' 35) It makes
use of the fact that the electrooptic response of the nematic gets
progressively steeper as the twist angle ^ is increased, until at a certain
112 3. Continuum theory of the nematic state
twist' and 'optical bounce' effects, will be explained very briefly in a later
section while discussing the dynamics of the Freedericksz transition (see
§3.8).
where rj = 2z/d, d being the sample thickness, and the subscripts denote
partial derivatives, e.g.,
etc. (3.4.16)
114 3. Continuum theory of the nematic state
1
— ^ tanh q 2 — tan qx = 0,
(3.4.17)
where
- 0.8 RH
Fig. 3.4.11. Threshold plots of RH (the ratio of the periodic distortion threshold
and the normal (homogeneous) Freedericksz threshold) and of Qyc (the di-
mensionless wavevector of periodicity at threshold) versus k1±/k22. Periodic
distortion is possible only when kxjk22 ^ 3.3; for kxjk22 ^ 3.3 the normal
Freedericksz deformation is favourable. (After reference 42.)
0 x
Fig. 3.5.1. Director orientation (indicated by arrows) along a polar line making an
angle a. Incident light that is linearly polarized at angle ^ or (j>±n/2 will be
extinguished by a crossed analyser and will give rise to a dark brush.
* = • *
5=3/2 5=2
Fig. 3.5.2. Molecular orientation in the neighbourhood of a disclination. (After
Frank.(3))
the disclination line. Rotate one face of the cut with respect to the other by
a relative angle 2ns about an axis perpendicular to the director. Remove
material from the overlapping regions or add material to fill in the voids,
and allow the system to relax. If the axis of rotation is parallel to the line
L, as is true for the case under consideration, the disclinations may be
referred to as wedge disclinations.(67) This distinguishes them from twist
disclinations, which will be considered in §3.5.4.
We shall now show that s = ^number of brushes). If light is incident
normal to the film and linearly polarized at an angle (p with respect to the
120 3. Continuum theory of the nematic state
x axis, it is seen from fig. 3.5.1 that the polarization will be unchanged at
all points on the polar line a and hence will not be transmitted by the
analyser. This will result in a black brush at an angle a. A similar situation
will arise when <j> changes by n/2. The angle between two successive dark
brushes is therefore Aa = A<p/s = n/2s. Thus the number of dark brushes
per singularity is 2n/\Aa\ = 4|s|. Also if the polarizers are turned through
angle co the brushes rotate by an angle co/s. The rate of rotation of the
brushes of the two-brush disclination (s = ± §) is therefore twice as fast as
that of the four-brush variety (s = ± 1). If the polarizers are kept fixed and
the microscope stage is rotated by co the brushes turn by co{s— \)/s.
Observations in polarized light therefore enable one to determine s both in
sign and magnitude. The existence of |.s| = \ in nematic liquid crystals
establishes the absence of polarity in this phase.
If the structure is one in which the director is not normal but inclined
with respect to the z axis (as in the case of smectic C, see §5.8), half integral
values of s are not possible even if the molecular order is apolar.
The molecular orientation in the neighbourhood of a disclination as
given by (3.5.3) is shown in fig. 3.5.2 for a few values of s. For s + 1, a
change Ac in the constant c merely causes a rotation of the figure by
Ac/(1 — s), while for s = 1, the pattern itself is changed.
When the strengths of two neighbouring disclinations are equal and
opposite, the brushes connecting them are circular. By superposition of
solutions of the type (3.5.3)
W= \FAxAy. (3.5.4)
3.5 Disclinations 121
Fig. 3.5.3. Curves of equal alignment around a pair of singularities of equal and
opposite strengths. The orientations marked on the circles refer to the case 5 = 1 ,
{a)
independent of R. (This is also true if there are many defects in the layer
and YJ si — O.(7O)) The interaction energy is given by the second term on the
right-hand side of (3.5.7). The force between two singularities is therefore
2nks1s2/r12. Accordingly disclinations of like signs repel and those of
opposite signs attract, the force being inversely proportional to the
distance.
The properties of disclinations in nematics bear some striking similarities
with screw disclinations in crystals (7172) and vortex filaments in super-
fluids/ 73 ' 74) but at the same time there are important differences that
cannot be overlooked while drawing detailed analogies. (64)
3.5 Disclinations 123
(a)
(b)
SO/mi
Fig. 3.5.5. (a) s = ± 1 disclinations and (b) s = \ disclination in a nematic film; (left)
between crossed linear polarizers; (right) between crossed circular polarizers.
(Meyer.(76))
I
\ !
(a)
Fig. 3.5.6. (a) Director 'escape' at the centre of a disclination of strength s = 1 in
a thin capillary: the wall alignment is homeotropic and changes by 90° from wall
to axis. (Williams, Pieranski and Cladis(77).) (b) Projection of the structure on a
plane normal to the capillary axis. Nails signify that the director is tilted with
respect to the plane of the paper. Solutions with positive and negative tilts are
equally probable.
surface). With the planar solution this would lead to the structure s = + 1,
c = 0 (see fig. 3.5.2). However, if we allow for the possibility of a director
tilt towards the capillary axis (z axis), we may assume in the region
0 < r < r0, nx = sin <j> sin 0, ny = cos $ sin 0 and nz = cos 0. The energy of
deformation per unit length is then
r
W = \k\ [(V0)2 + sin2 0(V</>)2 + 2 sin 0cos 0{V<p x V0}] dr. (3.5.8)
(3.5.9)
= 0.
We look for a solution with (j> = ^(a) and 9 = 6{r). Therefore, (3.5.9)
reduce to
- l - f r ? \ - sin 0 cos 9(V</>)2 = 0, (3.5.10)
8V = 0. (3.5.11)
The solution of (3.5.11) is
1 8 / 80>
= 0.
5.5 Disclinations 125
^ S* T \ ^
- ** ** ' ^ ^ -
( _^ _\^ ^_ f
\ \ I//
(a) (b)
Fig. 3.5.7. Escaped configurations of (a) s = I, c = n/2 and (b) s = — 1 dis-
clinations. Nails signify that the director is tilted with respect to the plane of the paper.
0 at r = 0,
= n/2 at r = rQ,
we get
(3.5.12)
This is an escape involving bend and splay (fig. 3.5.6).
In (3.5.8), the first two terms in the square brackets represent volume
integrations, which together give 27^1^1, while the third term is a surface
integration whose value is nks. Thus the total energy
_ (3nk for s = + l,
\nk for s = — 1.
Interestingly, the energy is independent of r0. On the other hand, the planar
structure gives
W=nk\n(rjrc)+Wc
for s = ± 1, where rc is the core radius and Ec the core energy. As rc is
expected to be of molecular dimensions, the planar solution has much
higher energy than the continuous structure if r0 is large enough for optical
observations. On the other hand if the capillary radius r0 is extremely small,
or the elastic constant very large (as can happen in the vicinity of a
nematic-smectic A transition) the planar solution may be more favourable
energetically.
The escaped configurations for s = 1, c = n/2 (involving bend and
twist), and for s = — 1 (involving twist, bend and splay) are shown in fig.
3.5.7. Structures with the nails pointing in the reverse direction (i.e., with
nz being replaced by —n z) are equally probable.
126 3. Continuum theory of the nematic state
z>0 z>0
K
z=0
-\//'--—-
z<0 z<0
= 1 \ ^--* z>0
z>0 \ -v - ^ ^
\ w \\\ z=0
\\\ \\ \
z<0
z<0
1 1
1 1
\ 2
z=0
1 1
z<0
/ / • * • - •
z<0
• \
(a) (ft)
Fig. 3.5.8. Twist disclinations: the director patterns for (<z) s = J, c = 0, n/4 and
7r/2; and (Z?) s = 1, c = 0, rc/4 and n/2. In each case, the disclination line is shown
as a full line in the middle of the z = 0 plane. The patterns for (s, c) and ( —s, —c)
are mirror images of each other.
(f> = s t2Ln~\z/x) + c
each other. It is seen that all three types of elastic distortions, splay, twist
and bend, are now present whereas planar solutions for the wedge
disclination involve only splay and bend.
In the elastically isotropic medium, the expressions for the energies and
interactions derived for wedge disclinations are exactly applicable to the
present case. Similarly, the non-singular solution (3.5.11) for s = 1 is valid
in this case, except that the energy for the escaped configuration turns out
to be 2nk\s\ per unit length.(76) The structure of the escaped configuration
is, of course, rather more complicated than that for the wedge disclination.
From the nature of the director patterns it is clear that dark brushes of
the schlieren type will not be seen under the polarizing microscope for light
propagating normal to the film (see §4.1.1). Twist disclinations may
therefore be expected to be less conspicuous than wedge disclinations, and
few observations have been reported of their existence in ordinary
nematics. They do, however, reveal themselves under favourable cir-
cumstances in twisted nematics, often as loops separating regions of
different twist.(79)
The Volterra process for creating a loop, i.e., a closed disclination line,
in a nematic is as follows. Let £ be the surface enclosed by the loop L. Call
the two sides of the surface S + and S~. Rotate the molecules in contact with
I + by an angle sn and those in contact with Z~ by —sn about an axis
normal to the unperturbed orientation of the director, where s = ± |, ± 1,
etc., is the strength of the disclination line. At finite distances from S the
director will adjust itself and the resulting configuration will be continuous
everywhere except on I .
We now consider a twist disclination loop in a twisted nematic. The
nematic is supposed to have a planar structure with the director parallel to
the xy plane and an imposed twist of q per unit length about the z axis, and
the disclination loop of radius R is supposed to be in the xy plane. The
director distortions are planar, nx = cos^, ny = sin^, nz = 0. On going
once round the disclination line at any point on the loop, the director
orientation <f> changes by 2ns, the sign of which may be either the same as
that of q or opposite.
The net energy of such a structure is(78)
When s and q are of the same sign, W has a maximum value when
128 3. Continuum theory of the nematic state
Fig. 3.5.9. Shrinking of twist disclination loops: (a) thin thread |s| = |, (b) thick
thread \s\ = 1 with an escaped (coreless) structure. Each thread was photographed
twice several seconds apart. (Nehring.(80))
The energy decreases for higher and lower values of R. Thus large loops
with R> Ro may be expected to occur. Smaller loops shrink (fig. 3.5.9) and
disappear. When s and q are of opposite signs, loops may not be expected
to occur at all.
A stability analysis(81) has shown that twist disclinations are less
favourable than wedge disclinations in elastically anisotropic media. This
may explain why the former are so rarely seen in ordinary nematics.
3.5 Disclinations 129
(a)
Fig. 3.5.10. Singular points in droplets: (a) spherically symmetric radial (hedgehog)
configuration with the director normal to the surface; (b) bipolar structure with the
director tangential to the surface; (c) singular points in a capillary.
c)29
—: = 0.
oo do
Selecting solutions with 9 -> S for p -> 0,
tan
D-M9I
For \s\ = 1,9 = S. On the other hand, if 9 -> n — S as p -> 0, then c becomes
c + n.
Fig. 3.5.11 gives the director configurations for some typical cases. The
sections through the (x, y), and the (x,z) or (y,z) planes are identical with
the patterns for the +1 and — 1 wedge disclinations in two dimensions.
Any pattern on the left-hand side of fig. 3.5.11 may be combined with any
one on the right to give a possible point singularity.
130 3. Continuum theory of the nematic state
y
s = — 1, c = n
Fig. 3.5.11. Director field around singular points. Any pattern on the left may be
combined with any one on the right to give the field around a possible point
singularity. (Saupe.(68))
0 = tan" 1 rz
R2-r
it turns out that for this bipolar structure(82)
E « 5nkR.
Elastic anisotropy modifies the idealized configurations shown in fig.
3.5.10.(83>84) More complex structures with an oblique orientation of the
director at the surface have also been reported/ 85 ' 86)
Point singularities of equal and opposite strengths attract one another
and are annihilated(68'87) (see fig. 3.5.12). As the total energy of elastic
deformation around a point defect increases linearly with the radius of the
3.5 Disclinations 131
volume enclosed, it has been suggested that the interaction energy of two
defects grows linearly with separation, analogous to quarks interacting
through a gluon field.(65)
X —l
y ,| + ,stan(
-DJ \x-D
which implies a uniform alignment of the director on the surface of the
cylinder. Thus in the presence of a disclination the cylindrical cavity can be
replaced mathematically by two disclinations, one of strength (1 — s) at its
centre and another of strength s at the conjugate point.
3.5 Disclinations 133
(a)
(b)
Fig. 3.5.13. Stable dipole pairs formed between —1 point disclinations and air
bubbles in a nematic between (a) crossed linear polarizers and (b) crossed circular
polarizers. (Meyer.(87))
134 3. Continuum theory of the nematic state
<x,y)
s2
D D—D
J
r0 being a unit vector directed away from the centre towards the singularity.
At large distances from the cylinder (D $> R)
H H
Fig. 3.5.15. Helfrich walls: (a) a twist wall parallel to thefield,(b) a bend-splay wall
parallel to the field, and (c) a splay-bend wall perpendicular to the field.
(a) A twist wall: The field is along the z axis and the director is confined to
the yz plane and twists about x (fig. 3.5.15(#)). The wall, which is
parallel to the field direction, is analogous to the Bloch wall in a
ferromagnet.
(b) A bend-splay wall: The field is along z and the director is confined to
the zx plane (fig. 3.5.15 (b)). The transition from + n to — n takes place
mainly through a bend deformation, though some splay is also present.
The wall is parallel to H and may be compared with the Neel wall in
ferromagnetic systems.
(c) A splay-bend wall: In this case the transition from + n to — n is
predominantly through splay but there is some bend as well (fig.
3.5.15(c)). It is an 'inversion' wall perpendicular to H.
The thickness of the Helfrich wall is of the order of 2£, where £ is the
magnetic coherence length defined as H'^k/xJ* (see §3.4.1), and the wall
energy per unit length
136 3. Continuum theory of the nematic state
Brochard-Leger walls
Such walls are associated with the Freedericksz deformation. (90) With the
homeotropic geometry of Fig. 3.4.1 (c), the possible distortions for H > Hc
are illustrated in fig. 3.5.16. Since the director tilt has a degeneracy in sign
with respect to H, there can arise twist walls parallel to the field (fig.
3.5.16(&)) or splay walls perpendicular to the field (fig. 3.5.16(c)). Similarly
with the homogeneous geometry, there can arise bend walls.
In this case the wall thickness t ~ £/a, where
a2 = 31 1 —
d2
W---1
Umbilics
Consider a nematic film of negative dielectric anisotropy (ea < 0) aligned
homeotropically between glass plates. If an electric field is applied along
the director axis (z axis) a distortion will set in when the field exceeds the
critical Freedericksz value given by
Ec = (n/d)(k3S/Ej.
5.5 Disclinations 137
I I I I I lllll
11111 T T T T T
lllll TT TTT
iilll T T T T T
lllll l l l l l
[1 T 1
N
\
Fig. 3.5.17. The structure of umbilics of strength 5 = 1 . Nails signify that the
director is inclined with respect to the plane of the paper.
from the centre of the defect, the director gradually tilts towards the z axis,
the tilt angle becoming exactly zero at r = 0. In this sense, umbilics have
a collapsed core, but the structure is not exactly the same as that of the
s = ± 1 defects discussed in §3.5.3.
(a)
Fig. 3.5.19. Planar soliton produced by a field acting on (a) s = \ and (b) s = — \
disclination lines.
3.5 Disclinations 139
ccccc
ccccc
Fig. 3.5.20. Linear soliton produced by afieldacting on a point defect of strength
^= 1.
ending in a singular point (fig. 3.5.20). This has been called a linear soliton.
The occurrence of such solitons in the phases of superfluid 3 He,
antiferromagnetics, etc. has been discussed by Mineev(93).
Other interesting cases have been investigated by Sunil Kumar and
Ranganath. (94)
F=^[l+£cos2(^-a)]/r2, (3.5.13)
(a) (b)
Fig. 3.5.21. The structure of s = \ in the extreme limits of (a)
e = (fcn-fcssV^u + A^) = 1 and (6) e = - 1 .
(3.5.15)
where c and c' are constants. The energy of the singularity (for s 4= 1) is
(3.5.16)
which may be compared with (3.5.5) for the isotropic case. It may be noted
that s and — s have different energies because of elastic anisotropy.
For s = 1, one obtains the elastically isotropic solution with c = 0 or n/2
to be a solution of (3.5.14) depending upon whether e is negative or
positive, and for s = 2 one gets the isotropic solution irrespective of e.
In the limit of e = 1, analytical solutions can be obtained for s = — \
and -l : ( 96 ' 97 >
(3.5.17)
(3.5.18)
For s = |, e = 1, one gets a solution with </> = 0 for a between — n/2 and
TT/2,and ^ = a —{n/2) for a between n/2 and 3TT/2. In this solution,
sketched in fig. 3.5.21 (a), splay is avoided as it requires infinitely greater
3.5 Disclinations 141
0.2 -
1.0
Fig. 3.5.22. Dependence of the energy on e = (k1±—k zz)/(kxl + A;33) for 5 = \ and — |
disclinations. Squares are from the Nehring-Saupe approximation and circles from
the perturbation calculation in the neighbourhood of s = 1. (After reference 97.)
(-L+!) (-1,+
c= 0
Fig. 3.5.23. The director patterns for (§, — §) and (1, —1) defect pairs in two
situations, c = 0 and c = n/2. The double-headed arrow at the centre indicates the
director orientation far away from the defect pairs. (After reference 98.)
where
= \[(O2x-Ol
with
6X = — and 0 y = —.
ox dy
The positive sign in (3.5.19) is taken for like singularities and the negative
sign for unlike singularities.
3.5 Disclinations 143
Molecules
Molecules Molecules perpendicular
parallel parallel to to flow direction
to flow velocity and to velocity
direction gradient gradient
/?-Azoxyanisole
122 °C 2.4 ±0.05 9.2 ±0.4 3.4±0.3
/7-Azoxyphenetole
144.4 °C 1.3 ±0.05 8.3±0.4 2.5±0.3
and
xy yx 2 x, y
Since director gradients are neglected, the elastic part of the stress tensor
t% = 0. Thus, for n = (1,0,0) we have from (3.3.5)
or
Similarly
= X-
Miesowicz's results for two compounds are presented in table 3.6.1.
O. (3.6.4)
For Q > Q c ,
2
^j) ( ^ ^ | Q c ) ^ - g , (3.6.5)
where
from (3.6.4), where V = nR2L is the volume of the cylinder. When Q < Q,c,
T = -Vkxa. (3.6.7)
The torque increases linearly with the angular velocity and offers a direct
method of determining Ar When Q = Qc,
T = \VX*H\ (3.6.8)
2 tan w
sin 2(p =
l+tan>
2{QC/Q + (1 -
1 + {Qc/Q + (1 - Q2/Q2)^ tan [(Q2 - Q2)i/ -10]}2'
f=-^Q2. (3.6.10)
Above the critical angular velocity, the torque decreases with increasing
Q. The predictions are generally in agreement with observations(105) (fig.
3.6.1). However, the shape of the experimental curve at higher angular
velocities appears to be rather sensitive to the nature of the solid surface in
contact with the liquid crystal, showing that a complete theory has to take
into account boundary effects and the production and migration of
disclination walls at the surface.(106)
Another method of determining A1 is by studying the damped torsional
oscillations of the nematic suspended in a static magnetic field.(107) For
i 1, where D is the torsion constant of the wire and V the
148 3. Continuum theory of the nematic state
1.0
0.5
Fig. 3.6.1. Variation of the torque as a function of the angular velocity of the
rotating magnetic field. Open circles: theoretical values; filled squares: exper-
imental values for PAA, T= 112°C, / / = 2 9 0 0 G (Tsvetkov(104)); crosses: ex-
perimental values for MBBA, T=24°C, 77 = 2230 G; triangles: experimental
values for the same compound, T = 22 °C, H = 2230 G, but using a solid teflon
cylinder immersed in the fluid to measure the torque. (After Gasparoux and
Prost.(105))
volume of the sample, the decay in the angular amplitude of the oscillations
can be expressed as
If a magnetic field with components (Hr9 0, Hz) is applied, the external body
force
2/d0 k
HzsinO) = 0, (3.6.11)
ar b\ „ , ^
where
(3.6.13)
(3.6.14)
a = -dp/dz,
and ft is a constant. Equations (3.6.11) and (3.6.12) are also applicable to
flow through the annular space between two coaxial cylinders. For flow
through a capillary we put ft = 0 to avoid the singularity in (3.6.12) at
r = 0. The two equations can then be used to obtain the orientation and
velocity profiles. At high flow rates, the contributions of the elastic terms
tend to become small and
Xx + X2 cos 2 0 ^ 0
in the absence of a magnetic field. The director orientation then approaches
an asymptotic value given by
V ^ (3.6.15)
or, assuming Parodi's relation (3.3.15),
(3.6.16)
In ordinary nematics //2 and //3 are both negative and the flow alignment
angle 0O is usually small. This equilibrium orientation of the director is
150 3. Continuum theory of the nematic state
«> 4.0
i
o (c)
3.0
g
a,
2.0
0.001 0.01 0.1 1.0
AQInR (cm2 s1)
Fig. 3.6.2. Apparent viscosity rj for Poiseuille flow of PAA at 122 °C (homeotropic
wall orientation) plotted against the ratio of the flow rate to the radius of the tube.
Open circles are experimental data of Fischer and Fredrickson,(110) (a) values
obtained from table I, (b) values obtained from table II with //1 = 0, (c) values
obtained from table II with ju± = —0.038. (After Tseng, Silver and Finlayson.(111))
Table I Table II
^ = 0.043 (g cm- 1 s-1) ju1 = 0or -0.038 (g cm"1 s"1)
H2 = -0.069 H% = -0.068
jus = -0.002 //3 = 0.000
ju, = 0.068 /i4 = 0.068
AiB = 0.047 Ai5 = 0.048
/z6 = -0.023 //6 = - 0 . 0 2 0
^ - ^ = ^ = -0.067 £/ o -#i, = A, = - 0 . 0 6 8
H - ^ = ; = 0.0705
attained in practice in relatively thick samples at high flow rates so that the
aligning effect of the walls has negligible influence.
The amount of fluid flowing per second
v(r)rdr
Jo
n =
By scaling the radius and the time as r' = hr and f = kt respectively, with
k = h2, it is easily shown(109) that in the absence of a magnetic field Q/R is
a unique function of aR3. Consequently n plotted versus Q/R should be a
universal curve for all tube radii and flow rates. This has been confirmed
3.6 Flow properties 151
0.001 0.01
AQInR (cm2 s ')
Fig. 3.6.3. Apparent viscosity rj for Poiseuille flow of PAA versus AQ/nR computed
for a tube of radius R = 55.5 jum. The values of/ a // 2 and 0(R), the orientation at
the wall, are respectively (a) 0, - T T / 2 , (6) 1.23, -n/2, (c) 0, - T T / 4 , (</) 24.2, - T T / 2 ,
(e) oo, - 7 i / 2 or 0,0. (After reference 112.)
-0.2
-0.4
-0.6
-0.8
(a)
-1.0
-1.2
-1.4
-a/2
0
-0.2
-0.4
-0.6
-0.8
-1.0
-1.2
-1.4
-ir/2
0.4 0.5 0.6 0.7 0.8 0.9 1.0
r/R
Fig. 3.6.4. Orientation profile for Poiseuille flow for different shear rates. Wall
alignment homeotropic. The values of z a // 2 are 24.2 for (a) and 1.23 for (b). The
values of AQ/nR in (a) are (i) 0.003045, (ii) 0.03354, (iii) 0.1345, and in (b) they are
(i) 0.001245, (ii) 0.004167, (iii) 0.032438, and (iv) 0.1372. (After reference 112.)
0.9
0.8
0.7
g 0.5
0.4
0.3.
0.2
0.1
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
y/R
Fig. 3.6.5. Velocity profiles for Poiseuille flow; the curves (a) and (b) are for
different values oiAQ/nR but for the samefield,while for curves (b) and (c) 4 Q/nR
is nearly the same but the fields are different. The values of / a H2 and 4Q/nR
are respectively (a) 1.23, 0.001245, (b) 1.23, 0.004167, (c) 24.2, 0.003045 and
(d) xaH2 = oo or 4Q/nR = oo (truly parabolic). (After reference 112.)
where 6 is the angle made by the director with x. Proceeding as before, the
differential equations for the velocity and the director orientation in the
presence of a magnetic field (Hx9 Hy, 0) turn out to be(7)
^1 + A2cos2g
-n+Tn\*7.) +(ay +
W)
+ 2xa(Hx cos 6 + Hy sin 0) (Hy cos 0-Hx sin 0) = 0, (3.6.17)
(3.6.18)
where f[6) and g(9) are defined by (3.6.13) and (3.6.14) respectively and
a = dp/dx is the pressure gradient and c the constant shear stress applied
to the fluid. If both plates are stationary a ==
| 0, and taking y = 0 half-way
between the plates, c = 0. On the other hand, if there is no pressure
154 3. Continuum theory of the nematic state
gradient, and the flow is caused by one of the plates moving at a uniform
velocity in its own plane, a = 0 and c + 0. Equations (3.6.17) and (3.6.18)
can be solved to yield the apparent viscosity, velocity and orientation
profiles under different boundary conditions.(113)
If the plate separation is large enough, boundary effects and elastic terms
can justifiably be neglected in (3.6.17). For large shear rates and zero
magnetic field the director orientation approaches the value 0O, defined by
(3.6.15). But if a magnetic field of moderate strength is applied, the
orientation profile is modified slightly. Gahwiller(114) has studied this
behaviour by measuring the change in birefringence. He used capillaries
(5 cm long) of rectangular cross-section (4 mm x 0.3 mm) and measured
the rate offlowdue to a pressure gradient. If H is along the flow direction
and shear rates are large, we obtain from (3.6.17) and (3.6.18)
an(
Thus the three measurements So, <5y and d± yield JU3//I2, JJLJXB. ^
3.6 Flow properties 155
1.5
1.0
0.7
IT
a
•s 0.4
0.2
0.1
20 30 40 50 60
Temperature (°C)
Fig. 3.6.6. The viscosity coefficients rj19 rj2 and rjs of MBBA as functions of
temperature. The temperature scale is linear in T~x. (After Gahwiller.(114))
By choosing 9 and (p appropriately, one can determine rj19 rj2, rjs and juv
Using these two sets of data, Gahwiller was able to determine all five
independent viscosity coefficients as well as / a . Some of his results are
presented in figs. 3.6.6 and 3.6.7.
156 3. Continuum theory of the nematic state
0.1 -
0.06 -
0.03
60 80 100 120
Temperature (°C)
Fig. 3.6.7. The viscosity coefficients rjx, rj2 and //3 of /?-n-hexyloxybenzylidene-//-
aminobenzonitrile (HBAB) as functions of temperature. The temperature scale is
linear in T~\ (After Gahwiller. (114))
+3 -
40 60 80 100
Temperature (°C)
Fig. 3.6.8. The ratio // 3 /// 2 versus temperature for MBBA (crosses), HBAB (open
circles) and 1:1:1 molar mixture of HBAB, /?-n-butoxybenzylidene-//-amino-
benzonitrile and ^-n-octanoyloxybenzylidene-^'-aminobenzonitrile (filled circles).
(After Gahwiller.(114))
3.6 Flow properties 157
90°
Fig. 3.6.9. (a) Ratio of transverse to longitudinal pressure gradient versus director
orientation <j> in plane Poiseuille flow of nematic MBBA. Sample thickness
d = 200 jum. Length of cell L = 4 cm and lateral width / = 4 cm. (b) Deflection
y/ of flow lines with respect to the y axis versus <f> in wide cells (L/l ~ ^ ) . Full line
represents theoretical variation. (From Pieranski and Guyon.(120))
Nematic
Fig. 3.7.1. Experimental arrangement for studying the reflexion of ultrasonic shear
waves at a solid-nematic interface.
the central region of the cell the flow lines were deflected by an angle y/(<f>)
with respect to y, which again showed the expected dependence on cp (fig.
3.6.9(6)).
Though this experiment deals with a particularly simple situation, the
basic principle that it illustrates is relevant to the discussions that follow on
hydrodynamic instability (§3.11).
(3.7.1)
160 3. Continuum theory of the nematic state
Now the velocities associated with the incident, reflected and transmitted
waves may be written as
vt = Ai exp (— F s z) exp (icot),
vr = Ar exp (F s z) exp (icot),
vt = At exp ( - Tn z) exp (icot),
respectively, where F may be complex and the subscripts s and n stand for
solid and nematic. Therefore, in the nematic medium
tzx = -ZnAt exp (-Tnz) exp (icot),
where Z n = |// 4 F n is the mechanical impedance, and
pvt = X(8 2iV8z 2).
We thus have
or
F n = (1 -\-i)(pco/ju^ (3.7.3)
and
Z n = |(1 + i) (pcoju^y. (3.7.4)
The complex reflexion coefficient is given by
A y _ z
r _ 111 _ ^ s ^n
Ax Z s + Z n'
where Z s is the mechanical impedance of the solid which may be assumed
to be a real quantity. If
r= |r|exp(-i0),
l-Hexp(ifl)
n s
l + |r|exp(i0)
=
^s i . .12 , OI«I /3- (3.7.5)
Since according to (3.7.4) the real and imaginary parts of Z n are of equal
magnitude, it follows that
-^t (3.7.6)
3.8 Dynamics of the Freedericksz effect 161
d28 2 . W
22
8 ? *a Sm C0S x
dt ~ '
where
or
- 1] exp {- (2
Thus 0max(O attains the value 0(oo) with a time constant T(H) given by
H2). (3.8.2)
If the field is now reduced to a value less than i/ c , the decay rate is still given
by the same expression only with a negative sign.
If the field is switched off from H > Hc to zero,
^ ^ ^ = 0 (3.8.3)
dz dt dz
where
and r = (l2-
3.8 Dynamics of the Freedericksz effect 163
Neglecting inertial effects, (3.3.1) reduces in the present case to
i=° (3-8-7)
and
/ H\2 Ay/2 (iff/A) — tan y/ ,. o o ,
= (18 8)
(HJ le p-tan, ' -
where A = k'b/a and y/ = qd/2. From numerical calculations, Pieranski,
Brochard and Guyon(123) have shown that the relaxation rate can be
expressed in the form
Fig. 3.8.1. Velocity profile in the homeotropic to planar transition (seefig.3.4.1 (c)).
The velocity has two components, one linear in z and the other oscillatory, the
wavelength A of the latter diminishing with increasing value of H.
Fig. 3.8.2. Torques acting on an elementary volume of the fluid when the molecules
are rotating with angular velocity D: (a) homeotropic to planar transition,
F a = |(2 1 —A 2)Q; (b) planar to homeotropic transition, Tb = ^(<X1 + X2)Q. As a
rule, |FJ > | r j .
and
where Q is the angular velocity (fig. 3.8.2). In many nematic liquids, Ax and
X2 are of opposite signs and of comparable magnitude (see, e.g., legend of
3.8 Dynamics of the Freedericksz effect 165
30
25
20
r(0)
r(h) 15
10
0 a
10 15 20
fig. 3.6.2) so that F is small. In other words, A is small and the solutions of
(3.8.7) and (3.8.8) reduce to y/ = n/2 and
Fig. 3.8.4. (a) Velocity profiles at (i) 1.09 s, (ii) 1.744 s, (iii) 2.397 s, (iv) 2.943 s, (v)
4.469 s, (vi) 4.905 s and (vii) 8.61 s after the magnetic field is switched off from
H ^> Hc to zero in the Freedericksz experiment of fig. 3.4.1 (a). The values are
computed for a sample of MBBA of thickness 200 jum using the equations of Clark
and Leslie.(125) (b) Director orientation profiles at (i) 0 s, (ii) 0.109 s, (iii) 0.654 s, (iv)
3.161 s, (v) 6.648 s after switch off. (U. D. Kini, unpublished.)
d/2
J
V
x
-d/2
(a) (b)
Fig. 3.8.5. Interpretation of backflow and kickback effects (see text(126)).
The elastic torque will be greatest around z = ± d/4 where the curvature is
greatest, and this is balanced by the magnetic torque. When the field is
switched off the unbalanced elastic torque causes a clockwise rotation of
the director in this region (as indicated in fig. 3.8.5(b)). Because of the
coupling between director rotation and hydrodynamic motion, fluid flow is
induced as shown by the long arrows. The fluid motion, in turn, results in
a counterclockwise torque on the director in the middle region (z ~ 0).
This overcomes the elastic torque, which is weak in this region, and gives
rise to a counterclockwise rotation of the director. The director tilts over to
an angle greater than n/2; when it relaxes back to 6 = 0, it produces a small
amount of fluid motion in the reverse direction. Finally at large values of t
the system settles down to the undistorted equilibrium configuration.
This transient effect manifests itself in a direct way in the behaviour of a
twisted nematic cell (see §3.4.2). When the external field (assumed to be
sufficiently strong) is switched off, the light transmission shows an ' optical
bounce effect', i.e., it does not decrease monotonically but rises again to a
peak before decaying to its 'off' value. Calculations have confirmed that
the peak in transmission corresponds approximately to a perpendicular
alignment of the director in the central portion of the cell. This is caused by
fluid motion, which also gives rise to a reverse-twist. (124127)
dfidcu
where e = (e||+2e 1 )/3 is the mean dielectric constant (at optical fre-
quencies), £a = £||— e_L is the dielectric anisotropy assumed to be <^£,
n{: = n • i and nf = nf. An electric vector polarized along i induces a
displacement Df = eifEt along f. The director at r
n(r) = n0 + dn,
(c)
Fig. 3.9.1. (a) The two uncoupled modes Snx and Sn2; (b) components of the
deformation in the SnY mode, bend and splay; (c) components of the deformation
in the 3n2 mode, bend and twist.
.(r,/)>. (3.9.3)
The fluctuations can be analysed into Fourier components. For a given
Fourier component of wavevector q, we may conveniently resolve Sn into
two components 5nx and Sn2, the former in the q, n0 plane and the latter
perpendicular to it (fig. 3.9.1). Let us therefore introduce two unit vectors
ex = e2 x n0,
where qL is the component of q perpendicular to n0. Defining ia = e a i and
/a = e a f ( a = l , 2 ) ,
170 3. Continuum theory of the nematic state
Hence
where
Too
aq,w j ^ na q,
and
where
3.9 Light scattering 171
Optic axis Q
(3.9.11)
100
50
0 ^
50 100 150 200
cot 2 (<p/2)
Fig. 3.9.3. Angular dependence of the intensity of scattering for PAA. Circles give
the experimental values of Chatelain and the line represents the theoretical
variation. (After de Gennes.(129))
(3.9.12)
3.9 Light scattering 173
Fig. 3.9.3 compares this relation with the experimental data of Chatelain
and as can be seen the agreement is good. In principle a measurement of the
intensity of the scattering and its angular variation offers a method of
determining the elastic constants.
0. (3.9.14)
\+vm q\ ql)/q\
Is =
) = 0, (3.9.17)
which has two roots. Typically, k ~ 10~ dyn, p ~ 1 g cm" ,77 ~ // ^ O.li5,
6 3
2
, C(q)
Consequently /?A:a(q) is negligible compared to ^ ^(q) and Ca(q)Qa(q), and
therefore the two roots of (3.9.17) are
P M ( 3 9 1 8 )
(3919)
We have seen that due to the thermal agitation, there are spontaneous
fluctuations in n whose mean square value is defined by
7a(q, co) = (SnJt - q, 0) Sna(q, co)}.
According to the fluctuation-dissipation theorem,(132) the relation between
and
h X, is
/a(q, co) = ^ J l m (xJLq, co)), (3.9.20)
AaVM
' ' [pco-iPM][ttiO)+K(<i)]-c«(q)QMv
or
where
um = -ico s o c a n d uta = -icof(X. (3.9.22)
Thus 7a is a superposition of two Lorentzians. However, as wfa > wsa, we
may ignore the second term in the square brackets of (3.9.21) and rewrite
the power spectrum as
176 3. Continuum theory of the nematic state
200
150
100
50
0 10 20 30 40
Fig. 3.9.4. Angular dependence of the width of the Lorentzian spectral density for
mode 2 in PAA at 125 °C. Open circles denote experimental values in the [ke,k^]
configuration and open squares the values in the [ko, k^] case. The curve is obtained
by a least squares fit with the theory. (After the Orsay Liquid Crystals Group.(131))
The light scattering is therefore determined entirely by the slow mode. The
integrated intensity
(3.9.24)
3.10 Electrohydrodynamics 177
(3.9.25)
The integrated intensity gives the elastic constants ku while the half width
yields uS(X. It is therefore possible to measure the viscosity coefficients from
an analysis of the scattered light using appropriate geometries.
As an example, we present in fig. 3.9.4 a convenient geometry for
isolating mode 2. The director is aligned parallel to the walls of the glass
plates. The incident beam is polarized parallel to the director and the
scattered beam perpendicular to it. If ne and no are the extraordinary and
ordinary indices of the liquid crystal, and cp the scattering angle,
ke = Innjk, k'o = Innjk,
qz = k'o sin q>9 q± = ke- k'o cos q>.
For small angles of scattering,
3.10 Electrohydrodynamics
3.10.1 The experimental situation
From dielectric studies in the radio frequency region,(133) it has long been
known that PAA is negatively anisotropic, i.e., £a = el{ — e± < 0. However,
in a number of early investigations on the effect of an external DC electric
field it was noticed that the PAA molecules align themselves parallel to the
field, rather than perpendicular to it as would be expected of a material of
negative dielectric anisotropy. This observation gave rise to some contro-
178 3. Continuum theory of the nematic state
Transparent conductive coating
Glass
Glass
t Light beam
versy in the 1930s but it has since been confirmed by the systematic
experiments of Carr, (134) who proved that the anomalous alignment is due
to the anisotropy of the electrical conductivity of the liquid crystal. His
studies showed that there is a critical frequency of the applied field below
which the alignment of PAA is anomalous, and that this frequency
increases with the conductivity of the material, ranging from 2 to 100 kHz
in the samples examined by him.
Macroscopic motion of the fluid induced by electric fields was ob-
served many years ago by Freedericksz and Zolina, (18) Tsvetkov and
Mikhailov,(135) Bjornstahl(136) and Naggiar.(137) Tsvetkov also noted that
the flow decreases with increasing frequency of the applied field, and
probably recognized the fact that the phenomenon may be connected in
some way with the electrical conductivity. More recently, Williams (138)
discovered that a thin layer of a nematic material of negative dielectric
anisotropy between conducting glass plates forms regular striations when
a DC voltage of sufficient magnitude is applied. At higher voltages, the
regular pattern gives way to turbulence accompanied by intense scattering
of light, which has come to be known as dynamic scattering and has found
practical applications in display devices. (139) Similar observations have
been reported by other authors. (140)
The experimental arrangement for observing the Williams domains is
shown in fig. 3.10.1. The nematic film of negative dielectric anisotropy
(e.g., PAA or MBBA) is aligned with the director parallel to the glass
Fig. 3.10.3. (a) Flow and (b) orientation patterns of Williams domains. The
periodic orientation pattern and the consequent refractive index variation has a
focussing action for light polarized in the plane of the paper. This gives rise to the
bright domain lines as indicated by the stars above and below the sample. (After
Penz.(143))
400 -
2
"o
100 -
100 (Hz)
400 600
Frequency (Hz)
Fig. 3.10.4. Threshold voltage of the AC instabilities versus frequency for MBBA.
Sample thickness 100 jum. Region I: conducting regime (stationary Williams
domains); region II: dielectric regime ('chevrons')- Full line is the theoretical
curve. The cut-off frequency / c = 89 Hz. (After the Orsay Liquid Crystals
Group.(142))
the sample. Below coc, i.e., in the so-called conduction regime, the regular
Williams pattern becomes unstable at about twice the threshold voltage
and the medium goes over to the dynamic scattering mode. Above coc, in
the dielectric regime, another type of domain pattern is observed. Parallel
striations, again perpendicular to the initial orientation of the director but
with a much shorter spacing (a few microns), are formed in the midplane
of the sample. When the field is increased very slightly above the threshold,
the striations bend and move to form a chevron pattern (fig. 3.10.2(b)). In
this regime, the threshold is determined by a critical field strength rather
than a critical voltage. Both the threshold field strength and the spatial
182 3. Continuum theory of the nematic state
100
B
-a
vi Region of stability
50
25
No domains
20 o o
"o o " o
Optic axis_L field
Domains
/
10
--_ /C7H15
No domains
5
H 15 C 7
0
1 10 100 1000 10000
Frequency (Hz)
Fig. 3.10.6. Frequency dependence of the threshold voltage in /?,//-di-n-hept-
oxyazobenzene, a nematic of positive dielectric anisotropy. (After Gruler and
Meier.(144))
3.10 Electrohydrodynamics 183
periodicity of the pattern are frequency dependent - the former increasing
with frequency (as OP) and the latter diminishing with it. The relaxation
time of the oscillating chevron pattern is a few milliseconds while that of
the stationary Williams pattern is typically about 0.1 s for a thickness of
25 jum. The oscillating domain regime is therefore sometimes called the fast
turn-off mode. The chevron pattern also gives way to turbulence at about
twice the threshold field. An applied magnetic field parallel to the initial
orientation of the director increases the threshold voltage in the conduction
regime, but has no effect in the dielectric regime except to increase the
spacing between the striations. The threshold curve has a pronounced
sigmoid shape with square wave excitation (fig. 3.10.5) indicating that at
high electric fields there is a quenching of the conductive instability even
when co < coc.
DC and very low frequency AC voltages produce electrohydrodynamic
instabilities in the isotropic phase also (T> Tm), the threshold being
comparable to that in the nematic phase. It has been suggested that this is
due to charge injection at the electrodes. A frequency of about 10 Hz is
usually enough to suppress this effect showing that charge injection is not
the primary mechanism for the AC field instabilities in the nematic phase.
If the initial alignment of the director is homeotropic, domains as well as
turbulence can be produced. The threshold voltage for the domains is
somewhat higher than in the case of parallel alignment, but the patterns
persist even when the voltage is reduced to a lower value.
We have so far discussed only materials of negative dielectric anisotropy.
Electrohydrodynamic distortions are observed even in weakly positive
materials,(144) but only when the initial orientation of the director is
perpendicular to the applied field. Striations appear above a threshold
voltage but vanish at still higher voltages and there is no dynamic
scattering. The frequency dependence of the threshold voltage is shown in
fig. 3.10.6.
schematically in fig. 3.10.7. The applied field acts on the charges to give rise
to material flow in alternating directions which, in turn, exerts a torque on
the molecules. This is reinforced by the dielectric torque due to the
transverse field created by the space charge distribution. Under appropriate
conditions, these torques may offset the normal elastic and dielectric
torques and the system may become unstable. The resulting cellular flow
pattern and director orientations are sketched in fig. 3.10.3. Even a
conductivity of the order 10"9 Q" 1 cm"1 is enough to produce this type of
fluid motion. Indeed unless very special precautions are taken, the impurity
conductivity is usually greater than this value.
With a DC field, there may be injection of charge carriers at the
solid-liquid interface but its role in the electrohydrodynamics of the
nematic phase is not yet fully understood. However, as remarked earlier, a
frequency of about 10 Hz is enough to suppress charge injection. We shall
therefore neglect it in the present discussion.
We shall now outline the theory of electrohydrodynamic instabilities
proposed by Helfrich(145) and extended by Dubois-Violette, de Gennes and
Parodi(146) and Smith et fl/.(147) We consider a nematic film of thickness d
lying in the xy plane and subjected to an electric field Ez along z. Let the
initial unperturbed orientation of the director be along JC, and let there also
be a stabilizing magnetic field along the same direction. We consider a bend
3.10 Electrohydrodynamics 185
fluctuation in which the director is in the xz plane and makes an angle cp
with x. We ignore wall effects and assume that the deflexion cp is a function
of x only.
Due to the anisotropy of conductivity, space charges will develop as
indicated in fig. 3.10.7 till the transverse electric field stops the transverse
current. The local transverse field in the steady state is easily seen to be
The space charge per unit area produced on any plane normal to the x axis
is
± On cos 2 (p + e ± sin 2 (p) (Ez - EEX)/4n,
the positive and negative signs standing for the two sides of the plane under
consideration. The applied field Ez acting on these charges causes a flow
along the z axis; the resulting shear stress is evidently
4 = (e^cos2 (p + eLsm2 cp)(Ex- EEX) EJ An. (3.10.1)
From the Ericksen-Leslie theory, we know that the viscous torque is
rvisc = n x g ' , (3.10.2)
where g' is given by (3.3.13). This is the frictional torque exerted by the
molecules on the hydrodynamic motion. Clearly in the present geometry
(3.10.2) reduces to
^^t) (3.10.3)
where Ax = H2—H3 and X2 = fii~/j,6. Also, in the present geometry, the
viscous stress tensor t'n given by (3.3.5) can be simplified to
where
JV
G 6
\\ \\
Also assuming a spatially periodic fluctuation of the form
cp = (p0coskxx,
we have
JEZ)
3.10.3 DC excitation
In the DC case, we may set <p = 0 and the analysis becomes simple. Using
(3.10.1), (3.10.3) and (3.10.4),
3.10 Electrohydrodynamics 187
where rj^ = rj'[2X1/(X1 — X2)]2. Applying (3.10.5), we obtain the threshold
field
(3.10.7)
where
(3.10.9)
\% (3.10.10)
where
888
°" '
We have treated the distortion as a pure bend but this is not exactly true.
Since the thickness of the sample is of the same order as the periodicity of
the distortion, the orientation of the director will vary in the z direction
also. There will therefore be a non-negligible splay component. To allow
for this, it has been suggested(147) that the bend elastic constant k33 should
be replaced by
where the wavevector in the z direction kz ~ n/d. With this correction, the
DC threshold given by (3.10.10) is in good agreement with the experimental
value. For MBBA it is about 8 V.
and
11
\ fin
- — — E2
(3.10.19)
T is the decay time for curvature, and rj is an effective viscosity coefficient
given by
n «
Equations (3.10.14) and (3.10.18) are two coupled equations which cannot
be solved analytically for any general value oiEz(i) since y itself depends on
Ez and t. However for a square wave
J + £, 0<t<n/co
A )
\-E, n/(D<t<2n/oj.
In this case y remains constant in any half-period and the solutions are
simpler and enable a physical interpretation of many of the observed
phenomena. If the solutions are taken in the form (147)
y/ = Cw exp (At/z\ q = Cq exp (At/x),
the general solutions become
/T)9 (3.10.20)
where
190 3. Continuum theory of the nematic state
-expH; ±
1—exp (3.10.22)
A2t
-l-Ao exp
Eo^x
sx —
-exp
2vx
exp
-\-Ax
where v = co/2n is the frequency of the voltage. Here q changes sign with
E, but y/ does not, which is the situation in the conduction regime.
+ expl ^ 2 - ^ 1
\ 2VT
(3.10.23)
sx — Ax
1+exp
2vx
1 ^T. n
A2-Ax • ^ / -
In this case y/ changes sign with E, but q does not. This corresponds to the
dielectric regime in which the director oscillates.
In the above equations, s is a real number which determines whether the
system is stable or not, and which takes the value 0 at the threshold. Setting
s = 0 and defining
3JO Electrohydrodynamics 191
\ t
\
\ j1
\ i / i
(a)
\ / t
\ I
^ q
Fig. 3.10.8. Time dependence of the charge q and the curvature y/ over one period
of the square wave excitation, (a) Conduction regime (coz <4 1, T> z). The charges
oscillate but the domains are stationary, (b) Dielectric regime (coz ^> 1, T < r). The
charges are stationary and the domains oscillate. (After Smith et «/.(147))
<3l0 24)
-
and in the dielectric regime
TTA
±+i = U-l sinh (3.10.25)
'2COT'
These equations show clearly that the problem falls naturally into two
distinct parts. For T > z (3.10.25) has no solution and consequently there
is no dielectric regime, while for T < z (3.10.24) has no solution and there
is no conduction regime. For T = T, neither equation has a solution (except
when co = 0).
The theoretical variation of q and y/ over a full period of the exciting
wave is illustrated in fig. 3.10.8 for two values of co, one at low frequency
in the conduction regime (coz < 1, T > z) and the other at high frequency
192 3. Continuum theory of the nematic state
in the dielectric regime (coz > \,T 4, z). In the former case one obtains
essentially stationary domains and oscillating charges and in the latter case
vice versa. The transition from the conduction to the dielectric regime
occurs at a critical frequency coc such that coc z ~ 1.
Certain other interesting conclusions can be drawn from the above
equations. For example, even at frequencies less than coc, there can be
quenching of the conductive instability at high fields. This is because
T = (AEl + AQ)" 1 decreases with increasing Ez9 and when it becomes equal
to T there can be restabilization. At higher fields, T < z and the system
goes over to the dielectric regime. This gives a physical insight into the
origin of the sigmoid shape of the experimental threshold curve. Indeed,
theoretically the threshold field as a function of frequency for conductive
instability may be expected to form a closed loop.
Another result that follows from the theory is that the conduction
regime can be suppressed altogether by using very thin samples. We have
seen that at low frequencies, kx ~ n/d. Now a decrease in sample thickness
increases Ao, where from (3.10.19)
This, in turn, reduces the curvature relaxation T and when T < z the
conductivity instability is eliminated and only a dielectric instability is
possible. A similar quenching can be achieved by applying a stabilizing
magnetic field.
Greubel and Wolff(150) and Vistin(151) observed that for thin and pure
samples the spatial periodicity of the pattern in DC excitation decreases
with increasing voltage above the threshold. Smith et <z/.(147) have suggested
that this variable grating mode(150) is due to non-linear (saturation) effects
at higher voltages in samples that are so thin and pure that the conductivity
instability has been quenched.
— coscot = 0, (3.10.27)
3.10 Electrohydrodynamics 193
where
we have
=
# —i^— M 2 2 (cos ^ +C0T s m w
0J
so that
F2 — —
194 3. Continuum theory of the nematic state
where £ is the magnetic coherence length (see §3.4.1). For low magnetic
fields, £ > d, we get a voltage threshold independent of the thickness of the
sample:
__v_w_fv (3.10.31)
where
47T£II j
V
33 '
HV> O.10.32)
rv<o
(a)
Fig. 3.11.1. The mechanism for homogeneous instability: the flow is along y and
the velocity gradient along z. (a) An angular fluctuation 6 = nz > 0 results in a
viscous torque Yz > 0 such that a small twist (/> = ny > 0 is produced, (b) a
deformation <j> > 0 results in a torque Yy < 0 such that the initial deformation 0 is
enhanced.
(3.11.4)
Hcl and H are the Freedericksz threshold fields for the splay and twist
geometries. It is seen that Scccd~2, and for large Hx, ScccH2x; these
predictions are in agreement with observations. For a sample thickness d
of 200 //m, the zero field critical threshold velocity v c= 11.5 jum s"1 for
MBBA.(159)
3.11 Hydrodynamic instabilities 197
100
80
60
40
20
1 2
Frequency (Hz)
Fig. 3.11.2. Experimental roll instability threshold curves for MBBA as functions
of the applied voltage and frequency of shear for different values of the effective
plate velocity veU; d = 240 //m, Hx = 3200 G. (From Pieranski and Guyon.(159))
100
v'3
Y
v3
> \
Z | Stable
X
/ ,
TR
s
.' Y
0.6 0.8
Frequency (Hz)
Fig. 3.11.3. Roll instability threshold curve for vett = 0.148 cm s 1 from fig. 3.11.2
showing the regimes Y,Z and TR (see text). (From Pieranski and Guyon.(159))
To understand these curves let us examine the curve for a given vm (fig.
3.11.3). Let us suppose that the frequency of shear is kept constant at
0.8 Hz and the voltage Vz is increased. At V = 0, the instability is of the Y
type; at Vx the instability disappears; at V2 > Vx the instability reappears
but is now of the Z type; and finally at V3 > V2 it disappears again. The
spatial periodicity of the rolls remains of the order of the sample thickness,
though it is somewhat larger in the branch just above the cusp. At a
frequency slightly less than that at the cusp, 0.6 Hz say, the instability is of
the Y type at V = 0. At much larger voltages it is of the Z type, but for
V = V's the rolls disappear. The changeover from Y to Z takes place in a
transition regime, TR, that is defined by extrapolating the two branches to
lower frequencies. In TR the rolls do not extend over large regions but
seem to correspond to an interchange between the Y and Z types along a
given roll. The laser diffraction pattern now has satellite spots in the y
direction and also shows that the spacing between the rolls has doubled.
The principal mechanism for the onset of RI is shown schematically in
fig. 3.11.4. A spatially periodic <j>fluctuation(or ny fluctuation) of the form
cos qx x results in a secondary velocity vz that is also periodic in x. This
effect has been referred to as hydrodynamic focussing. Under appropriate
conditions, vz can have a destabilizing effect and generate convective rolls.
200 3. Continuum theory of the nematic state
c = 45.70
o)Ty/2n
Fig. 3.11.5. Calculated roll instability curves fitted to the results of fig. 3.11.3 by
adjusting the values at zero frequency, at the cusp and at a point P to define the
frequency scale. (From Pieranski and Guyon.(159))
For a given <p there is the torque ju3 S</> due to the primary velocity (as in HI)
as well as a torque due to the secondary velocity gradient vZt x and together
the total viscous torque Yy brings about a distortion 6. In turn, a 6
distortion gives rise to a torque Tz that increases <f>. (We have already seen
in the case of HI that Tz = — ju2 S6, but this value is now modified slightly
by a torque due to vy z.)
The complete calculation of the threshold for RI involves a solution
of the form exp \{qx x + qz z) with boundary conditions for 6, </>, vx9 vy,
and ^.<159'160'163> We present only the salient results of the theory.
Assuming fcn = k22 = fc33 = k, and ignoring material derivatives in (3.3.1),
3.11 Hydrodynamic instabilities 201
the behaviour under A C shear c a n be expressed in terms of two coupled
equations with ny( = <p) a n d nz( = 0) as the variables;
09 (3.11.5)
y 0, (3.11.6)
where the relaxation rates are
(3.11.7)
;o
(a)
T+AT
(b)
Fig. 3.12.1. (a) Thermal instability in a nematic heated from below. Initial
orientation of the director is horizontal (along y). A bend fluctuation causes 'heat
focussing' because of the anisotropy of thermal conductivity (K^ > K±) and gives
rise to warmer ( + ) and colder ( —) regions. The warmer regions move up and the
colder regions down due to buoyancy effects and this, in turn, results in a velocity
vy (the fluid being assumed to be incompressible). The transverse velocity gradient
vz y induces a major destabilizing viscous torque, while the vertical gradient vy z
induces only a very weak stabilizing torque. The resulting torques, shown by the
curved arrows, are destabilizing. Here the long straight arrows represent the
translational velocities vz and vy9 the short straight arrows the heat fluxes, (b) The
same geometry as in (a) but with the top plate at a higher temperature. The system
is stable.
T+AT
(a)
T+AT
Fig. 3.12.2. (a) The initial orientation of the director is along z. A splay fluctuation
gives rise to warmer and colder regions. In this case, vyz causes a dominant
stabilizing viscous torque while vz y causes only a very weak destabilizing torque.
The system is therefore stable against stationary convection, (b) The same geometry
as in (a) but with the top plate at a higher temperature. The system is unstable (see
legend of fig. 3.12.1
where y/ = d6/dy is the director curvature and 019 vz0, T'o are amplitudes of
fluctuations. In (3.12.4) T¥ = — ^x/kzzq^ is the relaxation time for the
director in the absence of any coupling. Ignoring vz0 in (3.12.2) and
3.13 Flexoelectricity 205
eliminating vz0 in (3.12.3) and (3.12.4) one finds the condition for threshold
to be
3.13 Flexoelectricity
3.13.1 Determination of the flexoelectric coefficients
If the molecule possesses shape polarity in addition to a permanent electric
dipole moment then the possibility exists that a splay or bend deformation
206 3. Continuum theory of the nematic state
(c) id)
Fig. 3.13.1. Meyer's model of curvature electricity. The nematic medium composed
of polar molecules is non-polar in the undeformed state {{a) and (c)) but polar
under splay (b) or bend (d). (After Meyer.(171))
(b)
Fig. 3.13.2. Interpretation of the origin of flexoelectricity in an assembly of
quadrupoles: (a) in the undeformed state the symmetry is such that there is no bulk
polarization, (b) a splay deformation causes the positive charges to approach the
upper plane and to be pushed away from the lower one. This dissymmetry gives rise
to a dipole moment.
will polarize the material, and conversely that an electric field will induce
a deformation (fig. 3.13.1). This phenomenon, which is somewhat
analogous to the piezoelectric effect in solids and is therefore termed as the
3.13 Flexoelectricity 207
Fig. 3.13.3. A hybrid aligned cell for the determination of the anisotropy of the
flexoelectric coefficients. In this geometry, the director has a splay-bend distortion
which gives rise to a flexoelectric polarization Px. On applying an electric field Ey,
the director is twisted by an angle $ oc (e1 — e3) which can be measured optically.
(Dozov, Martinot-Lagarde and Durand. (174) )
<
-30
-50 0
Electric field (V mm"1)
Fig. 3.13.4. ^(0) versus is for two twin domains in the sample. The linearity of the
slope confirms the validity of (3.13.2). (Dozov, Martinot-Lagarde and Durand. (174) )
small, since the dielectric free energy is proportional to E2.) The twist angle
is maximum close to the bottom plate (fig. 3.13.3) where the curvature is
maximum and is given by
Ed
(3.13.2)
(a)
(b)
d = 35 /^m
/ c = 120 Hz
4 -
Normal
rolls
50 90
Frequency (Hz)
4.1.1 Propagation along the optic axis for wavelengths <^ pitch
Basic theory
We shall first consider the propagation of light along the optic axis for
wavelengths much smaller than the pitch so that reflexion and interference
213
214 4. Cholesteric liquid crystals
effects may be neglected. The problem was investigated by Mauguin (1) with
a view to explaining the optical rotation produced by twisting a nematic
about an axis perpendicular to the preferred direction of the molecules. He
used the Poincare sphere(4) and ' rolling cone' method, but we shall adopt
an identically equivalent formalism, viz, the Jones calculus/ 5 ' 6)
The basic principle underlying the Jones method is that any elliptic
vibration can be represented by the column vector
D = JD,
and S"1 is the inverse of S so that SS"1 = S-1S = E, the unit matrix.
If Do is the complex column vector with respect to x, y representing the
incident light, the emergent light after passing through the first layer is
E, (4.1.2)
where
cos 6 = cos p cosy.
216 4. Cholesteric liquid crystals
Now, as stated earlier, the layer thickness is assumed to be very small, say
a few A, while the pitch P is taken to be at least a few wavelengths of light,
so that both ft ( = 2np/P) and y are small quantities. Therefore
(4.1.3)
From (4.1.1) and (4.1.2)
_ tan/? . _. _ . sinra# . ,
a = cos rap cos rat/H -sin rap sinrat/— i ——— sinycos(ra + l)p,
tan 6 sin 6
(4.1.4)
tan/? _. _ . _ _ .sinra# . . ,
b= -cosmpsmmu — smmpcosmu — I—-—— sinysin(ra + l)p,
tan 6 sin 6
(4.1.5)
c = — b* and d=a*,
where a* and &* are respectively the complex conjugates of a and b.
It is a standard result in optics (6) that such a system can, in general, be
replaced by a rotator and a retarder. If p is the rotation produced by the
system, 2(p the phase retardation and y/ the azimuth of the principal axes of
the retarder,
ip) 0 1 _ r _ r
L 0 exp (i#>) J [ — sin y/ cos^J
m
4.1 Optical properties 217
0 1 2 3 4 5 6
I/A2 (Mm-2)
Fig. 4.1.1. Rotatory dispersion of a cholesteric liquid crystal for wavelengths <^
pitch. Solution of poly-y-benzyl-L-glutamate (PBLG) in chloroform (18 g/100 g).
(After Robinson.(12)).
taking P = 5 jum and X = 0.5 jum, p ~ 2000° mm" 1. This equation has been
verified experimentally in considerable detail by Robinson (12) in lyotropic
systems and by Cano and Chatelain (13) in thermotropic systems.
Robinson discovered that solutions of some polypeptides in organic
solvents, for example, poly-y-benzyl-L-glutamate (PBLG) in dioxan,
methylene chloride, chloroform etc., spontaneously adopted the choles-
teric mesophase above a certain concentration. Under suitable conditions
the solutions exhibited equi- spaced alternate bright and dark lines when
observed through a microscope (see fig. 4.2.7). The lines may be interpreted
as a view of the structure at right angles to the screw axis, so that the
periodicity of the lines is equal to half the pitch. Robinson confirmed this
interpretation by observations between crossed polaroids and also by the
use of a quartz wedge; the retardation plotted against distance in a
direction perpendicular to the lines had an oscillating value, as is indeed to
be expected from the structure. The pitch for any given polypeptide
depended on factors such as concentration, solvent, temperature etc. When
viewed along the screw axis no lines were seen, but a very high optical
rotatory power was present. The rotation in every solution, with a very
wide range of values of P was found to be proportional to \/k2 (fig. 4.1.1).
Robinson substituted the observed values of p and P in (4.1.13), and
4.1 Optical properties 219
calculated the layer birefringence Sn per volume fraction of the polypeptide
in solution. The birefringence was remarkably constant despite the widely
varying values of p and P. He then prepared a solution with equal
quantities of the D and L forms (PBDG and PBLG) which too under
certain conditions adopted the spontaneously birefringent phase, only, in
this case, it was not the twisted cholesteric, but the untwisted nematic
structure. He was therefore able to measure the birefringence directly and
the value agreed well with that derived from (4.1.13).
Similar studies have been carried out by Cano and Chatelain(13) on
mixtures of nematic and cholesteric liquid crystals. The birefringence of the
nematic being very large, Sn of the mixture could be assumed without
sensible error to be equal to that of the nematic itself. The pitch P of the
mixture was measured directly from the Grandjean-Cano steps formed in
a wedge (fig. 4.2.9). The values of Sn and P when inserted in (4.1.13) gave
a rotatory power in quantitative accord with observations.
When P is comparable to or less than y9 the system is no longer a pure
rotator. For large values of the pitch, (4.1.1) may be expressed as(14)
+ sin m6
\sin 9 [Sl exp( -iy)] . (4.1.14)
\sin0 ^
pitch and sample thickness derived from (4.1.14) and (4.1.15) for very thin
cholesteric or twisted nematic films (the sample thickness being smaller
than the pitch). (1415) Here the rotation is defined as the quantity that is
most conveniently measured, viz, the angle between the incident plane of
polarization, assumed to be parallel to the director axis on the entrance
side of the film, and the major axis of the emergent ellipse. Unlike p given
by (4.1.10), this rotation is not independent of the azimuth of the plane of
polarization of the incident light/ 16 ' 17) but the general conclusions that we
may draw from these curves are still valid. We observe firstly that in
contrast to an ordinary optically active substance the optical rotation per
unit length in the twisted nematic (or cholesteric) is a function of the
thickness. A noteworthy feature is the reversal of the sign of rotation as the
pitch is varied.(17) In the neighbourhood of the Mauguin limit, the rotation
has the same sign as that of the helical structure. With decrease of P the
rotation drops to zero and then reverses sign; thus for lower values of P the
sense of the rotation is opposite to that of the helix, in conformity with
(4.1.13). With increase of sample thickness the peaks in the rotation
increase in height and become sharper. The predicted trends have been
confirmed experimentally.(18)
exp(-iy) 0
0
where ka, kb are the principal absorption coefficients of the layer, and
y= y-lKK-
4.1 Optical properties 221
Proceeding as before, the Jones matrix for m layers is
j m = Sm(GS"1)ro. (4.1.16)
r = ^—f-GS-'-AxA/ 1 . 7 E, (4.1.17)
where
^ = exp (-<![) exp (i0),
A2 = exp(-£)exp(-i/9),
and
cos^ = cos 7 cos )8.
J^exp(-^S-[^GS-^Sin(m-1)'El. (4.1.18)
L sin 6 sin 9 J
Such a system can be resolved uniquely into a rotator, a retarder, a
circularly dichroic plate and a linearly dichroic plate. The unique matrix
resolution is given by
where
_ [cos ^ - sin y/1
[sin y/ cos y/ J '
_ [cos/? — sin/7
[sin/7 cos/7
K = [exp(-/c) 0 1
L 0 exp(fc)J'
Here p is the rotation, a the circular dichroism, 2#? the linear phase
retardation, 2K the linear dichroism, / the attenuation coefficient and y/ the
222 4. Cholesteric liquid crystals
_x/sec2^
-IK = COS"1 r m0/ (4.1.20)
Vsec
X=
with
ICLL
j
n \ tan<9
and
a = -myju/p.
Therefore, the linear dichroism of the layers not only results in circular
dichroism but also makes a small contribution to the optical rotation
which is opposite in sign to that due to linear birefringence. However, this
contribution is usually negligibly small. Another consequence of the theory
is that o changes sign whenever /? or ju changes sign. Further, the parameter
o exhibits a marked dependence on pitch and sample thickness. These
predictions are in qualitative agreement with observations.(18"20)
4.1.2 Propagation along the optic axis for wavelengths ~ pitch: analogy
with Darwin's dynamical theory of X-ray diffraction
When the wavelength is comparable to the pitch, the optical properties are
modified profoundly. Before discussing the rigorous electromagnetic
treatment of the problem it is instructive to examine it first from the
standpoint of X-ray diffraction theory/ 7 ' 21) Since the dynamical theory of
X-ray diffraction from perfect crystals and its applications are now quite
thoroughly understood, this approach may be useful in elucidating the
optical behaviour of cholesterics and in looking for new optical analogues
of certain well established X-ray effects. An example of a new phenomenon
is the Borrmann effect in cholesterics.(22)
4.1 Optical properties 223
i (4.1.22)
where cps+1 = 2nnn(s+ \)p/X, p being the thickness of each layer. At the
boundary, the £ vibration emerges from a medium of refractive index
na and the rj vibration from a medium of refractive index nh. Qualitatively,
it is obvious that since the principal axes of the (s + 2)th layer are rotated
slightly with respect to those of the (s+ l)th layer, one of the components
of (4.1.22) will on emerging from the (s+ l)th layer meet a 'rarer' medium
while the other will meet a ' denser' medium. One component therefore gets
reflected without any change of phase and the other with a phase change of
n. Thus, in contrast to reflexion from a normal dielectric, the sense of
circular polarization remains the same after reflexion. Applying the
f Right- and left-circular polarizations are denned from the point of view of an observer
looking at the source of light. If the electric vector rotates clockwise with progress of time,
then it is right-circular. Thus, at any instant of time, the tip of the electric vector forms a
right-handed screw in space for right-circular polarization.
224 4. Cholesteric liquid crystals
standard formulae for reflexion at normal incidence from the surface of a
non-aborbing anisotropic crystal, the reflected components £', rj\ referred
to the principal axes of the (s + 2)th layer, are
rf
where q = fidn/2n. We make the approximation here that sin/? « /?, since ft
is assumed to very small (~ 10" 2 rad). On reflexion a very slight ellipticity
is introduced in the transmitted beam but we shall ignore it in the present
discussion. Transforming back to x,y the reflected wave on reaching the
surface of the liquid crystal will be
GI--UJ
which represents a right-circular vibration travelling in the negative
direction of z. Clearly the phase difference between this wave and that
reflected at the boundary between the first and second layers is 2(sp—(p s).
When h = nnP, we have 2nnnp/A = /? and <ps = s/3 (since mp = P and
mp = 2n, where m is the number of layers per turn of the helix). Hence the
phase factor exp[2i(s/$—(p 8)] becomes unity irrespective of the value of s,
and there results a strong interference maximum. For a left-handed
structure, /? is negative and (s^—(p s) does not vanish; therefore, the waves
from the different layers will not be in phase and the vibration will be
transmitted practically unchanged.
Using the kinematical approximation, i.e., neglecting multiple reflexions
within the m layers, the reflexion coefficient per turn of the helix is
|g| = m\q\ = ndn/n. (4.1.23)
,., | f Sr+1
r+1
Fig. 4.1.3. Notation for the primary (T) and reflected (S) waves in the dynamical
theory.
and
-i v-2.._, ,(v-4)(v-3) _
(4.1.29)
226 4. Cholesteric liquid crystals
Similarly from (4.1.25), (4.1.26) and (4.1.28)
where
When
y = exp ( 0 + exp (-£) = 2cosh£,
the series in (4.1.29) is given by(24)
4.1 Optical properties 227
1.0
:J
0.8 (a)
0.6
I
9S 0.4 -
I 0.2 -
8 o.o
o ^
'% 1.0 -
<S
ib)
0.8 -
0.6 -
_A 1
0.4 -
0.2 -
00
0.45 0.47 0.49 0.51 0.53 0.55
Wavelength (jum)
Fig. 4.1.4. Reflexion coefficient 0t at normal incidence versus wavelength for a non-
absorbing cholesteric: (a) semi-infinite medium, (b) film of thickness 25P, where P
is the pitch. Curves are derived from the dynamical theory; circles represent values
computed from the exact theory (§4.1.3) assuming that the medium external to the
cholesteric (e.g., glass) has a refractive index 1.5. The parameters used in the
calculations are n = 1.5, Sn = 0.07, X0 = nP = 0.5 jum. (After reference 21.)
So_ -iQexpjie)
(4.1.36)
or
+ cf cothV
For the semi-infinite medium, v = oo in (4.1.36) and
So Q (4.1.37)
To e±i(Q2-ey
When - Q < e < Q, £ is real and
o 2
01= — = 1.
228 4. Cholesteric liquid crystals
0.75
0.50
0.25
0
0.70 0.68 0.66 0.64 0.62 0.60 0.58 0.56
Wavelength (jum)
Fig. 4.1.5. Reflexion spectrum from a monodomain cholesteric film at normal
incidence. Full curve: experimental spectrum for a mixture of cholesteryl
nonanoate, cholesteryl chloride and cholesteryl acetate in weight ratios 21:15:6 at
24 °C (intensity in arbitrary units). Broken curve: spectrum computed from the
exact theory for a film thickness of 21.0 //m and pitch 0.4273 jum. (After Dreher
et
The reflexion is total within this range. The spectral width of total reflexion
is therefore A/I = Qkjn. Using (4.1.23),
A/I = Pdn, (4.1.38)
(3)
a result first derived by de Vries. Outside this range, the reflexion
decreases rapidly on either side. When X > Ao, e is negative and hence the
negative value of the square root in the denominator of (4.1.37) has to be
taken because @ can never exceed unity; when X < l0 the positive root has
to be taken.
Illustrative curves of M as a function of wavelength are shown in fig.
4.1.4. The semi-infinite medium gives the familiar flat topped curve of the
dynamical theory, while the thin film gives a principal maximum
accompanied by subsidiary fringes. The fringes are somewhat difficult to
observe as even slight inhomogeneities in the specimen and small variations
in its thickness tend to obliterate them, but careful experiments by Dreher,
Meier and Saupe(25) have confirmed that they do occur (fig. 4.1.5).
4.1 Optical properties 229
Inside the totally reflecting range, £ is real and the wave is strongly
attenuated. In X-ray diffraction theory, this phenomenon is referred to as
primary extinction. The extinction length, defined as the distance over
which the amplitude of the incident wave decreases to l/e of its value, is
P/Q at the centre of the reflexion band.
Outside the range of total reflexion, £ is imaginary and primary
extinction vanishes. Fig. 4.1.6 gives a plot of the wavevectors Kn
( = 2nnn/X) and KL ( = innJX) for right- and left-circular polarizations
respectively, as functions of the wavelength. The real part of Kn shows a
gap within the reflexion band - analogous to the familiar band gap in solid
state physics - while the imaginary part grows rapidly in the same region.
When e2 > Q2, ^ — i(e2 — Q2)* and may be positive or negative. The
optical rotation per pitch is clearly
n(5n)2P niX — X
P= 7TT- + 5-
230 4. Cholesteric liquid crystals
17.0 -
18.0 -
| 19.0 -
& 20.0 -
21.0?-
When Q2 > e2, i.e., within the region of total reflexion, p given by
(4.1.39) becomes complex, showing that the medium is now circularly
dichroic. The real part which represents the rotatory power is
n{Sn)2P
F (4.1.40)
~ U2 ' Pk '
sinh(v
*r« £ cosech v^
k 4- £ coth v£
(4.1.41)
and
- 1.
Fig. 4.1.7. Rotatory power versus wavelength for a non-absorbing cholesteric: (a)
semi-infinite medium, (b) film of thickness 25P. Curves are derived from the
dynamical theory; circles represent values computed from the exact theory. «, Sn
and Xo same as in fig. 4.1.4.(21)
where
tan vy/ =
and
n{8nfP yj-e
P
~ W~ ~^p~'
The theoretical variation of p with X is shown in fig. 4.1.7. As observed
232 4. Cholesteric liquid crystals
-30 r
-20 0.8
0.6
-10 0.4
0.2
U
0.0
o
10
20
0.4 0.5 0.6 0.7 0.8 0.9 1.0
Wavelength (//m)
Fig. 4.1.8. Experimental circular dichroism (open circles) and rotatory dispersion
(closed circles) of cholesteric cinnamate at 177 °C. Sample thickness ~ 3 jum.
(After reference 26.)
-1.0
0.45 0.47 0.49 0.51 0.53 0.55
Wavelength (jim)
Fig. 4.1.9. (<z) Reflexion coefficient 0t at normal incidence, (Z?) imaginary parts of Kn
and ATL, (c) rotatory power /? (the real part of />), plotted against the wavelength for
an absorbing semi-infinite medium calculated from the dynamical theory, K = 0.02,
SK = 0.028 and other parameters same as in fig. 4.1.4. (After reference 21.)
this case also except that Q, q>n, etc. have to be replaced by the
corresponding complex quantities:
Q = nSn/n,
2nnnP 2nnP n(Sn)2P2
<Pn = X X 4/1 2
2nnP n(Sn)2P2
4X2
yi yi \rr yt yi i -is
n
a — na 1K
a> U
b ~ n
b lK
b>
where Ka,Kb are the principal absorption coefficients. Fig. 4.1.9 gives the
reflexion coefficient 0t and the dependence of the real part of p and the
234 4. Cholesteric liquid crystals
0.00 -
£ cosech v£
-0.8
Wavelength (//m)
Fig. 4.1.11. Circular dichroism versus wavelength computed for different K and SK.
Sample thickness 25/>, n = 1.5, Sn = 0.07 and X0 = 036jiim. The absorption
coefficients were assumed to be Gaussian curves having a maximum at 0.36 jum and
of halfwidth 0.06 jum. The maximum values of K and SK are, respectively, as
follows: (a) 0.0125, 0.0157; (b) 0.0250, 0.0314; (c) 0.0375, 0.0471; (d) 0.0500,
0.0628; (e) 0.0625, 0.0785. (After reference 28.)
absorbing case 3T^ shows an enhanced value on the short wavelength side
of the reflexion band, which is the analogue of the Borrmann effect.
The phenomenon is shown up even more convincingly in the circular
dichroism curves (fig. 4.1.11). For a left-handed structure (i.e., negative)?),
«yL exhibits an anomalous increase and for SK < 0, the peak transmission
occurs on the long wavelength side of the reflexion.
236 4. Cholesteric liquid crystals
-0.4 -
0.2 -
0.1 •
0.0
-0.1 -
-0.2 -
-0.3
-0.4
0.32 0.34 0.36 0.38
Wavelength (//m)
Fig. 4.1.12. Experimental circular dichroism curves versus wavelength, (a) Pure
cholesteryl nonanoate (CN), (b) CN + 0.98 per cent by weight of PAA. Sample
thickness in both cases 6.5 jum. (After reference 28.)
4.1.3 Exact solution of the wave equation for propagation along the optic
axis: Mauguin-Oseen-de Vries model
We next consider the exact solution of the wave equation for propagation
along the optic axis. The complete theory is contained in the papers of
Mauguin,(1) Oseen(2) and de Vries,(3) and has since been presented in
various forms by other authors. (30~3) We shall discuss an elegant treatment
of the theory developed by Kats, (30) and by Nityananda. (31)
We represent the dielectric tensor by a 'spiralling ellipsoid' whose
principal axis Oc is always parallel to z; the other two principal axes Oa
and Ob (with principal values sa and eb) spiral around z with a twist angle
q = 2n/P per unit length. If Oa, Ob are taken to be along x, y at the origin,
the tensor s at any point z may be expressed with respect to x, y as
ocsin2qz , (AAA2)
[_ asin2#z e — acoslqz •]•
where sa = n2a, sb = n\, e = %ea + eb), a = \(ea-eb) = \{na + nb)(na-nb) =
nSn. The wave equation for propagation along z is
e2E
=--jeE. (4.1.43)
8?2 c
We introduce the variables
E" = 2~\Ex-xEy\
E' is right-circular and E" left-circular for propagation along -fz and vice
versa for propagation along — z. Substituting in (4.1.43) we obtain
co2[ e aexp(2ig.
,22 l « ^ ^ / -»:^_\
c [aexp( — 2\qz) e» Ilr7//I' (4.1.44)
[A'cxp[i(k-q)z]\'
which is a superposition of two waves of opposite circular polarizations
238 4. Cholesteric liquid crystals
-0.5
\JLJLJLJ
I
500 600 700
A (nm)
Fig. 4.1.13. Circular dichroism in a mixture of 91.5% nematic ROTN 103 (of
Hoffman-La Roche) +7.5 % optically active L-menthol + 1 % dye/?-nitrobenzene-
bis(benzalazo)-/?'-dimethylaniline. Sample thickness 11.3/mi. Crosses represent
experimental values and the solid curve gives the theoretical variation. (After
Aronishidze et al.{29))
(4.1.46)
(k-qf-t
kt, k, = (4.1.47)
4.1 Optical properties 239
A' *K2
A"
and } (4.1.48)
A"
A' -qf-Kl')
When a is small, (4.1.47) and (4.1.48) give for the k2 solution A' I A" ~ a,
and for the k± solution A" I A' ~ a. In other words, each normal wave is
made up of two oppositely polarized circular components with one of the
components generally dominating. The mixing of these two components
with wavevectors differing by 2q is a consequence of the Bragg reflexion.
Equation (4.1.45) may conveniently be rewritten as
U_ T exp(i^z)
U
I exp(iK2z) ]'
where
Kx = k1+q = q + [K2m + q2-(4Klq* + a*K^]K (4.1.51)
2 2 2
K2 = K ~ q = - q + [Kl + q + ( 4 ^ q + a K*)i\\ (4.1.52)
The fact that the wavevectors Kx and K2 are different is responsible for the
optical activity of the medium, the optical rotation per unit length being
p = K ^ — ^g) rad. However, as emphasized in previous sections the phe-
nomenon is not identical with natural optical activity because the normal
waves are not pure circular waves.
P=
where
240 4. Cholesteric liquid crystals
When x2 < a2K*, p becomes a complex quantity. The real part gives the
rotatory power and the imaginary part the circular dichroism. Since no
dissipative mechanism is built into the model it follows that the imaginary
part of p is associated with the reflexion of one of the components. The
reflexion band is centred at x = 0, i.e., at Km = q or Xo = nP where Xo is the
wavelength in vacuo. The range of reflexion extends from x = +aK2 to
x = —OLK2, i.e., from + q\dn/ri) to -q\dn/ri). Since
AX = PSn (4.1.54)
n{dnfP
(4.1.55)
This is known as the de Vries equation. The sign of the rotatory power
reverses on crossing the reflexion band (Ao). When X <^ Ao, (4.1.55) reduces
to (4.1.21), and when X > 20, p tends asymptotically to 0. The behaviour on
either side of the reflexion band has been confirmed experimentally(26) (fig.
4.1.8).
Thin films
(16)
Nityananda and Kini have applied the theory to obtain exact solutions
for reflexion and transmission by a plane parallel film bounded on either
side by an isotropic medium. The treatment allows for the contribution due
to reflexion at the cholesteric-isotropic interface. In general, for each
circular polarization at normal incidence the reflected and transmitted
waves consist of both circular polarizations. Four coefficients, two for
reflexion and two for transmission, are required to describe the problem
fully and the solution consists of matching the incoming and reflected
waves on one side of the slab with four waves within the slab (two in the
forward direction and two in the backward direction) and the transmitted
wave on the other side. An extension of the treatment to absorbing media
yields the theory of the Borrmann effect.(22)
4.1 Optical properties 241
Some calculations for the semi-infinite medium and for the thin film are
shown in figs. 4.1.4, 4.1.6 and 4.1.7. In these calculations, the isotropic
medium external to the liquid crystal is assumed to have a refractive index
equal to n = \{na + nb) so that the contribution of the ordinary Fresnel
reflexion coefficient at the cholesteric-isotropic interface is eliminated. It is
clear from these figures that the results of the exact theory differ only
slightly from those of the dynamical model, indicating that the latter is
probably adequate for most practical calculations. However, the simple
formulation of the dynamical model presented in §4.1.2 does have some
inherent limitations: (i) it is valid only for integral values of the pitch, (ii)
it is developed for small e (= —2U{X — XQ)/X) and therefore does not give
exact values for wavelengths away from the reflexion band, and (iii) it fails
when the film thickness is very small, or when the extinction length is of the
order of a pitch. These limitations arise primarily because of the
kinematical approximation made for the reflexion from the m layers per
turn of the helix. We shall now show that when multiple reflexions within
the m layers are also included, the simple difference equations become
matrix difference equations and the resulting solutions turn out to be fully
equivalent to the exact electromagnetic treatment. Proofs of this result
have been given by Joly(32) and by Nityananda. (3134) We shall follow the
latter's treatment(34) which is simpler.
rn = --
/„ =
(„„+!)*-(„„-1)* T J'
where xa — exp (ina Kp), K is the wavevector in vacuo and p the layer
thickness.(35) Exactly similar expressions may be written for the other
polarization also.
We define Is and Js as the amplitudes incident on the sih layer in + z and
242 4. Cholesteric liquid crystals
s s+\
Fig. 4.1.14. Notation for the incident and reflected waves. Is and Js are the
amplitudes of the waves incident on the 5th layer in the positive and negative
directions respectively, and Es and Ss the amplitudes emerging from the 5th layer in
these two directions.
(4.1.56)
The second two lines can also be similarly combined. However, in what
follows we shall write them in the form
(4.1.57)
Strictly these equations should include a phase factor allowing for the air
gaps between the layers, but the gap may be taken to be infinitesimally
small compared with the thickness of the layer, which itself tends to zero.
Using (4.1.58), (4.1.59) and (4.1.57)
M -3EMS-*
244 4. Cholesteric liquid crystals
ASA"1 =
i/0 0 "I
0 exp(iy9)J'
Since r and t are functions of the thickness p of the layer, we expand them
in powers of/?. It is sufficient to retain the first power in each case:
F=l(s-l)iKp,
where as before e = |(£a + eb) and a = |(e o — £„). Writing fi = qp and q> = kp
(and remembering that since r is of order p, rS ~ r to this order) (4.1.62)
may be expressed as
(4.1.63)
-1
K
Uk + qf-eK* -*K* 1
2 ( 6 )
1 -a* (k-q)*-eK'\-
Since the first matrix on the right-hand side is non-singular we may
premultiply by its inverse to obtain (4.1.63) in the form
Uk + qf-
[ -<xK2 (k-q)2-sK2\[F_\ '
which is precisely the same as (4.1.46). The dynamical theory applied in this
4.1 Optical properties 245
manner to a twisted pile of birefringent layers is then exactly valid for any
arbitrary thickness of the sample and for the entire range of wavelengths.
.kceT
— 1- 0 Ex
CO
CO
\HV -e 0 iHy
c b
•
x
l Ey
kcY
_ 0
CO CO 1
or
QZ
exx =
eyy = e — occos2qz,
([
r
0.2 -
00 , ji^
Second
0.2 — order
jV
First
order Observed spectra
0.6 _
i I 1
1.0 1.4
Fig. 4.1.15. First and second order reflexion spectra of a cholesteric liquid crystal
film (0.45:0.55 mole fraction mixture of 4/-bis(2-methylbutoxy)-azoxybenzene and
4,4'-di-n-hexoxyazoxybenzene) 15 pitch lengths or 11.47 jum thick. Angle of
incidence 45°. Polarizer and analyser are parallel to the plane of reflexion for 0tn and
normal to it for 0to measurements. The small oscillations are interference fringes
from the two cholesteric-glass interfaces. (After Berreman and Scheffer.(38))
4.1 Optical properties 247
0.2
0.1
£ -0.1
-0.2
-0.3
30 34 38 42 46 50 54
Temperature (°C)
Fig. 4.1.16. Variation of inverse pitch with temperature in a 1.75:1 weight mixture
of right-handed cholesteryl chloride and left-handed cholesteryl myristate as
determined by laser diffraction. The mixture becomes nematic at 42 °C. (Sackmann
et
4.2 Defects
4.2.1 %-disclinations
We now consider defect structures in the cholesteric liquid crystal. Treating
the cholesteric as a spontaneously twisted nematic,
nx = cos 0, ny = sin #, nz = 0,
6 = qz, q = 2n/P,
P being the pitch. The free energy density is then expressible as
(4.2.1)
4.2 Defects 249
(4.2.2)
and V26> = 0.
disclinations
Such disclinations are closely analogous to nematic wedge disclinations
(§3.5.1). The singular line is along the z axis (parallel to the twist axis) and
the director pattern is given by
nx = cos 9, ny = sin 6, nz =
0 = s tan" 1 (y/x) + qz (4.2.3)
s = ±N/2,
where N is an integer. The presence of the disclination does not alter the
pitch. Fig. 4.2.1 illustrates the director patterns for disclinations of strength
s = 1 and 1. Many of the conclusions arrived at in §3.5.1 are valid in this
case as well, and in the one constant approximation the expressions for the
energies and interactions are the same as for nematic wedge disclinations.
As already indicated briefly in §3.5.8 the effect of elastic anisotropy has
some interesting implications for cholesterics, especially for long-pitched
structures. We have seen that disclination pairs in nematics have angular
forces in the presence of elastic anisotropy. For all practical purposes, the
solutions that were obtained for nematics will hold good for each nematic-
like cholesteric layer, except that the layers now twist continuously in the
250 4. Cholesteric liquid crystals
(a)
Fig. 4.2.2. A pair of like /-screw disclinations forming a stable double helix in a
cholesteric: (a) a pair of s = \ disclinations (after Cladis, White and Brinkmann(42)),
(b) a pair of s = 1 disclinations (after Rault(43)); see fig. 3.5.24.
medium. Therefore, for a pair of disclinations, angular forces will lock the
line joining the disclinations at the same orientation with respect to the
local director n (of the defect-free sample) in every layer. Hence while single
disclinations may be straight, pairs of disclinations in a cholesteric may be
expected to have a helical configuration (see fig. 3.5.24). For a pair of like
disclinations, mutual repulsion increases the separation between them, but
in the helical state this will be opposed by the line tension in each
disclination. In the end the two opposing processes should balance to result
in a stable double helix. This is indeed found to be the case experimentally
4.2 Defects 251
&
Fig. 4.2.3. A helical %(s = — 1) disclination wound round a straight %(s = +1)
disclination in a cholesteric liquid crystal (Rault(44)); see fig. 3.5.24.
(fig. 4.2.2). On the other hand, if the individual disclinations of the pair
have different line tensions (as is the case for 1 and — 1, both of which are
escaped structures) then the disclination with a lower tension should wind
around the one with the higher tension. This again appears to be in
conformity with experimental observations (fig. 4.2.3). The escaped
configurations for 1 and — 1 in the cholesteric are rather complex,(45) which
may perhaps account for the fact that the two do not annihilate one
another.
252 4. Cholestenc liquid crystals
H H -I
h- I- h- I- h-
Fig. 4.2.4. The director pattern for s = \ /-edge disclination in a cholesteric. Dots
signify that the director is normal to the plane of the diagram, dashes that it is
parallel to and nails that it is tilted.
X~edge disclinations
In this case the singular line is perpendicular to the twist axis. On going
round this line, one gains or loses an integral number of half-pitches. The
director pattern around the /-edge disclination was first worked out by de
Gennes(46) who proposed a nematic twist disclination type of solution:
nx = cos 0, ny = sin 0, nz = 0,>
9 = s tan"1 (z/x) + qz, (4.2.4)
s = N/2.
The cholesteric pitch is altered around the singular line where TV is an
integer. The pattern for s = \ is shown in fig. 4.2.4. Again, the energies and
interactions in the one-constant approximation are the same as for nematic
twist disclinations. A somewhat more elaborate treatment of this model
has been presented by Scheffer(47) and the effect of elastic anisotropy has
been investigated by Caroli and Dubois-Violette.(48)
The Volterra process for creating these disclinations is the same as for
nematic disclinations. For the screw disclination the plane of cut is parallel
to the cholesteric twist axis while for the edge disclination it is perpendicular
to it.
(a) (b)
\ ••N
id)
Fig. 4.2.5. The configurations for (a) A", (6) A , (c) T" and (d) T+ disclinations in a
+
cholesteric. Dots, dashes and nails have the same significance as in fig. 4.2.4.
(a)
(d)
Fig. 4.2.6. Examples of pairing of X and z disclinations of opposite signs in a
cholesteric. Edge disclinations composed of (a) X' and A+, (b) T~ and T+, (C) T~ and
A+, (d) X~ and T+ and (e) pincement composed of z+ and T~.
4.2.3 Dislocations
Because of the layered structure, defects in the cholesteric can be likened in
many respects to those in smectic A. Both of them exhibit focal conic
textures(52) and both allow for the existence of screw and edge dislocations.
To discuss these similarities we employ a 'coarse-grained' approximation
in which the cholesteric distortions are considered to be small and to vary
slowly over a pitch. In this approximation the free energy of distortion may
be expressed in terms of layer displacement u parallel to the twist axis:
where B = k22 q2 and K = |fc33 (see (4.6.22)). This expression first derived
by de Gennes is exactly of the same form as (5.3.3) for smectic A. We shall
now consider some applications of this model.(53)
Screw dislocations
The deformation around a screw dislocation may be written as
NP
u = -^Uur1(y/x)9 (4.2.5)
where PQ is the pitch and TV is an integer. The singular line is along the twist
axis. A circuit around the singular line results in a displacement of the
layer along the helical axis by an integral number of half-pitches. Equation
(4.2.5) can be recast to give the director orientation, and it is easily verified
that it becomes identical to (4.2.3) for the /-screw disclination and leads to
same results for the energies and interactions.
Edge dislocations
Let the layers be in the xy plane and the line of singularity along y.
Following the theory for smectic A (§5.4.2), one may write,
p Y If 00 H/r 1
u(x,z) = -£ 1 + - T-exp(-Aic a |z|+iK*)
(a)
(b)
(iv)
Fig. 4.2.7. Disclinations and dislocations in (a) fingerprint textures of cholesterics.
(b) interpretation of (i), (ii) and (iv) of (a). (After Bouligand and Kleman.(49))
256 4. Cholesteric liquid crystals
<4 2 6)
)\ - -
0.6nkP
h
where Ec is the energy of the core and C the core radius, which in this model
can probably be assumed to be of the order of Po. Hence the energy turns
out to be finite and does not diverge logarithmically with sample size as
does a nematic-lilce solution of the form (4.2.4).
If there are two like dislocations, one at (0,0) and the other at (x0, z0) the
forces Fx and Fz (along and perpendicular to the layers) acting between
them are
„ kPl
normal to the helical axis and to the dislocation line, the 'double'
dislocations get distorted (fig. 4.2.9 (b)). This is because a cholesteric
composed of molecules of positive diamagnetic anisotropy prefers to have
its helical axis normal to the field, but the region between the disclination
pair has its axis along the field. Energetically, therefore, it is favourable for
the lines to adopt a zig-zag shape. Qualitative arguments suggest that the
lowering of the energy is greater the larger the separation between the
disclinations. This probably explains why the weaker lines, which are
composed of Xx pairs, remain stable.
where Q is the heat supply per unit volume, qt the heat flux vector per unit
area per unit time and the other symbols have the usual meanings (see
§3.3). If /?^ is the entropy flux vector per unit area per unit time, it is
convenient to introduce a vector cpi such that
with
<Pt = ^m^(Nk + dkpnp),
where a is a constant. The inequality (4.3.5) then becomes
260 4. Cholesteric liquid crystals
Resolving tip gt and pt into their static and hydrodynamic parts,
we have
~~^nk,p (4.3.8)
P°t = 0 , (4.3.9)
and (4.3.6) reduces to
(4.3.16)
where // 15 ...,// 6 are the six viscosity coefficients already defined in the
continuum theory of the nematic state; ju7 and ju8 are two additional
viscosity coefficients coupling thermal and mechanical effects; A^1?...,AT4
are the coefficients of thermal conductivity.
The free energy of elastic deformation per unit volume is given by (3.2.7).
Martin, Parodi and Pershan(57) and Lubensky(58) developed a general
4.3 Leslie's theory of thermomechanical coupling 261
A _ 87* +. (4A)
^ M* *)
820 _ 60 8/ 7 80\
^)-{x^-x^k> (4A2)
where
de
Af -k k \-)idT-o
2 22 3
dz\ dz) 6z
giving
CT
Jo
4.4 The Lehmann rotation phenomenon 263
and
K
^ Jo 22 \ Jo / Jo ^22
One can then work out a simple solution if the material constants are
assumed to be independent of temperature. Let 9 = cot +/(z) and T = g(z);
(4.4.1) and (4.4.2) then reduce to
^ 2 2 0 - ^ +^ = 0, (4.4.3)
a2? a?
oz oz
Equation (4.4.4) gives
Fig. 4.4.2. A spherical drop of a long-pitched cholesteric liquid crystal showing the
characteristic/-line (from Robinson(62)). The structure of this defect was explained
by Frank and Pryce(61).
The cholesteric material was then doped with a small quantity of a non-
mesomorphic epoxy compound, Lixon, which lowered the cholesteric-
isotropic transition temperature and gave rise to a broad two-phase
region. Because the glass plates have greater affinity for Lixon than for the
liquid crystal compound, the cholesteric drops were surrounded on all
sides by the isotropic phase. With thick cells, spherical drops with the
characteristic /-line of strength 2 were formed (fig. 4.4.2). In thin cells
(~ 8 jum thick) flattened drops were obtained in which the central portion
266 4. Cholesteric liquid crystals
had an essentially planar structure with the helical axis normal to the flat
region and the /-line was confined to the periphery. Since the anchoring
energy at the cholesteric-isotropic interface may be expected to be
negligible, these flat drops proved to be most suitable for studying the
phenomenon. In principle, any transport current can produce a cross-
coupling effect and hence a DC electricfieldwas used for convenience. At
2 V DC, the dark brushes emanating from the /-line became curved, and
then the whole structure started to rotate, apparently without any further
distortion. Fig. 4.4.3 shows the photographs of the rotating drops, which
can be seen to be closely similar to Lehmann's diagrams reproduced in fig.
4.4.1. Systematic observations on a number of drops established the
following results: (a) all the drops rotate in the same direction for a given
sense of the field: the right-handed helix has an anticlockwise rotation
when viewed along the field direction. When the voltage is reversed, the
curvature of the dark brushes and the sense of rotation of the structure are
reversed; (b) the angular velocity increases linearly with applied voltage up
to ~ 3.5 V, beyond which the structure of the drop changes and the
rotational velocity becomes a non-linear function of the applied voltage
(fig. 4.4.4); (c) nematic drops do not rotate under the action of E; (d) when
the handedness of the helix is reversed, the angular velocity also reverses
sign for any given sense of the field E; (e) the angular velocity does not
depend on the radius of the drop, showing that it is a rotation of the
structure rather than a rigid body rotation of the drop as a whole. All these
observations are in conformity with the theory. Though the angular
velocity was approximately the same for all drops, some drops which had
dust particles attached to them rotated with a lower velocity. For the sake
of completeness, even these values have been plotted in fig. 4.4.4. The
extrapolated angular velocity becomes zero for V « 1.9 V (fig. 4.4.4). The
last point indicates that the DCfieldis totally screened up to « 1.9 V and
that the redox potential of at least one of the components in the mixture is
about 1.9 V.
For a defect-free planar structure, the angular velocity in the presence of
an electric field E is in analogy with (4.4.7),
0.6 D
OX
0.5 -
0.4 - A
0.3 -
0.2 -
0.1
J^ ? T 1 . 1
1 2 3 4 5
Voltage (V)
Fig. 4.4.4. The rotational velocity against applied voltage. The different symbols
denote measurements on different drops. The angular velocity was noticeably less
for drops which accidentally had dust particles attached to them (see the circles in
thefigure),but only the data for the fastest rotating drops were considered in the
calculations. Between 3.5 and 5 V there was visible disturbance within the drop and
measurements were not possible. At 5 V and above, the drop regained a uniform
texture. (After reference 60.)
Using the slope of the linear part of the |o>| against |E| curve (fig. 4.4.4),
and putting Xx = 0.7 P, it was found that |vE| = 0.28 cgs, and vE/q =
— 2 x 10~5 cgs for the material used in the experiment.
105
Is
1O4
103
102
1 Cholesteric r
Isotropic
lO"1
I
io- 2 ^ - — - ^
1 I 1 I i l l 1
100 110 120 130 140
Temperature (°C)
Fig. 4.5.1. Apparent viscosity of cholesteryl acetate versus temperature. Capillary
shear rate (s"1): open inverted triangle, 10; cross, 50; open square, 100; filled
inverted triangle, 1000; filled square, 5000. Rotational shear rate (s"1) open
triangle, 104; open circle, high shear rate and normal liquid behaviour. (After
Porter, Barrall and Johnson.(65))
0.30 -
0.28
0.26
0.24
fe)
0.22
1.5 V-
1.0
0.5
10 15 20
lAP 2 (10 6 cm- 2 )
Fig. 4.5.3. Threshold of shear rate above which the fluid becomes non-Newtonian
plotted against 1/P2, where P is the undistorted value of the pitch. The arrows
represent the upper and lower limits of the shear rate (see fig. 4.5.2). (After Candau
66
et
270 4. Cholesteric liquid crystals
where dp/dz is the pressure gradient. The quantity of fluid flowing per
second is
Q = _nR\dp/dz)
/ X
/app = \ • (4.5.1)
0. (4.5.4)
2
In the above equations 9 x = d9/dx, 9 xt = 9 ^/8x9z etc. Similarly, under
the same approximations, (4.3.2) becomes
P,x = -%(»*+Hz)+ vAqSCwtX, (4.5.5)
py = [M.C'-^ + lfi.iC'-S^qw^ (4.5.6)
P,z = S^ik^-k^qS-cp^ik^S^k^C^q-y^k^q
-^, I (A; 22 + fc33)^C + > ^ 4 + ^6-/u2)C2]. (4.5.7)
From (4.5.2) and (4.5.3) we get
^ - p . , = 0. (4.5.9)
272 4. Cholesteric liquid crystals
We make a 'coarse-grained' approximation and replace |[// 4 + (JU5—JU2) C2]
by an average value if and rewrite (4.5.9) as
nw.xx + n*i42-P.z = 0. (4.5.10)
A solution of (4.5.10) with the boundary conditions w(±h) = 0 is(68)
Q= w(x)dx = 2 w(x)dx
/app
3Q 3[1
Taking 2h = 100 jum and P= 1 jum, the velocity attains 0.99 of the
maximum value within a thickness of 0.5 //m of the boundary. Thus in all
practical situations the velocity profile is flat over most of the region
between the plates and
* a p p « - ^ (4.5.14)
Poiseuille flow
In cylindrical polar coordinates, we seek solutions of the form
nr = cos(qz—y/ + <p)cos8, n¥ = sin(qz—y/ + (p),
nz = sin 0,
where 9 and (p are functions of r, y/ and z. Considering very small pressure
gradients we obtain to a first order in 6 and (p,
^ ^ w q \ (4.5.15)
A =
~ffIQ(KRY
and
where R is the radius of the capillary. The quantity of liquid crystal flowing
per second
KI0{KR)\
where Ir is the modified first order Bessel function of the first kind.
Hence
/aPP 8{ x _ [2ii(KR)/KRI0(KR)]}'
Again, in practical situations the velocity profile is flat except very near the
boundary and
which is identical with (4.5.1). Thus Helfrich's idea of permeation along the
helical axis of a cholesteric can be justified in terms of the Ericksen-Leslie
equations.
274 4. Cholesteric liquid crystals
and
H2 = (2//x sin2 6 + jus + ju6) cos2 6.
From (4.3.4) we obtain
\dz/
d^?
2 = 0 (4.5.26)
dz
and
2 2 sin#cos#-;—al = 0, (4.5.27)
dz2 d# dz dz dz
where
Q = ( ^ _|_ ^ 2 cos20)/(/f 1 + /f2)
and
P = (A 2 -.^ s i n ^ c o s ^ / ^ .
Leslie assumed the following boundary conditions:
_ a
17app
~ K/2A
2
(4.5.29)
276 4. Cholesteric liquid crystals
1.2
l.l
100 1000
Fig. 4.5.5. Theoretical variation of the apparent viscosity //app with pitch P = 2n/q
for flow normal to the helical axis of a cholesteric (or twisted nematic) at low shear
rates. Plot ofrjapp(q)/rjapp(0) versus P for twisted PAA. The separation between the
plates = 100 jum. The horizontal dashed line corresponds to f] (co)/rfapp(0). (After
ref. 70.)
3.7
3.3
2.9
2.5
I
'50 51 52 53 54
T(°C)
Fig. 4.5.6. Evidence of oscillatory behaviour in the variation of the apparent
viscosity with temperature in a cholesteryl chloride-cholesteryl myristate mixture
in the neighbourhood of the nematic point 7^ (see fig. 4.1.16). (After Bhattacharya,
Hong and Letcher.<72))
4.6 Distortions of the structure by external fields 277
Detailed analytical and numerical calculations have been presented by
K i n i (7o,7i) w h e n a i s
It is seen that for pitch values of the order of the sample thickness, ?/app
should exhibit oscillatory behaviour with varying pitch because of the term
sin qh/qh in (4.5.30). A representative theoretical curve is presented in Fig.
4.5.5. This prediction has been verified qualitatively. (72) Measurements of
the apparent viscosity on the cholesteryl chloride-cholesteryl myristate
mixture, whose pitch, as we have seen earlier, is sensitive to temperature
(fig. 4.1.16), showed evidence of oscillations as the temperature was varied
(fig. 4.5.6).
Often, in practical cases, qh is so large that sin qh/qh is negligibly small
and ?/app approaches a maximum limiting value which is independent of the
pitch or gap width. This value is several orders of magnitude less than that
for flow along the helical axis and is comparable to that for a nematic.
When a is sufficiently large
q> = 0 and 0 = 00 = i c o s - 1 ^ / ^ ) ,
i.e., the helix is unwound completely except in a layer of thickness of the
order of the q~x at the boundaries, and
which is again independent of the pitch or gap width. This lower limit is
reached when a & k22 q2 or more. All these predictions are in qualitative
agreement with the observations of Candau et #/.(66) (see fig. 4.5.2).
>H >H
Taking the helical axis to be along z, H = (H, 0,0) and n = (cos cp, sin q>,
0), the free energy of the system is
X H sin COS 9 =
* * f
which yields
z = 2AZK(A),
where
22/
and
72
K(A) =
is the complete elliptic integral of the first kind; A is a constant which can
4.6 Distortions of the structure by external fields 279
1.5
1.0
H/Hc
Fig. 4.6.2. Dependence of the pitch P on the magnetic field strength H in PAA
mixed with a small quantity of cholesteryl acetate. Curve represents the theoretical
variation predicted by de Gennes's equation (4.6.1). (After Meyer.(76))
where
rnr. 4
=2 ?)2 dcp = —
Jo A
and
E(A) =
t
V///////////////////////A
W7/7///////////////////.
2*
Fig. 4.6.3. Deformation of a planar structure due to a magnetic field acting along
the helical axis of cholesteric liquid crystal composed of molecules of positive
diamagnetic anisotropy. A similar deformation superposed in an orthogonal
direction results in the square-grid pattern (see fig. 4.6.4). (Helfrich. (79))
(4.6.1)
and
(4.6.2)
2E(A)'
When l, E(A) -> 1, K(A) -> oo and H-> Hc, so that h = n/2 or
Hc = Inqo(k22/XJK (4.6.3)
which is the critical field at which the structure becomes nematic.
The variation of pitch with magnetic field strength predicted by (4.6.1)
has been verified experimentally (76'77) (fig. 4.6.2). It has also been confirmed
that Hc is inversely proportional to Po the pitch of the undistorted
structure.(77) It turns out that with the usually available magnetic field
strengths, the experiment is conveniently performed only with cholesterics
of relatively large pitch. For example, in a typical measurement using
nematic PAA doped with a small amount of cholesteryl acetate Hc was
8.3 kG for PQ = 26 jum.
4.6 Distortions of the structure by external fields 281
4.6.2 Magnetic field along the helical axis: the square grid pattern
We next examine the effect of a magnetic field acting along the helical axis
of a cholesteric film having a planar texture. If / a > 0 and boundary
constraints are absent, there is a possibility of a 90° rotation of the helical
axis because \{X\\+X±) > X±- I£ o n t n e other hand, boundary effects are
such as to maintain the orientation of the helix, an expected type of
deformation is for the director at every point to be tilted towards the field,
i.e., a conical distortion/ 75 ' 78) However, it was pointed out by Helfrich(79)
that yet another type of deformation can set in, viz, a corrugation of the
layers (fig. 4.6.3). This has since been confirmed experimentally using both
magnetic(80) and electric fields/81'82) and takes place at a much lower
threshold. It results in the so-called square grid pattern (fig. 4.6.4), the
theory of which was first proposed by Helfrich(79) and subsequently
elaborated by Hurault. (84) We shall discuss first the magnetic field case.
For the unperturbed cholesteric
where we take z normal to the film. For small perturbations we may put
M\ , • * ?>d( n d<p\
#- = \FdV.
Now
Fig. 4.6.4. The square grid pattern in a cholesteric liquid crystal induced by (a) a
magnetic field and (b) an electric field. (Rondelez.(83))
4.6 Distortions of the structure by external fields 283
where (ffm dQ
A = - (fc u sin 2 q0 z + fc33 cos 2 q0 z) ( ^ + q0 —
0
dx
(4A7)
and
H
8>
c)2Q
O A- rvn wS 2 ^ 0 Z—r. (4.6.8)
oz oz
K<kx<<lo (4.6.10)
and we shall assume this to be true in what follows. The condition
• = 0 yields
- ^ i i ) ^ > i = 0, (4.6.11)
Kl^ql <P, - q0 K 0O)+K*S3 - *n) ( ^ ^o - q» K e0)+ife+*n) /c2 ^ = o,
(4.6.12)
where we make a 'coarse-grained' approximation, i.e., take into con-
sideration only the slowly varying parts of A. The minimum energy density
O 00 ~ K <Po) (*11 + ^
-ko K <Pi(2k22+^33 - ^11)] cos K z s i n K x- ( 4 - 6 - 13 )
284 4. Cholesteric liquid crystals
From (4.6.11) and (4.6.12) we get
^i^Z^o (4.6.14)
and
1
ffo ^o ~ \i(ic +L. \ + k ^±\±(k +k } - (k k ^*1* ~ 1
\ (4.6.16)
where P is the local value of the pitch. We know that the twist energy of
deformation of the cholesteric structure can be written in terms of the pitch
as \k22(q — q0)2 where q = 2n/P and q0 = 2n/P0. Comparing this with the
first term on the right-hand side of (4.6.18), it is clear that
B*k22q*. (4.6.19)
In order to evaluate K, one may use the following argument. Suppose that
4.6 Distortions of the structure by external fields 285
the film is rolled up into a cylinder, i.e., the screw axes are oriented radially
about the cylinder axis and the layers form coaxial cylinders. In cylindrical
coordinates, the components of the director are now
nr = 0, riy = cos 0(r), and nz = sin 6{r)
and the local free energy is given by
sin0cos0\ 2 1f cos 4 0 , „X
+
j ^-^^- (4-6.20)
The optimum value of 6{r) compatible with the periodicity 6{r) = 6{r + Po)
corresponds to
d0 1 . . .
—- = # n + - s m 0 c o s 0 .
dr r
where
(£)V (4-6.24)
^ a = ^ ~x± being the anisotropy of diamagnetic susceptibility. Applying
the condition dF/du = 0 and using (4.6.22), (4.6.23) and (4.6.24)
= 0. (4.6.25)
Thus H^oo when kx^co as also when kx->0. This is because the
perturbation u is made up of two components, bend and twist: kx -> oo
286 4. Cholesteric liquid crystals
excites the bend mode while kx -> 0 excites the twist mode whose amplitude
diverges in the limit. The optimum wavevector corresponds to an
admixture of both modes and is given by
8
7 4 ^ 2 2 2 / 2 tA<LK\
kx = — ^ q\ k\, (4.6.26)
or
kxK(Pod)-K (4.6.27)
and the threshold field
1 i
H^ = —(6k 22 k 33 ) 2 q 0 k z , (4.6.28)
/a
or
77HocOP0 </)-". (4.6.29)
It is interesting to note that this threshold field is lower than that for a
conical distortion or that for cholesteric-nematic (unwinding) transition.
For a conical distortion, the theory is closely similar to that discussed in
§3.4.2 and has been treated by Leslie (78); the critical field is given by
HI = —(k, J
/a
G ~ A ^ 2 2 V/0>
Aa
Jx = °±*Ex-(°\\*-Ort)E^ (4.6.30)
which should be zero (V-J = 0). Here Eo is the applied field and Ex that
caused by the Carr-Helfrich mechanism. Therefore
OX (Tl
, c 4v
An
( £ E) = An e.
^ (4.6.32)
An -°\E0 U^
from which it follows that the contribution to the vertical force is
ox <+n alh ox
_87T 3 <7 | | +a 1
)-\ (4.6.34)
where crn and aL are the conductivities parallel and perpendicular to the
288 4. Cholesteric liquid crystals
preferred molecular direction and el{ and e± are similarly defined. It may be
noted here that we have neglected the contribution of the viscous torque
altogether. This is because, as remarked earlier, fluid motion takes place
only by permeation, and, moreover, the distortions are infinitesimal and of
such long wavelength {kx <4 q0) that the effect of shear flow will be very
small indeed. The dependence of the spatial periodicity of the pattern and
the threshold field on d and Po is similar to the magnetic field case, and is
borne out by experiments/ 81 ' 8285)
Hurault(84) has extended the treatment to AC fields. The method is
somewhat analogous to the one discussed in §3.10 for nematic instabilities
and leads, in the conduction regime, to the following threshold for
distortion:
where
where P(x) = 7Va(x) •F(x) is the polarization (or the dipole moment per
unit volume) at x, a is the polarizability of the molecule at x, G(x — x', k0)
a tensor representing the field at x due to a dipole at x', k0 the wavevector
of the incident radiation, v the volume of the Lorentz cavity which is not
supposed to contribute to the effective field and V the total volume.
290 4. Cholesteric liquid crystals
35
40
35
30
25
I 20
o 60.5 61.0 61.5 62.0 62.5 63.0 63.5
"S3 15
Temperature (°C)
Writing
) + <SP(x).
where Po is the polarization in the absence of correlations and SP
a small correction term,
2
f dV<<5a(x)-G-<Ja(x')>-F(x'),
J V
where n is the refractive index of the isotropic phase, a the mean molecular
polarizability and aa = a,, — a ± the polarizability anisotropy. Expressing
the integral in terms of the Fourier components,
0 + q) •<s*(q) •s(q)> J.
4.7 Anomalous optical rotation 291
or an optical rotation
The rotation exists because of the correlations (s%asyfiy which are non-
vanishing in the case of a cholesteric. The averages may be evaluated on
the basis of de Gennes's model(89) (see §2.5). To allow for the non-
centrosymmetric ordering in the cholesteric, we include an additional term
of the form s • V x s in the free energy of the isotropic phase
/? c = /5 N + 2 t f 0 L ' ^ ^ - i f e , (4.7.1)
oxy
where FIN is the free energy per unit volume in the isotropic phase of a
nematic given by (2.5.15) and (2.5.22), q0 is a pseudo-scalar and L is a
constant. The average can then be worked out. For example
292 4. Cholesteric liquid crystals
BPIII y
BPII
Disordered
-
* = = -- BPI
Helicoidal
Inverse pitch
Fig. 4.8.1. Schematic phase diagram, showing the three experimentally observed
blue phases (BP).
where
A = a(T-T*),
l\ = LJA,
Fig. 4.8.2. (a) Faceted single crystals of BP I in equilibrium with the isotropic phase
(58 wt% mixture of cyano-4-methylbutylbiphenyl (CB15) in nematic ZLI 1840 of
Merck). (From Cladis, Pieranskio and Joanicot(95).) (b) Optical Kossel diagram of
BP I, {110} direction, X = 5290 A (42.5 wt% mixture of CB15 in nematic E9 of
BDH). (From Cladis, Garel and Pieranski.(96))
293
(a)
Fig. 4.8.3. Unit cells of BP disclination lattices. O2 is simple cubic, O5, O 8 + and
O8 — are body-centred cubic. The tubes represent disclination lines whose cores are
supposed to be isotropic (liquid) material. (From Berreman.(98))
Fig. 4.8.4. A representative phase diagram calculated from the Landau theory.(110)
The normalized ordinate t is proportional to T— T* and the normalized abscissa K
is proportional to 1/P, where P is the cholesteric pitch. The diagram illustrates how
different BPs can occur by changing the chirality. (From Crooker.(104))
where A is the coefficient of the cubic anharmonicity term, (106) a>0 the
angular frequency and / the moment of inertia of the molecule. Thus the
pitch P (oc 1/(6}) may be expected to decrease slightly with temperature.
However, in many substances the rate of variation is extremely high. It is
now established that if the cholesteric phase is preceded by a smectic phase
at a lower temperature, the pitch increases very rapidly as the sample is
cooled to the smectic-cholesteric transition point (see fig. 5.5.3).
The strong temperature dependence of the pitch has practical appli-
cations in thermography, as was first demonstrated by Fergason. (107108)
The material has to be so chosen that the pitch is of the order of the
wavelength of visible light in the temperature range of interest. This is
achieved by preparing suitable mixtures. Small variations of temperature
4.9 Some factors influencing the pitch 297
are shown up as changes in the colour of the scattered light and can be used
for visual display of surface temperatures, (109) imaging of infrared(110) and
microwave(111) patterns, etc.
O H
II I
N = C — Q — C H = N — ® — C H = C H — C —O— C —CH 2 CH 2 CH 3
I
X
X = H, nematic; X = D, cholesteric.
The C—H and C—D bond lengths are the same, 1.085 A,(129) when one
takes into account the anharmonicity of the vibrations. Thus it would seem
that steric effects are not essential for the helical arrangement.
5
Smectic liquid crystals
300
5.7 Classification of the smectic phases 301
Smectic A(SA) Liquid-like layers with the molecules upright on the average
(fig. 1.1.5(a)); negligible in-plane and interlayer positional
correlations. Thus the structure may be described as an
orientationally ordered fluid on which is superimposed a one-
dimensional density wave. A number of polymorphic types of
smectic A have been discovered (see §5.6).
Smectic B(SB) Two distinct types of smectic B have been identified: {a)
Crystal B - three-dimensional crystal, hexagonal lattice with
upright molecules. Though the structure has three-
dimensional long-range positional order, the interlayer
ordering is extremely weak energetically because of the weak
interlayer forces, (b) Hexatic B - stack of interacting 'hexatic'
layers with in-plane short-range positional correlation,
negligible interlayer positional correlation and long-range
three-dimensional six-fold bond-orientational order (see fig.
5.7.1). Here, the term 'bond' signifies the line joining the
centres of mass of the nearest neighbours.
Smectic C(SC) Liquid-like layers, as in SA, but with the molecules inclined
with respect to the layer normal (fig. 1.1.5 (/?)).
Smectic C*(SC*) Chiral S c with twist axis normal to the layers.
Smectic D(D) Cubic lattice with about 103 molecules per unit cell. (46) The
detailed molecular arrangement is not known, but is generally
assumed to be of the micelle type. Thus this phase should
probably be labelled as ' D ' rather than 'Smectic D \ At
present only four compounds are known to exhibit this phase,
4'-n-hexadecyloxy- and 4 /-n-octadecyloxy-3 /-nitrobiphenyl-4-
carboxylic acid and two similar acids with CN replacing NO 2 .
Interestingly, D occurs between S c and SA or between S c and
the isotropic phase. The manner in which such a structural
rearrangement takes place is yet to be resolved.
Smectic E(S E) Three-dimensional crystal, orthorhombic with interlayer
herringbone arrangement of the molecules. (2)
Smectic F(SF) C-centred monoclinic (a > b) with in-plane short-range
positional correlation and weak or no interlayer positional
correlation: tilted hexatic.
Smectic F*(SF.) Chiral SF with twist axis normal to the layers.
Smectic G(SG) Three-dimensional crystal, C-centred monoclinic (a > b).
Smectic H(S H) Three-dimensional crystal, monoclinic (a > b), herringbone
structure.(2)
Smectic H*(SH*) Chiral SH with twist axis normal to the layers.
Smectic I(ST) C-centred monoclinic (b > a), tilted hexatic with slightly
greater in-plane correlation than SF.
Smectic I*(SIA) Chiral Sz with twist axis normal to the layers.
Smectic J(ST) Three-dimensional crystal, C-centred monoclinic (b > a).
Smectic J*(SJ#) Chiral Sj with twist axis normal to the layers.
Smectic K(SK) Three-dimensional crystal, monoclinic (b > a), herringbone
structure.(2)
Smectic K*(SK*) Chiral SK with twist axis normal to the layers.
302 5. Smectic liquid crystals
3cos 2 0 1 2 -l __,.
^ — , (5.2.1)
_ /3cos2fl-l\
5.2 Extension of the Maier-Saupe theory to smectic A 303
1.0
s
• — •
— - —
— - . _
^ ^
0.5 -
I 1
4 - - - '20
< o
opi
tic
is - 15
3 -
B
on
§ 2 - 10
>
1 - - 5
3 cos2 0 - 1
o = /cos(27iz/d)f : (5.2.6)
where the angular brackets denote statistical averages over the distribution
fv The parameter s defines the orientational order, exactly as in the
Maier-Saupe theory, while a is a new order parameter which is a measure
of the amplitude of the density wave describing the layered structure. The
last two equations can be solved numerically to obtain the following types
of solutions:
(i) o = s = 0 (isotropic phase)
(ii) a = 0, s =1= 0 (nematic phase)
(iii) a H= 0, s ^F 0 (smectic phase).
304 5. Smectic liquid crystals
The free energy of the system can be calculated in the usual manner:
F=U- TS,
where
(5.2.7)
and
1
-TS = NV0(s2 T dz T d(cos 0)/^, cos 0)1.
Jo Jo J
(5.2.8)
The two parameters characterizing the material are Vo, which determines
5.2 Extension of the Maier-Saupe theory to smectic A 305
1.0
0.5
)I 1
<
4
~
-
o /
1 .a
a,
o
- 20
•s
- 11 //
o? 3 - 15
I
- 10
1 - - 5
0
0.8 0.9 1.0
Reduced temperature
Fig. 5.2.3. Order parameters s and cr, entropy S and specific heat cv versus reduced
temperature for a = 0.6 showing a second order smectic A-nematic transition and
a first order nematic-isotropic transition. (After McMillan. (7))
Isotropic /
1.0
Nematic
/ Smectic A
0.9 -
Transition temperature
\. Isotropic
Nematic\.
0.8 - or \ ^ ^
cholesteric^^"^^^^-^^
/ Smectic A
I i 1
Alkyl chain length
0.7
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2
Model parameter a
Fig. 5.2.4. Phase diagram for theoretical model parameter a. Inset: typical phase
diagram for homologous series of compounds showing transition temperatures
versus length of the alkyl end-chains. (After McMillan.(7))
K12(r12,cos012) = _ (5.2.9)
1.0
0.5
Fig. 5.2.5. Smectic A-nematic (or cholesteric) transition entropy versus ratio of
transition temperatures TAN/Tm. Solid line is theoretical curve taken from fig.
5.2.4; open circles are experimental values of Davis and Porter (MoL Cryst. Liquid
Cryst., 10, 1 (1970)); open triangles are data of Arnold (Z. Physik. Chem. (Leipzig),
239, 283 (1968); ibid., 240, 185 (1969)). (After McMillan.(7))
~ 200
(a)
•S 100
Smectic A Isotropic
I
60 70 80 90
Temperature (°C)
Fig. 5.2.6. Measured intensity of X-ray scattering at the Bragg angle versus
temperature for cholesteryl myristate. The dashed line is the calculated diffuse
scattering and fluctuation scattering contribution. The full lines represent the
theoretical curves for the total intensity due to Bragg, diffuse and fluctuation
scattering derived from (a) the simpler model potential and (b) the refined one. The
theoretical intensity has been adjusted to be equal to the experimental value at the
lowest temperature. (After McMillan. (11))
308 5. Smectic liquid crystals
0.8
0.6
(a)
0.4
0.8
Z. 0.6
0.4
0.8
0.6
(c)
0.4
same as those obtained with the simpler model but there are some
quantitative improvements. A number of other refinements and extensions
have been proposed, (1221) but McMillan's model remains the simplest
which brings out all the qualitative features of the A-N and A-I transitions.
A direct method of studying the translational order (or the amplitude of
the density wave) is by measuring the intensity of the Bragg scattering from
the smectic planes. McMillan's experimental results on cholesteryl myr-
istate(11) are shown in fig. 5.2.6 and as can be seen there is excellent
agreement with the refined model. The X-ray intensities reveal an
appreciable pretransitional smectic-like behaviour in the cholesteric
(nematic) phase. This aspect of the problem will be dealt with in a later
section.
The orientational order parameters in the smectic and nematic phases,
studied by magnetic resonance and other techniques also follow the
5.2 Extension of the Maier-Saupe theory to smectic A 309
1.5 -
N==C
O O-C 8 H 17
1.0
0.5
1.2 -
90 °C
0 J
50 60 70 80 90 100 110
Temperature T (°C)
Fig. 5.2.8. Temperature dependence of the orientational order parameter s
determined by 14 N quadrupolar splitting measurements for CBOOA. The inset
shows the discontinuity in slope at the smectic A-nematic transition. (After
Cabane and Clark. (23) )
i-dr (5.3.1)
nTTTTTTT
Fig. 5.3.1. Flexibility of smectic A layers: only such deformations as preserve the
interlayer spacing take place readily.
I n , l III 1 , 1 , 1 , 1 ,
Fig. 5.3.2. A diagram depicting the molecular arrangement in (a) the nematic and
(b) the smectic A phases. In the nematic phase the molecules are randomly
distributed so that any horizontal line intersects the same number of molecules. In
the smectic A phase the number of molecules intersected by a line varies sinusoidally
with the position of the line, being 50 per cent more than the average at the
positions indicated by the arrows and 50 per cent less than the average half way
between. This represents a density wave whose amplitude is 50 per cent of the mean
density, which is far greater than what actually occurs near the A-N transition in
a real system. (After Schaetzing and Litster.(26))
kBT L (5.3.8)
For the crystalline lattice, this is the familiar Debye-Waller factor. In the
case of smectic A, one gets from (5.3.4)
(5.3.10)
This was evaluated by Caille (28): for d <^ \r\ < L, the correlation functions
for the two principal directions vary as
n = ~~zi, (5-3.12)
lK\qz-q0\-*+i, q± = 0, (5.3.13)
Ioc\q±\-*^, qz = 0, (5.3.14)
where
q0 = In Id.
10°
: / \
6
10"1 \\ v
M \
\ \ \
ry = 0.38
A
\\ V
O
^ = 0.17
\\
10"2
1 1
\ \ 1 1 I
-1
Fig. 5.3.3. X-ray scattering intensity profile from the smectic A phase of 80CB at
two reduced temperatures, ( r A N - T)/TAN = 9 x 10"4 (filled circles) and 10"6 (open
circles). The dashed line is the experimental resolution function as would be seen if
smectic A had true long-range order. The full lines are the best fits of the theoretical
line shape \qz — qo\~2+n folded with the resolution function. The values of rj so
obtained agree with those calculated from (5.3.12) using experimentally determined
values of q0, B and k1±. (Als-Nielson et al.(m)
where kz = n/L and L is the sample thickness, and evaluating the average
free energy, one obtains
F =- (5.3.15)
where
X= (5.3.16)
is a characteristic length of the material of the order of the layer thickness.
Proceeding as in §4.6.2, the optimum value of the distortion wavevector is
is, however, rather large compared to that for cholesterics. For example,
taking k = 20 A and L = 1 mm, Hc ~ 50 kG, and thus far no experimental
studies of this effect appear to have been carried out.
The same type of distortion can be achieved more easily by mechanical
means, i.e., by increasing the separation between the glass plates (3132) (fig.
5.3.4). In the absence of a magnetic field, and taking u to be independent
of y, (5.3.3) reduces to
(5.3.18)
However, in the present case we note that a bending of the layers alters the
effective layer spacing along z and therefore makes a second order
contribution to the layer dilatation in that direction. Hence (5.3.18) needs
a correction term:
V/////////////////7/A
Y/////. 777/77//A
Y////X
277/*, .
Fig. 5.3.4. The Helfrich deformation in a smectic A film subjected to a mechanical
dilatation A.
50 100 150
k T
» — (5.3.23)
<53 25)
-
is quite small; consequently, in certain geometries, e.g., when a homeo-
tropically aligned sample is held against an extended source of light and
viewed normally, the medium will not appear very turbid.
Strictly speaking, one should take into account the contributions of k 22
and k33, since the layers are assumed to be compressible. Following the
procedure outlined in §3.9, the fluctuations may be decomposed into two
modes, and choosing the wavevector q in the xz plane, one gets the general
expressions(34)
,,*„ , , s = kBT[l+(B/D)(qJqLn
xl? l j
^ k q i + k^ + iB/DHD +k q l +k ^ D i q J q r
Fig. 5.3.6. Distortion caused by an irregularity on the glass surface. The bending of
the layers can be relaxed only by compression, which requires considerable energy,
so that the surface distortion extends to appreciable depths inside the specimen.
or
C = (V)
(whereas in nematics, £ ~ q x ). These long-range static undulations give
rise to an intense scattering of light which completely swamps that due to
the thermal fluctuations. Indeed in the first experiments*36'37) it was the
static effects that were observed as was confirmed by a temporal analysis of
5.3 Continuum theory of smectic A 319
105 r-
104
103
77 °C
102
§
S 10
79 °C
74 C
0.1 I
10" io 101 102
1
Shear rate (s" )
Fig. 5.3.7. Apparent viscosity versus shear rate for cholesteryl myristate at different
temperatures: full line, smectic A; dashed line, cholesteric; chain line, isotropic.
(After Sakamoto, Porter and Johnson.(41))
Aodz
so that
B = B0-(2C20/A0) (5.3.29)
and (5.3.28) reduces to the simpler form (5.3.3) assumed previously.
If vt is the velocity of the particle, the equation of motion is
where gt is the force on the layers and t'n the viscous stress tensor which, in
contrast to the nematic case, is assumed to be symmetrical and dependent
on the velocity gradients only. In the problem under consideration we have
(5.3.31)
and
g = -SF/Su. (5.3.32)
The force g normal to the layers will be associated with permeation effects.
The idea of permeation was put forward originally by Helfrich(40) to
explain the very high viscosity coefficients of cholesteric and smectic liquid
crystals at low shear rates (see figs. 4.5.1 and 5.3.7). In cholesterics,
permeation falls conceptually within the framework of the Ericksen-Leslie
theory(42) (see §4.5.1), but in the case of smectics, it invokes an entirely new
mechanism reminiscent of the drift of charge carriers in the hopping model
for electrical conduction (fig. 5.3.8).
The rate of entropy production may be written as (see §3.1.4)
TS=t'ndij+g(u-vz), (5.3.33)
where dtj = \{v{ j + Vj t), and (u — vz) describes the permeation. Treating t'n
5.5 Continuum theory of smectic A 321
Fig. 5.3.8. Helfrich's model of permeation in smectic liquid crystals. The flow takes
place normal to the layers in a manner similar to the drift of charge carriers in the
hopping model for electrical conduction.
10 --
A
\
<»\
L
\
\
| \
\
J \
5 T
T ^ ^ f
I 1 1
10 15 20 25
q2 (108 cm- 2 )
Fig. 5.3.9. Damping rate of the undulation mode in the smectic A phase of CBOOA
determined by laser beat spectroscopy for two different sample thicknesses, 200
and 800 /zm. Solid lines represent the theoretical curves calculated from (5.3.40)
and (5.3.41). (After Ribotta, Salin and Durand.(38))
and g as fluxes and dtj and (u — vz) as forces, and expanding t'n one obtains
the following relations:
For small q, the last term may be neglected (except very near the boundary,
but we shall ignore the boundary layer). This results in a purely damped
mode whose relaxation rate is
1 k n2
l
L= h±3_. (5.3.39)
T rj
More generally, taking into account the thickness L of the sample one may
write
y and 6 being the independent variables. This leads to the secular equation
co{\pco2 - (Bo + Co) q% (po? - Ao q\) -(Au + Co) q\{paf + Co q\)} = 0.
(5.3.45)
We are interested here in propagating modes and ignore the case co = 0.
Solving for the velocities c = co/q, we get
c\ + c\ = p-\AQ cos2 <p + (Ao + Bo + 2C0) sin2 p], (5.3.46)
2 2 2 2 2 2
c c =/7- (^0^0-C )sin cos ^, (5.3.47)
where cp is the angle between q and its projection on the layer.
Ultrasonic velocity measurements have been reported on oriented
smectic A samples of 4,4/-azoxydibenzoate. The first studies by Lord(43) for
two values of (0° and 90°) established the anisotropy of the velocity of
propagation. Subsequently, Miyano and Ketterson(44) investigated the
angular dependence of the sound velocity and from a least squares fit with
(5.3.45) were able to determine the elastic coefficients Ao, Bo and Co. By
analogy with the elasticity theory of solids(45), we may write
C —C — —C
^33
Their estimates show that Ao is much larger than Bo or Co (fig. 5.3.10). This
enables us to give a simple physical interpretation of the two branches
324 5. Smectic liquid crystals
1.6 r
1.5
1.4
110 115 120
Temperature (°C)
0.3 r
0.2
0.1
i A
8- -8-
0 I I
no 115 120
Temperature (°C)
Fig. 5.3.10. Temperature dependence of the elastic constants of the smectic A phase
of diethyl 4,4/-azoxydibenzoate determined by ultrasonic velocity measurements:
open circles, 2 MHz; filled circles, 5 MHz; triangles, 12 MHz; crosses, 20 MHz.
(After Miyano and Ketterson.(44))
described by (5.3.46) and (5.3.47): the density and layer oscillations are, in
effect, uncoupled. Hence one of the branches corresponds to the normal
longitudinal wave whose velocity can be seen from (5.3.46) to be
Cl « (AJp)\ (5.3.48)
which is practically independent of the direction of propagation. The other
branch corresponds to changes in the layer spacing, without appreciable
density changes and may be compared with the phonon branch in
superfluids known as second sound.m) The velocity of this mode
c 2 « (B0/p)* sin q> cos <p (5.3.49)
is strongly orientation dependent. It becomes zero for propagation along
5.3 Continuum theory of smectic A 325
the layers as well as perpendicular to them. When the wavevector is
parallel to the layers (qz = 0), it becomes the highly damped undulation
mode which we have already examined in detail. When q is normal to the
layers permeation effects set in and the wave is again strongly damped.(39)
Neglecting density changes for this mode, it is clear from (5.3.43) that for
q along z,vz = 0. Thus from (5.3.35)
u = vpg (5.3.50)
or using (5.3.24)
u = vpBd2u/dz2. (5.3.51)
Therefore, when the wavevector of second sound is normal to the layers, it
becomes a purely dissipative mode with a relaxation rate
\/T = vvBq\ (5.3.52)
Furthermore, second sound is a critical mode, i.e., its velocity goes to zero
as r - TAN.
A direct confirmation of the existence of these two branches has been
found by Liao, Clark and Pershan(47) from their Brillouin scattering
experiments on a monodomain sample of ^-methyl butyl /?((/?-methoxy-
benzylidene)amino) cinnamate. This compound shows the nematic,
smectic A and smectic B phases. Choosing both the incident and the
scattered light to be polarized either as ordinary or extraordinary waves,
they observed two peaks corresponding to the two modes, the angular
dependence of which is in excellent agreement with the theory (fig. 5.3.11).
1.5
1.0
0.5 (a)
0
1.0 2.0
2.0
1.5
1.0
(b)
0.5
0 1.0 2.0
Sound velocity (105 cm s"1)
Fig. 5.3.11. Dependence of the sound velocities on the polar angle q> from Brillouin
scattering experiments on ^-methyl butyl /?((/>-methoxy-benzylidene)amino) cin-
namate. (a) Smectic A (T = 60.7 °C), (b) smectic B (T = 48.1 °C). The dashed lines
are calculated from theory. The presence of a third component in (b) indicates that
the shear modulus does not vanish in smectic B at these very high frequencies.
Circles, triangles and squares represent measurements at different scattering
angles. (After Liao, Clark and Pershan.(47))
a (say), (5.3.53)
where the subscripts h and a stand for the harmonic and anharmonic parts
5.4 Defects in smectic A 327
of F, and V± and A± are the gradient operator and Laplacian respectively
in the xy plane. Using a renormalization procedure, Grinstein and
Pelcovits(48) showed that the effect of Fa at non-zero temperature is to
change (5.3.22) into a form where the elastic constants are replaced by q
dependent functions with
(a)
(b)
Circle L(.
Hyperbola Lh
to
Ellipse Le
Fig. 5.4.1. (a) Smectic layers in concentric cylinders to form a myelin sheath with
a singular line L along the axis; (b) the cylinders are closed to form tori: there are
two singular lines, a circle Lc and a straight line Ls; (c) the general case when the
smectic layers form Dupin cyclides: the circle becomes an ellipse L e and the straight
line a hyperbola Lh.
rise to beautiful optical patterns known as focal conic textures. These were
studied in considerable detail by Friedel, (55) to whom we owe the
explanation of their origin. We shall now examine the structures of these
focal conic domains. (56)
(a) The simplest case is shown in fig. 5.4.1 (a). The layers are wrapped
round in concentric cylinders to form a myelin sheath and there is a
singular line L along the axis, (b) When the myelin sheath is bent and closed
to form tori, the singular line L becomes a circle Lc (fig. 5.4.1 (b)). In
addition, the structure now has another singular line Ls - a straight line
through the centre of the circle and perpendicular to it. Such a structure is
5.4 Defects in smectic A 329
{a) (b)
Fig. 5.4.2. A rare example of a pair of singular lines, one almost straight and the
other almost circular in a toric domain in the (a) smectic A and (b) smectic C
phases. Additional disclination lines develop near the centre in the smectic C phase
for reasons discussed in §5.8.3. (From A. Perez, M. Brunet and O. Parodi, J. de
Physique Lettres, 39, 353 (1978)).
observed only very rarely (fig. 5.4.2). (c) In the most general case, the
smectic layers lie on Dupin cyclides and not on tori. The circle Lc is then
transformed to an ellipse Le and the straight line into a hyperbola Lh (fig.
5.4.1 (c)). Le and Lh are conic sections in perpendicular planes, one going
through the focus of the other (figs. 5.4.3 and 5.4.4). It is these structures
that are most commonly seen under the polarizing microscope (fig.
1.1.7 (a)).
Based on the fact that the layers are bent into Dupin cyclides, one can
derive expressions for the principal curvatures ox and cr2, and thus work out
the energy,
f
330 5. Smectic liquid crystals
(a)
Fig. 5.4.3. (a) Geometry of a pair of focal conies. (After Friedel.(55)). (b) A section
of (a) in the plane of the hyperbola, showing parts of Dupin cyclides. (After
Bragg.(56))
For the general focal conic structure, Kleman (57) has shown that
(a)
Fig. 5.4.4. (a) Arrangement of a set of cones within a pyramid. The hyperbolas
belonging to the ellipses meet at the vertex of the pyramid, (b) The base of the
pyramid and the axial directions radiating from the foci at the base of the
hyperbolas. (After Bragg.(56))
In principle, the focal lines can both be parabolas. Such parabolic focal
conies have been observed by Rosenblatt et al.{58) but they are not
common. Kleman(57) has shown that in this case
4/rJ'
where/is the focal length of the parabola and R the sample radius. The
energy increases with R and diverges as f-+ 0. Thus, in general, such
structures are not energetically favourable. However, it turns out that
when R < 3/, they can have smaller energies and Kleman argues that this
may explain the observations of Rosenblatt et al
A remarkable property of the smectic liquid crystal is that an open
332 5. Smectic liquid crystals
-cpn-dr = TV
dj
along a closed path about L in the anticlockwise direction. Clearly N = + \
in fig. 5.4.6 (a) and — 1 in fig. 5.4.6 (b). Accordingly, we may refer to the two
cases as positive and negative edge dislocations of unit strength re-
spectively. Topologically these defects are very similar to their counterparts
in crystals, but they differ significantly from the point of view of energetics,
as we shall see presently.
From the free energy expression (5.3.18), we obtain the equation of
equilibrium
where
A. = (k11/B)* and u = u(z, x).
We now proceed to work out the singular solutions of (5.4.1). For an edge
dislocation with the extra half-plane on the side x > 0, the boundary
conditions are
m \0 for i < 0
"(0, x) = i
[b/2 for x > 0 .
334 5. Smectic liquid crystals
n n
(a) (b)
Fig. 5.4.6. (a) Positive and (b) negative edge dislocations of unit strength.
We then have
(5.4.3)
The tilt in the layer normal 6 = du/dx, and the dilatation in the layer
spacing S = Ad/d = —Xffl/dx; 6 and 5 can be derived explicitly from the
form of u:
|= J b__ex i__x' (5.4.4)
x Xb
(5.4.5)
From (5.4.5) it is seen that there is a compression of the layers for x > 0 and
an extension for x < 0.
The stresses associated with the dislocation cannot be derived uniquely.
However, one acceptable set of values can be obtained from the equation
of motion. (63) They are
Bb -x
17-3 e x P -: (5.4.6)
2 72
XBb -x
(5.4.7)
2 AX\z exp - AX\z\
/15Z? z I x
(5.4.8)
2X\z exp - 4A|zj
Apart from the exponentially decaying term, a33 varies as l/n, GX1 and a13
as \/n.
In contrast, all these stress components vary as 1 /r in the case of crystal
5.4 Defects in smectic A 335
edge dislocations. The displacement u around the crystal dislocation is
given by
where v is Poisson's ratio. Again the form of this expression can be seen to
be quite different from (5.4.2) for u in smectic A.
The energy of a single edge dislocation
The total energy is given by
E= I \Fdxdz. (5.4.10)
(5.4.13)
for z > z0,
(5.4.14)
336 5. Smectic liquid crystals
Here e is 1 for like dislocations and — 1 for unlike ones. The interaction
energy
^ ( ^ f f ^ ) (5.4.17)
From this we get two forces Fx and Fz along and normal to the smectic
planes:
Since k.JX2 = b,
Fx = -ebaS3 (5.4.20)
and
Fz = ebals. (5.4.21)
Here cr33 and <713 are the stresses at the origin, where the first dislocation is
situated, due to the presence of the other dislocation at (x o,zo). This is
known as the Peach-Koehler force(65) on a dislocation arising from the
stress field of the other. This can be generalized to mean that under
application of a stress oip a dislocation experiences a force Fi whose exact
relationship is given by the above expressions.
It is seen from (5.4.18) that Fx is always repulsive for a pair of like
dislocations and always attractive for an unlike pair. On the other hand,
Fz can be attractive or repulsive depending on the relative positions of the
two dislocations. For example, Fz is repulsive for like dislocations when
xl < 2Xz and attractive when x\ > 2Az0. This provides a mechanism for the
5.4 Defects in smectic A 337
Fig. 5.4.7. Clustering of like edge dislocations in smectic A to form a domain wall
or 'grain boundary'. (After Pershan.(63))
(a)
vllllIMIIIII
^11111111111
1 III 1
r 1HIM
11111 1,111,1.1,1,1,1.1.1
dmmmii
II
(c) (d)
Fig. 5.4.8. Disclinations in smectic A: (a) £la(n); (b) Qb(n); (c) Qo( - n); (</) Qb( - n).
u = —tan"1 r-
2n \x
where u is the layer displacement along z, and b the Burgers vector is equal
to an integral multiple of the layer spacing d. For a positive screw
dislocation one gains a step of height b on going once round the line L in
the anticlockwise direction, while for a negative dislocation one loses a
step.
A noteworthy aspect of the above solution is that it does not involve
either lattice dilatation du/dz or layer undulation V-n. Therefore, within
the approximations of the linear theory considered here, screw dislocations
in smectic A have no self energy (apart from the core), nor do they interact
amongst themselves. In this respect they are entirely different from screw
dislocations in crystals.
5.4.4 Disclinations
The geometrical process for creating a disclination in smectic A is as
follows.(67) Cut the material by a semi-infinite plane that runs parallel to the
layers, the limit of the cut being the disclination line L. Rotate the two faces
5.4 Defects in smectic A 339
41 El III! I I I II
(«) (b)
(a) (b)
of the cut about L through a relative angle + Nn, N being an integer. Fill
in the voids (or remove overlapping material) to get positive (or negative)
disclinations, and allow the system to relax. The structures so obtained
depend on whether the cut is made at the extreme end of the molecule or
through its middle. The resulting disclinations, designated as Q a and Q&,
are illustrated in fig. 5.4.8. It is obvious that Q a and Qb are not the same
- their core energies are different, and they also have different con-
figurations at large distances. The creation of Q disclinations also gives rise
to disclinations of strength s = ± | in the smectic director n.
The energy of an isolated disclination being large, disclinations of
opposite signs may be expected to occur in pairs to form edge dislocations
and what Bouligand has called 'pincements' (see figs. 4.2.6 and 4.2.8).
Some possibilities are shown in figs. 5.4.9 and 5.4.10.
340 5. Smectic liquid crystals
For a wide nematic range x(TAN) is small, /?' > 0, and the transition is of
second order. For a small nematic range x(TAN) is large, /?' < 0, and the
transition is of first order; in this case one must add a positive sixth order
5.5 The smectic A-nematic transition 341
term in the free energy to ensure stability. The tricritical point occurs when
/?' = 0, i.e., x(TAN) = 2/3/C2. This is in agreement with the prediction of the
microscopic theory, according to which the tricritical point occurs at
7; N /r NI = 0.87 (see §5.2). /(7^ N ) may be altered by varying the length of
the end-chain, or by preparing mixtures, or by the application of
pressure.(70)
In the smectic phase (T < T*), the amplitude of the density wave may be
taken to be constant, so that only q> varies. The gradient terms of F
therefore become
Comparing this with (5.3.3) it is at once clear that cp is related to the layer
displacement u:\q>\2 = q2\u\2 and B =\y/\2 ql/Mv. The terms d<p/dx and
dcp/dy represent the tilt of the layers with respect to the director. If the
director orientation is not fixed, it is the relative tilt between the layers and
the director that should be considered and therefore (5.5.6) takes the
generalized form
^(^)\± (5.5.7)
2Mv\dz) 2M T '
where VT is the gradient operator in the plane of the layers. This equation
342 5. Smectic liquid crystals
is reminiscent of the Landau-Ginsburg expression(72) for the free energy of
superconductors; n corresponds to the vector potential A, V x A being the
local magnetic field.
The analogy may be extended further. By including the Frank elastic
free energy terms in (5.5.6), we may define (as already shown in §5.3.3) a
characteristic length X = (k/B)*. Making use of the condition dF/dy/0 = 0
and ignoring the difference between MT and Mv,
—, , (5.5.9)
<f(Vn)2, (5.5.13)
1V1
Skoc^t (5.5.15)
Since the coherence lengths diverge rapidly near the A-N transition, the
elastic constants for twist and bend should also show critical behaviour. In
the mean field approximation
£ oc ( r - r * ) ~ 1 / 2 . (5.5.16)
However, invoking the analogy with superfluids, de Gennes predicted
£ oc (T- T*)~2/\ (5.5.17)
Using scaling arguments, Jahnig and Brochard(73) have shown that in
the anisotropic case
<J* M ocft/£,, (5.5.18)
<**„«£„, (5.5.19)
and that, below T* (i.e., in the smectic phase),
Bazit/Zl, (5.5.20)
Dccl/£r (5.5.21)
The theory continues to be valid even if the A-N transition is weakly first
order, except that T* represents a hypothetical second order transition
temperature slightly below 7^N.
The first X-ray scattering experiments of McMillan(74) on /?-n-octyl-
oxybenzylidene-/?-toluidine, which exhibits a first order A-N transition,
agreed with the mean field theory. On the other hand, CBOOA showed
appreciable anisotropy in the temperature variation of the longitudinal
and transverse coherence lengths. Later studies on a number of materials
have confirmed that anisotropy is a general feature exhibited by all of
them.
The increases in k22 and fc33 in the nematic phase near the A-N transition
over and above that given by the usual s2 law are now well established. Fig.
5.5.1 presents the data of Cheung, Meyer and Gruler(75) for CBOOA; &33
344 5. Smectic liquid crystals
70 r-
60
50
£« 40
Ax
30
20
10
,, 1 I I
0.1 1.0 10 30
r-r A
Fig. 5.5.1. The temperature dependence of the splay and bend elastic constants, kxl
(crosses) and k33 (circles) respectively, in the nematic phase of CBOOA prior to the
smectic A-nematic transition. The values are plotted as &../A/ where A/ is the
anisotropy of the diamagnetic susceptibility of the nematic. The full line shows the
order parameter s, normalized to fit fcn/A/ at higher temperatures. The splay
constant klx deviates only very slightly from ordinary nematic behaviour while the
bend constant kZ2> exhibitsa critical increase near 7^N due(75)to pretransition
fluctuations. (After Cheung, Meyer and Gruler. )
diverges rapidly while fcn exhibits normal behaviour. Similarly, it has been
verified that the layer compressibility constant B shows a critical variation
in the vicinity of the transition.
weakly first order. The shift in the transition point due to this effect,
relative to the second order transition point T*, was estimated to be of
the order of 10 mK. Whether or not the A-N transition can, in principle,
be of second order has been the subject of some discussion. (7981) From
high resolution experimental studies it appears that the second order
nature of the transition has been more or less established in at least a
few cases(82) (though Anisimov et al.m) have claimed to have observed
the 'Halperin-Lubensky-Ma effect' in three different systems). A
number of theories have been proposed, which have been reviewed in
authoritative articles,(84~6) but a precise description of the A-N transition
still remains elusive. We shall give a very brief summary of the current
situation.
5.5 The smectic A-nematic transition 347
Compound a v
n v± y a + 2v± + v|| Reference
T8 0.66 0.07 0.70 0.65 1.22 1.93 + 0.15 92
T7 0.71 0.05 0.69 0.61 1.22 2.06 + 0.15 92
40.7 0.926 -0.007 0.78 0.65 1.46 2.07 + 0.1 89,93
8S5 0.936 0 0.83 0.68 1.53 2.19 + 0.16 94,95
CBOOA 0.94 0.15 0.70 0.62 ]1.30 2.09 + 0.14 96,97
40.8 0.958 0.15 0.70 0.57 1.31 1.99 + 0.18 98
80CB 0.963 0.2 0.71 0.58 1.32 2.07 + 0.17 96,99
9S5 0.967 0.22 0.71 0.57 1.31 2.01 ±0.18 95, 100
8CB 0.977 0.31 0.67 0.51 11.26 2.00 + 0.13 101,82
10S5 0.983 0.45 0.61 0.51 ]1.10 2.08 + 0.18 95, 100
9CB 0.994 0.50 0.57 0.39 11.10 1.85 + 0.18 100, 82
XY model -0.007 0.669 0.669 ] .316 2.0 102, 103
Tricritical 0.5 0.5 0.5 11.0 2.0
Tn = 4-alkoxybenzoyloxy-4/-cyanostilbene n = 7,8
40.m = butyloxybenzylidene alkylaniline m = 7,8
nS5 = 4-n-pentylphenylthiol-4/-alkyloxybenzoate n = 8,9,10
0.40
0.35
0.30
0.25
72 76 80 84
Temperature (°C)
Fig. 5.5.3. Pitch versus temperature in cholesteryl nonanoate prior to the smectic
A-cholesteric transition (74 °C); the crosses are values obtained from observations
of the Grandjean-Cano walls and the circles from the wavelengths of maximum
reflexion. (After Kassubek and Meier.(111))
(5.5.31)
/Coo I* Ofcn
(5.6.1)
where
i t i
in, !!
1
! n
Ad 1 I — I I P IIII
1 •i
ii
1
I
1 1 i
II
II
ji
i i I
• K • vi
ri i if " "h i
} \ \ \
i, - .
i, , , ,
ii
\i I
i
'!
• >;
l> '
. •
\
• ,
11
n
i
i
II i i;
i ii ii i
Soliton region
D3I II—'7T-1I
I
Locked phase
region
JIT"
Wi Wn'fi nx.
Soliton region -
(a)
Fig. 5.6.2. Schematic representation of the molecular arrangement in (a) the weakly
coupled incommensurate smectic A, and (b) the strongly coupled incommensurate
smectic A. (After Prost and Barois. (115))
of the two waves are modulated (fig. 5.6.2(b)) exactly in accordance with
the theory proposed originally by Frank and Van der Merwe. (116) In the
latter case, the structure consists of large regions of A 2 separated
periodically by defect walls or phase solitons. Experimentally, however,
the occurrence of incommensurate smectic A phases has yet to be
established conclusively. (117~119)
Barois, Prost and Lubensky(120) have used the phenomenological model,
within the framework of the mean field theory, to construct phase diagrams
involving the polymorphic forms of the A phase. They have predicted three
kinds of critical points, the A d -A 2 critical point, the A x -A 2 tricritical point
and the A 1 -N-A d bicritical point, the salient features of which are
summarized below.
Since Ad and A2 have the same symmetry, it is to be expected that a first
order A d -A 2 phase boundary should terminate at a critical point. This has
been confirmed(121) in a binary liquid crystal system. Plots of wavevectors
against temperature for different concentrations (X) in the vicinity of the
critical point are shown in fig. 5.6.3. It is seen that the first order A d -A 2
transition manifests itself as a jump in the wavevector, accompanied by a
two-phase coexistence region. On increasing X the magnitude of the jump
as well as the width of the two-phase region decrease, until finally only a
5.6 Smectic A polymorphism 353
124 125 126 127
120 —
I
5 10 15
Concentration (molar % TBBA)
Fig. 5.6.4. Binary phase diagram for mixtures of 4-n-hexylphenyl-4/-cyano-
benzoyloxybenzoate and terephthal-to-butylaniline (TBBA) showing the A^-Ag
tricritical point (TCP). The solid line represents the first order phase boundary
and the dashed lines represent the second order phase boundaries. (After Chan
et tf/.(123))
52 53 54 56
Concentration, X (mol %)
Fig. 5.6.5. High resolution temperature-concentration (T-X) diagram for binary
mixtures of 4-n-octyloxy- and 4-n-decyloxy-phenyl-4 / -nitrobenzoyloxybenzoate in
the vicinity of the A 1 - N R - A d point. The solid lines denote first order phase
boundaries. The critical end point (CEP) for the A d - N R b o u n d a r y and the
approximate location of the tricritical point (TCP) for the A X - N R boundary are
indicated in the diagram. (After reference 127.)
A 1 -N R -A d point show that the bicritical point has, in fact, split into a
tricritical point (for the A X -N R boundary) and a critical end point (for
the A d -N R boundary, fig. 5.6.5). This new result, though predicted
theoretically for magnetic systems,(128) has not been envisaged in any of
the theories of frustrated smectics.
1.4
1.0
0.6
Smectic A Isotropic
0.2
50 70 90 110
Temperature (°C)
Fig. 5.6.6. Experimental pressure-temperature diagram for 80CB showing the re-
entrant nematic phase. (After Cladis et al.a30))
C 9 H 19 O OOC OOC
(a) (b)
Fig. 5.6.8. Schematic representation of (a) a dimer unit consisting of two
antiparallel molecules, (b) the mechanism of destabilization of the smectic A phase.
(After Cladis.(135))
C 13 H 27 O -COOC*H(CH 3 )C 6 H 13
33.7 °C
s4 < s,
43.7 °C
Fig. 5.6.9. The structural formula of (R)- and (S)-l-methylheptyl 4'-(((4"-n-
alkoxyphenyl)propioloyl)oxy)biphenyl-4-carboxylates, which show the smectic A*
phase.
Fig. 5.6.10. The structure of smectic A* or the twist grain boundary phase.
c
Six) = I0\c0+ t *ncos6,2(90-/)l + /bg, (5.7.1)
(a)
0'
(b) .
4 - (a)
7=68.1 °C
I o
15
(c)
10
r=63.9°C
ir/6
Rotation angle, x
Fig. 5.7.2. A 60° segment of a/-scan about an axis normal to the smectic layers of
the intensity of X-ray scattering from n-hexyl-4'-n-pentyloxybiphenyl-4-carb-
oxylate exhibiting the smectic A-hexatic B phase transition, (a) The scattering in
the A phase is a diffuse ring independent of/. For temperatures below the smectic
A-hexatic B transition the ring develops a sixfold modulation (Z>), which
eventually breaks up into six diffuse spots (c). (From Pindak et al.ai0))
5.8 Smectic C
5.8.1 Description of the structure
In S c the molecules are disordered within the layers, as in SA, but inclined
with respect to the layer normal. The structure has biaxial symmetry of the
monoclinic class, with a plane of symmetry as indicated in fig. 5.8.1. The
origin of the biaxiality may be explained as follows. The tilt angle 6 is
directly coupled with the layer thickness whereas the azimuthal angle <p is
not. Therefore, at any given temperature, the amplitudes of the 6
oscillations of the director are small compared with those of the (/>
5.8 Smectic C 363
^ Symmetry plane
' Molecular axis
'///////////////////A
V///////////////////,
* V////////////////A
oscillations, with the result that the uniaxial symmetry about the mean
molecular direction disappears, and there exists only a plane of symmetry.
Because of this, and also because of possible anisotropic polarization field
effects, S c is optically biaxial. The optic axial angle is generally quite small
(-10°).
S c is often followed by SA at a higher temperature, and in such a case the
tilt angle decreases to zero gradually with rise of temperature. If the C-A
transition is of second order, the tilt 6 decreases smoothly to zero, whereas
if it is of first order 6 drops abruptly from a finite value to zero at the
transition point.
If S c undergoes a transition directly to the nematic phase, 6 is generally
found to be temperature independent and usually about 45°. According to
the Landau rules, the C-N transition can be continuous, but when
fluctuations(175) are taken into account it is predicted to be of first order.(176)
Experimentally, only first order C-N transitions have been observed.
Some compounds exhibit transitions from S c to the isotropic phase.
Interestingly, a slight increase of 6 with increasing temperature has been
reported for two such compounds.(177)
As in the SA phase, Sc lacks true long-range translational order because
of the Peierls-Landau instability. Theoretically, the existence of molecular
tilt implies that there must be a certain degree of bond-orientational order
in the S c phase. (171178) This has been verified experimentally by a high
resolution synchrotron X-ray study of the transition from S c to Sx in a
monodomain freely suspended film.(172) It will be recalled that Sx is a tilted
hexatic phase. The bond-orientational order parameter C6 (as defined in
(5.7.1), but appropriately modified to allow for the fact that the molecules
are tilted) is plotted as a function of temperature infig.5.8.2. The weak
bond-orientational order in S c evolves continuously into ST showing
364 5. Smectic liquid crystals
"2
o
75 77 79 81
Temperature (°C)
Fig. 5.8.2. The hexatic order parameter C6 as a function of temperature in the S c
and Sj phases of racemic 4-(2-methylbutyl) phenyl 4 / -(octyloxy)-(l,r)-biphenyl-4-
carboxylate. The weak bond-orientational order in S c evolves continuously into Sx
showing that thermodynamically the two phases are not distinct in this compound.
(After Brock et a/.(172))
that thermodynamically the two phases are not distinct. Tilt angle
measurements (179) (using X-ray methods) have confirmed that there is
indeed a continuous evolution of S c into SI5 as the temperature is lowered.
Generally speaking, compounds exhibiting the S c phase have transverse
components of permanent electric dipole moments. A number of molecular
statistical models (including hard rod theories for systems composed of
oblique cylinders) have been developed. (1808) Goossens(189) has proposed a
model composed of ellipsoidal molecules with attractive interactions
arising from anisotropic dispersion forces as well as permanent quadrupole
moments. His calculations show that the interaction between the per-
manent quadrupole moments can produce a tilting of the molecules, but a
detailed comparison of the predictions with experimental data has yet to be
made.
When the molecule has a strong longitudinal dipole moment, several
modifications of the S c structure have been identified. They are shown in
fig. 5.8.3, and as can be seen they are closely analogous to the SA phases of
polar molecules (fig. 5.6.1). However, the theoretical situation for S c is not
as clear as for SA. Another modification of S c is the chiral S c or the Sc*
phase which will be discussed in §5.10.
5.8 Smectic C 365
(arbitrary units)
Fig. 5.8.4. Plot of qxl* versus qzl^ from light scattering measurements in the
smectic C phase of di(4-n-decyloxybenzal)-2-chloro-l-4-phenylene diamine. The
wavevector q relative to the layers is indicated in the inset at the top left-hand
corner. The experimental points lie on an ellipse as expected theoretically. However,
the minor axis of the ellipse does not coincide exactly with the molecular axis,
which is assumed to be inclined at 45° to the layer normal. (After Galerne et a/.(193))
coordinate system such that the projection of the mean molecular direction
on the basal (xy) plane is along x. If the layer displacement along z is
represented by w, we observe that
du/dy = £lx,
(5.8.1)
5.8 Smectic C 367
Making use of (5.8.1), and assuming the layers to be incompressible, the
free energy of elastic distortion may be written in the form
Here the A terms describe curvature distortions of the smectic planes, the
B terms the distortions of the director when the smectic planes are
unperturbed, and the C terms the coupling between these two types of
distortions. All the coefficients are approximately of the same order of
magnitude as the nematic elastic constants. A term of the type \B(<du/dz)2
may also be included to allow for the compression of the layers, but we
shall neglect it in the present discussion.
The fluctuations of the director are evidently related to fluctuations in Q.
From (5.8.2) and the equipartition theorem, we obtain for a general
wavevector q
0) (ii)
Fig. 5.8.5. Disclinations in the odirector field of smectic C. (a) 5 = 1 wedge
disclination with a radial configuration: (i) sink, (ii) source and (iii) meridian
section of (i). (b) s = 1 wedge disclination with a circular configuration: (i) vortex,
(ii) antivortex and (iii) meridian section of (i); the nails signifying that the director
is tilted with respect to the plane of the paper, (c) (i) s = — 1 wedge disclination and
(ii) s = 1 twist disclination.
Parodi and Pershan (MPP), (39) and by others.(194) Leslie, Stewart and
Nakagawa (195) have formulated a general non-linear theory, which in the
static case becomes identical with that proposed by the Orsay group. The
full implications of the dynamical aspects of this theory and its comparison
with the MPP theory have yet to be worked out.
5.8 Smectic C 369
(a) (b)
Fig. 5.8.6. Disposition of the molecules and layers in elliptical domains in (a)
smectic A and {b) smectic C. The mismatch of the molecular orientations in smectic
C gives rise to additional singular lines. (Bourdon, Sommeria and Kleman. (198))
Fig. 5.8.7. Edge dislocations in smectic C at a temperature very close to the smectic
C-smectic A transition. The sample, prepared in the form of a wedge, consists of
two domains of opposite molecular tilts. (Lagerwall and Stebler. (199))
K
3A1/2 -11/2
1--J - l j , T<TCA, (5.8.7)
where
R = (b/3cr\
t0 = b*/ac.
Substituting (5.8.7) in (5.8.6) and making use of the standard relation
we get
fC T>T
CA
C,= " (5.8.8)
l.C 0 H-^ii(i m —7 J , i < i CA
where
A = ^3/2 /[2(3c) 1/2 r3/A2],
(5.8.13)
where a = oc0(T— TCA), k119 k22 and A:33 are the elastic constants for in-plane
distortions, nx = 0cos(f>9 ny = 0sin(/> and nz&\. Assuming the one-
constant approximation and that the distortions are such that there is no
z dependence of 0 and <fi, the equations of equilibrium become
\k[V20-0(V(f>)2]-(x0-2p03 =0 (5.8.14)
and
= 0. (5.8.15)
Equation (5.8.15) allows solutions of the type
cj) = ± Nco,
/ 2 ) = o (5 8 i6)
' - -
2 2
where / = 0/0o, £ = r/£0, r = (x +y )*, 0O is the tilt angle at r-> oo, and
£o = { — k/2(xf is the coherence length. Equation (5.8.16) is of the same
form as the Ginsburg-Pitaevskii equation for a quantized vortex filament
in a superfluid or a magnetic fluxoid in a type II superconductor. The tilt
angle drops to zero at the centre of the singularity, most of the variation
taking place over a distance of the order of <J0 from the centre (fig. 5.8.9).
374 5. Smectic liquid crystals
This result appears to account for the experimental observation (206) that
there is an appreciable region near the centre of the + 1 singularity over
which 6 is very nearly zero, i.e., the material is smectic A-like.
Fig. 5.8.9. Variation of the superfluid order parameter with distance from the
centre of a quantized vortex filament as given by the Ginsburg-Pitaevskii equation
(5.8.16). The same curve describes the variation of the tilt angle in the core region
of the smectic C disclination.(206)
.8exp(ikT)/>(k)d8fc, (5.9.2)
-/. 87T
where /?(k) is the Fourier transform of the centre of mass density p(r). The
domain of integration D takes into account the fact that the X-ray
scattering in the S c phase will be a ring defined by (qp q±cos <fi, q±sin (/>). The
general form of the free energy is written as
C2
+ D±[V2y/-n• (n 3
+ Fel d r, (5.9.3)
where Fel is the Frank elastic energy for distortions of the nematic director.
The coefficients C , D and D± are positive and a = ao(T— 7^ A )/7^ A . The
type of fluctuations in the nematic phase is thus determined by the
coefficient C ± , i.e.,
if C ± > 0, SA-like fluctuations
if CL < 0, Sc-like fluctuations.
376 5. Smectic liquid crystals
4 -
3 -
<•>
N
U
1- A
/
X-
0 -
/DvM MX X*A*
-1
(a)
-2
_2
(4 data sets)
-1
l 1 1
*\ 1 x\
151.4
150.6 -
149.8 -
(b)
275 295 305 315 325
Pressure (bar)
Fig. 5.9.1. For legend see facing page.
5.9 The nematic-smectic A-smectic C multicritical point 311
Hence the CL = 0 point is a fluctuation cross-over point. The locus of such
points (a > 0, C± = 0) in a phase diagram, say the T-X diagram, gives the
Lifshitz line, and the point where both a and CL are zero is the Lifshitz
point.
The X-ray scattering intensity in the nematic phase can be obtained by
applying the equipartition theorem to (5.9.3):
k T
For C± > 0 this gives a peak at k = ±q]{ with a Lorentzian profile and
corresponds to SA-like fluctuations, and
q, = (q/2/),,)*.
For C± < 0, (5.9.4) can be rewritten as
k T
(5.9.7)
k T
At the Lifshitz point itself, there is a drastic change and Sk33 oc £, while dklx
and Sk22 oc In £.
Grinstein and Toner(226) applied the renormalization group technique
and presented a dislocation loop model for the NAC point. The most
striking conclusion of this theory is that a biaxial nematic phase N b should
intervene between the N and S c phases. Thus four phases, N, N b , SA and
S c , meet at a point giving rise to a tetracritical point topology. A
fluctuation corrected mean field theory developed by Lubensky(227)
supports this prediction, but points out that it may be difficult to detect the
presence of the N b phase through X-ray and calorimetric measurements.
All experimental studies but one have so far failed to detect the N b phase.
The one study is by Wen, Garland and Wand(228) whose high resolution
specific heat measurements have revealed anomalous variations near the
C-N transition very close to the NAC point, which they suggest may be
related to biaxial fluctuations. An attempt has been made to explain the
universal topology of the phase diagram in the vicinity of this multicritical
point.(258)
5.10 Ferroelectric liquid crystals
5.70.7 The properties of smectic C*
An interesting modification of smectic C is the Sc* phase, which has a twist
axis normal to the layers (fig. 5.10.1 (a)). The possibility of such a structure
being formed by the addition of optically active molecules to the ordinary
5.10 Ferroelectric liquid crystals 379
\\L
11/111/111] urn ii II
1111111111
miiiiui
Helical inn IIui
WWWY
pitch, p
mmmi
\
IIIIIIIIII
iiii/wmr
im/yini mil! mi'
{a) (b)
Fig. 5.10.1. (a) Helicoidal structure of the ferroelectric smectic C* phase, (b) a
' poled' sample with the helix unwound by an electric field applied normal to the
helical axis.
crystal - isotropic
Both Sc* and Sj* (the chiral forms of S c and Sx) were shown to be
ferroelectric.
380 5. Smectic liquid crystals
In SA the molecules are upright, and since there is no head-to-tail
ordering (the director being apolar) there is no polarization normal to the
layers. Moreover, even if the molecules themselves are chiral, there is equal
probability of their assuming any orientation about their long axes. Hence
the transverse component of the dipole moment is averaged out and there
is no net polarization parallel to the layers.
In the Sc* phase, on the other hand, the molecules are tilted, and their
rotation about their long axes is biased. The symmetry plane of the
ordinary S c structure (fig. 5.8.1) is now absent because the molecules are
chiral. The only symmetry element that remains is a twofold axis parallel
to the layers and normal to the long molecular direction. This allows the
existence of a permanent dipole moment parallel to this axis. (Of course,
these arguments apply to the Sx* phase as well.)
Thus in Sc* each layer is spontaneously polarized. Since the structure has
a twist about the layer normal, the tilt and the polarization direction rotate
from one layer to the next (fig. 5.10.1 (a)). This implies that there is a
constant bend around the helical axis, which gives rise to a flexoelectric
contribution to the polarization.
When an electric field E is applied normal to the helical axis, the helix
gets distorted in a manner somewhat analogous to that depicted in fig.
4.6.1 for the cholesteric case. Above a critical field given by
where p is the pitch of the undistorted helix and k the 'twist' elastic
constant (which may be expected to vary rapidly with the tilt angle 6), the
helix is completely unwound and the sample is poled (fig. 5.10.1 (£)). The
molecules are then aligned in a plane perpendicular to E with a tilt 6 with
respect to the layer normal. When the field is reversed, the polarization P
reverses direction, and because of the coupling between polarization and
tilt, the molecular orientation switches from 6 to —6. As we shall see later,
this effect finds important applications in electro-optic display devices.
The value of the spontaneous polarization in these materials is quite
small, usually between 10 and 1000 nC cm" 2, i.e, about one or two orders
of magnitude less than that for a solid ferroelectric like KH 2 PO 4 .
The coupling between P and 6 manifests itself even above the C*-A
transition: an electric field induces a tilt in the A phase as well. This is called
the electro clinic effect, and was first demonstrated by Garoff and Meyer.(233)
Induced tilt angles as high as 10° have been observed in high polarization
materials. Due to its submicrosecond response and its linear dependence
5.10 Ferroelectric liquid crystals 381
60 r
15
-r(K)
Fig. 5.10.2. Variation of the polarization P with relative temperature in the smectic
C* phase of DOBAMBC. The curve represents thefitobtained with the generalized
Landau theory. (After Dumrongrattana and Huang.(236))
15
Fig. 5.10.3. Variation of the tilt angle 6 and the ratio P/0 with relative temperature
in the smectic C* phase of DOBAMBC. The curves represent thefitsobtained with
the generalized Landau theory. (After Dumrongrattana and Huang.(236))
Is
f 5
5 10 15
TC.A-T(K)
Fig. 5.10.4. Variation of the pitch with relative temperature in the smectic C* phase
of DOBAMBC. (Ostrovskii et al.(237)). The curve represents the fit obtained with
the generalized Landau theory. (After Dumrongrattana and Huang. (236))
20 -
T(°C)
Fig. 5.10.5. The temperature variation of the field-induced tilt (or the electroclinic
effect) in the smectic A phase of 4-(3-methyl-2-chlorobutanoyloxy)-4 /-heptyloxy
biphenyl. (After Bahr and Heppke. (238))
shown in figs. 5.10.2, 5.10.3 and 5.10.4 and the variation of the electroclinic
effect with temperature in a high polarization material is shown in fig.
5.10.5. The static dielectric constant (for measuring field parallel to the
layers) increases slightly with temperature initially, but drops rapidly close
to 7^*A (fig. 5.10.6). From the dielectric relaxation one can study the two
important director modes, viz, the symmetry-recovering Goldstone mode
and the soft mode, in the vicinity of the C*-A transition. The Goldstone
mode is associated with the fluctuations of the azimuthal angle (<f>) of the
director, and the soft mode with the tilt (9) fluctuations. The former owes
its origin to the helical structure, and hence its frequency and strength
5.10 Ferroelectric liquid crystals 3
300
0.3 kHz
240 -
180
~" 0.4 kHz
120
0.5 kHz
60 -
10 kHz
0
1 i i i i i ,
- 3 - 2 - 1 0 1 2
r-r c . A (K)
Fig. 5.10.6. The dielectric constant for measuring field parallel to the layers as a
function of temperature in the smectic C* phase of [S]-4'-(2-chloro-4-methyl-
pentanoyloxy)phenylftYtfw-4//-n-decyloxycinnamate.The variation of the di-
electric constant with frequency is a consequence of the Goldstone mode relaxation.
(After reference 239.)
vanish in the SA phase (fig. 5.10.7(<z)). As for the soft mode, its frequency
decreases and strength increases on approaching the transition point from
either side (fig. 5.10.7 (b)). The coefficients of viscosity, y^ and y0, associated
with these modes are also strongly temperature dependent (fig. 5.10.8).
By virtue of their symmetry, ferroelectric smectics are piezoelectric.
Polarization can be induced by mechanical shear (2413) and, conversely, an
electric field can produce shear flow. They also possess pyroelectric
properties/ 244 ' 245)
An antiferroelectric smectic phase has been identified recently. (246) The
structure is expected to have an interlayer herringbone arrangement.
0
160 - 1
%
(a) 0
-6
1 1
-4 -2
1
10
T- TC*A (K)
0.16 • 200
• •
0.12 o— 150
w o
• o
kHz)
• / o
< 0.08 - < o 100
o 1
0.04 V o°
o
- 50
o ooc, • 6>°
- 0
b) ° ~ 1 i 1 1
-0.5 0 0.5 1.0 15
T--T A(K)
Fig. 5.10.7. The variation of the frequency (open circles) and dielectric strength
(filled circles) of (a) the Goldstone mode and (b) the soft mode in the vicinity of the
C*A transition. Material same as in Fig. 5.10.6. (After reference 239.)
10
fe, 1.0
0.1
90 80 70
T(°C)
Fig. 5.10.8. The temperature variation of the Goldstone mode and soft mode
viscosity coefficients, y^ and y0, in the smectic C* phase of DOBAMBC. (After
Pozhidayev et a/.(240))
5.10 Ferroelectric liquid crystals 385
(ferroelectric) coupling. Liquid crystalline ferroelectrics may therefore be
classified as 'improper' ferroelectrics: the primary order parameter is the
tilt (0) and not the polarization (P). Meyer (247) proposed a simple
phenomenological model that accounts for some of the observed phenom-
ena.
We shall suppose that the transition is of second order, and consider
first the spatially homogeneous case (i.e., the helix unwound completely,
q = 27r/pitch = 0), ignoring the effect of the spontaneous helical torsion
that appears below the transition. The free energy may then be written
as (247)
^eErj0P, (5.10.2)
oil
where A = a(T— TCA). The first two terms are the leading terms of the usual
Landau expansion, the next three terms describe the electrostatic free
energy and the last term expresses the coupling between P and 6.
Minimizing with respect to P and 0,
P = X(E+r,6), (5.10.3)
e = t,XE/A, (5.10.4)
and hence,
^ ±^!iy (5.10.5)
We may draw the following conclusions: (a) from (5.10.5), we see that
the P—B coupling produces a divergent component in the dielectric
constant, (b) from (5.10.3), that polarization can be induced by shear stress
in the absence of an electric field; this is the piezoelectric effect discussed
earlier, and (c) from (5.10.4), that the field-induced tilt, or the electroclinic
effect in the SA phase should diverge as the temperature approaches 7^*A.
However, this treatment is inadequate in many respects. For example,
fig. 5.10.5 shows that the dielectric constant does not exhibit a divergence
at all on approaching TC*A. In order to give a better description of the
properties of the Sc* phase, Pikin and Indenbom (248) proposed the following
free energy expression:
Here a = ao(T— To), To being the transition temperature for the cor-
responding racemate, b > 0 and is temperature independent, k the elastic
constant, s the high temperature dielectric constant (i.e., in the absence of
ferroelectricity), ju and C are the constants describing respectively the
386 5. Smectic liquid crystals
flexoelectric and piezoelectric types of coupling between P and 0; A is
called the Lifshitz invariant parameter characteristic of chiral molecules
and produces the helicoidal structure. Minimizing with respect to q, P
andfl,
A + suC
q = — -^r- 2 = constant,
k-sju
(5.10.7)
The main predictions of the model are: (i) the transition temperature of the
chiral compound is higher than that of the racemate, (ii) the tilt angle 0 and
hence P (which is proportional to 6) exhibit a power law variation with
temperature with the mean field exponent of 0.5, and (iii) the pitch and the
ratio P/0 are independent of temperature.
While this theory is an improvement over the previous one, its
predictions are still not quite in agreement with observations. The exponent
governing the 6 variation is generally found to be smaller than the mean
field value. Further, the theory is unable to account for the non-monotonic
temperature variation of the pitch and the anomalous behaviour of P/0.
More elaborate models have been proposed(249236) involving additional
phenomenological coefficients, including a sixth order term in 0 and a term
involving P292. A 'generalized' expansion of the form
F = \aO2 + \b6* + \c6« - AqO2 + \Kzq202
\\\\\\\\\\\\\\\\\\\\\\\ 11 ii mi mini mi
wwwwwwwwwww
\\\\\\\\\\\\\\\\\\\\\
wwwwwwwwwwww
Fig. 5.10.9. The SSFLC cell: The bookshelf geometry of a thin film of smectic C*
sandwiched between two glass plates (a) field ' up' (normal to the plane of the
diagram) and (b) field 'down'.
388
6.1 Liquid crystalline structures 389
RO
RO I = Cu M = Cu
(g) (h)
Fig. 6.1.1. Examples of disc-shaped mesogens: (a) hexa-n-alkanoates of benzene,(3)
(b) hexakis ((4-octylphenyl)ethynyl)benzene,(11) (c) hexa-n-alkanoates of scyllo-
inositol,(12) (d) hexa-n-alkanoates of triphenylene and hexa-n-alkoxytripheny-
lene, (1314) (e) hexa-n-alkyl and alkoxybenzoates of triphenylene, (1516) (/) hexa-n-
alkanoates of truxene, (1718) (g) bis(3,4-nonyloxybenzoyl)methanato copper(II),(19)
(h) octasubstituted metallophthalocyanine.(20)
Lattice Temperature
R Space group parameters (A) (°C)
C5HUO P6 2/m 2/m a= 18.95 ^80
C 7 H 15 O P6 2/m 2/m a= 22.2 ^80
C 8 H 17 O P6 2/m 2/m a= 23.3 ^80
C U H 23 COO PVa a= 44.9, b = 26.4 117
P6 2/m 2/m a= 26.3 105
C 7 H 15 COO P^/a a= 37.8,/? = 22.2 100
P 2x/a a= 51.8, 6 = 32.6 165
QH^-O-C.H.-COOf C2/m a= 30.7, 6 = 28.4 185
(b)
id) (e)
Fig. 6.1.2. (a)-(e) Columnar phases of disc-shaped molecules.(6) Plan views of the
two-dimensional lattice; ellipses denote discs that are tilted with respect to the
column axis: (a) hexagonal (P6 2/m 2/m); (b) rectangular (P2 1 /a); (c) oblique
(P^; (d) rectangular (P 2 /a); (e) rectangular face-centred, tilted columns (C2/m).
(/) The nematic phase.
long, with the column axis parallel to the axis of the strand/ 2 2 6) The results
of these studies are summarized below.
(a) The correlation length of the two-dimensional lattice of the
hexagonal columnar phase of (C 1 3 H 2 7 COO) 6 -truxene (fig. 6.1.1 ( / ) ) is
greater than 4000 A (or approximately 200 columns), the lower limit being
6.1 Liquid crystalline structures 391
0.40
10 0
rc-r(°c)
Fig. 6.1.3. Quadrupole splittings for the aromatic v™ and a-aliphatic VQ deuterons
of deuterated hexa-n-hexyloxytriphenylene (THE6) as functions of temperature
(T— Tc) in the mesophase region, where Tc is the mesophase-isotropic transition
point. The open circles correspond to measurements on neat THE6-ard 6 and
THE6-ad 12 separately, while the filled circles correspond to a 2:1 mixture of the
two isotopic species. The scale on the upper right-hand side gives the orientational
order parameter of the aromatic part. The curve at the bottom gives the ratio of the
quadrupole splittings for the a-aliphatic and aromatic deuterons (Goldfarb, Luz
and Zimmermann(27)).
stacking of the triphenylene cores in each column, and the latter one in
which the column is liquid-like. X-ray studies using freely suspended
strands,(26) have shown that in the ordered phase there is a helicoidal
stacking of the triphenylene cores within each column, the helical period
being incommensurate with the intermolecular spacing.(28) In addition, a
three-column superlattice develops as a result of the frustration caused by
molecular interdigitation in triangular symmetry. It may be argued that if
there is no intercolumn interaction true long-range translational order
6.1 Liquid crystalline structures 393
RO .OR
OC
R
=C12H25°- -coo-
(a) (b)
Fig. 6.1.4. (a) Cyclotricatechylene hexaesters, the cores of which are cone-shaped
(Malthete and Collet(29)), (b) hexa-(/?-n-dodecyloxybenzoyl) derivative of macro-
cyclic polyamines which is hollow at the centre (Lehn, Malthete and Levelut(33)).
Both (a) and (b) show columnar mesophases; the latter mesophase has been
described as 'tubular'.
H25C,2C> O O
12H25
4TT .
V 3d
V3
R \
C = A + B,
where d is the lattice constant.
The appropriate single particle potential, which depends on the
orientation of the short axis of the molecule as well as the position r of its
centre of mass, may be written in the mean field approximation as
V^x, y9 cos 0) = -Vo P2(cos 8) {s + a<r[cos (A •r) + cos (B •r) + cos (C •r)]},
(6.2.1)
retaining only the leading terms in the Fourier expansion. Here Vo is the
396 6. Disco tic liquid crystals
interaction energy which determines the nematic-isotropic transition, a is
the McMillan parameter given by
2exp[-(27rro/V3</)2], (6.2.2)
r0 being the range of interaction which is of the order of the size of the
aromatic core, s = </»(cos0)> (6.2.3)
is the usual orientational order parameter, and
a = |<[cos (A • r)+ cos (B • r)+ cos (C • r)] i>2(cos 9)} (6.2 A)
is an order parameter coupling the orientational and the translational
ordering. The angular brackets represent the statistical average over the
distribution function derived from the potential (6.2.1), the spatial
integrations being carried out over a primitive cell of the hexagonal lattice.
This form of the potential ensures that the energy of the molecule is
minimum when the disc is centred in the column with its plane normal to
the z axis.
The free energy can then be calculated using standard arguments:
(6.2.5)
Isotropic
1.0
I0-8 Nematic
I
c
Columnar
I
0.4
I J
0 0.2 0.4 0.6 0.8
Model parameter (a)
Fig. 6.2.1. Theoretical plot of the reduced transition temperature against the model
parameter a showing the hexagonal, nematic and isotropic phase boundaries. All
the transitions are of first order.
2 \ 9x dy ) 2 \_\ dx dy
where B and D are the elastic constants for the deformation of the two-
dimensional lattice in its own plane; ux and uy are the displacements along
x and y at any lattice point, and /r33 is the Frank constant for the curvature
deformation (bending) of the columns. (In the notation of the standard
crystal elasticity theory, B = | ( c n + c12) and D = \{clx — c12).) We neglect
here the splay and twist deformations because they give rise to a distortion
of the lattice and involve considerable energy. (51) We also neglect any
contributions from the surface of the sample. Writing the displacement u
in terms of its Fourier components,
H(r) = X>(q)exp(iq-r); (6.3.2)
Q
where L is the length of the columns, L the linear dimension of the lattice
in the xy plane and d its periodicity. Assuming that U > L
<W2> = [kB T/4B£Xd$\ [l-(d/L% (6.3.3)
(5>52>53)
where X = (ko/Bo)* is a characteristic length. The structure is
therefore stable as L -> oo. As is well known from the classical work of
Peierls(54) and Landau (55) , the two-dimensional lattice itself is an unstable
system with <w2> diverging as lnL. ( 5 6 5 7 ) Hence the curvature elasticity of
the liquid-like columns stabilizes the two-dimensional order in the
columnar liquid crystal. This result was first proved by Landau, who
observed: ' Thus bodies having such a structure could in theory exist, but
it is not known whether they do in fact exist in Nature.' (58)
(6.3.5)
400 6. Discotic liquid crystals
Thus, in contrast to smectic A and the two-dimensional lattice, for which
the displacement-displacement correlation is of logarithmic form, the
columnar liquid crystal gives the usual Bragg reflexions. As noted in §6.1,
this is borne out by high resolution X-ray experiments on well oriented
monodomain discotic strands.(25)
So far it has been assumed that the length (Z/) of the liquid columns
is much larger than L. One may similarly consider the opposite situation
Z/ <^ L. In this case, it turns out that for the bounded sample
— In Z/ for larger L.
If the surfaces are free <V> will have additional terms, which may be
analogous to those for a two-dimensional lattice. In any case, it is clear that
the mean square fluctuations of the lattice as well as the Debye-Waller
factor may be expected to show a certain dependence on the linear
dimensions of the sample.
Tco*
where q± = (ql + qffi and co is the angular frequency of the light.(41) The
scattering is similar to that from smectic A in certain geometries (see
§5.3.4), but is, of course, small compared to that from a nematic.
kS3 i
the columns buckle. This has actually been observed, (60) but there is a
significant discrepancy between theory and experiment which has not been
explained satisfactorily.
w (
l T+ «8^
402 6. Discotic liquid crystals
dt
dK
At
dK
6e
where
8
^2 ^2 ^2 ^2
A + 8
where y/ is the angle between the direction of propagation and the column
axis. We have ignored the coupling between the lattice and the curvature
deformation of the columns. The third mode is a transverse wave whose
polarization is orthogonal to that of second sound. This wave propagates
6.4 Defects in the columnar liquid crystal 403
Fig. 6.3.1. Dependence of the sound velocities on the polar angle y/ in the columnar
liquid crystal.
because the two-dimensional lattice can sustain a shear. Its velocity for any
arbitrary direction is given by
Fig. 6.3.1 depicts the variation of the velocities of the three waves with
polar angle. This angular dependence can be studied by Brillouin
scattering, as has been demonstrated for smectic A (see fig. 5.3.11). In the
present case, there should be one, two or three pairs of Brillouin
components depending on the orientation, but no experiments have yet
been reported.
Fig. 6.4.1. The hexagonal columnar phase with the symmetry elements in the
structure.
6.4.1 Dislocations
The Burgers vector b of a dislocation in the columnar structure is normal
to the columnar axis n. In general
b = /a + ma',
{B + D) 9 (%£ -DA(%*-%*) =0
ox\ax oy oy\ox oy J
6.4 Defects in the columnar liquid crystal 405
Fig. 6.4.2. The discotic liquid crystal appearing in the isotropic phase when a
sample is cooled very slowly. The growth pattern is diagnostic of the hexagonal
symmetry of the columnar structure: (a) Queguiner, Zann and Dubois (62), (b)
Bouligand(61).
406 6. Discotic liquid crystals
b= a ,M b
Fig. 6.4.3. Dislocations in the columnar phase: (a) and (Z?) longitudinal edge
dislocations; (c) and (d) transverse edge dislocations; (e) and (/) screw dis-
locations ; (g) a hybrid of screw and edge dislocations. It should be noted that the
Burgers vector b = a for (a), (c), (e) and (g), and b = a —a' for (b), (d) and (/).
(Bouligand.(61))
and
These are exactly like the equations for edge dislocations in crystals.(63) The
solutions are
B y2\
6.4 Defects in the columnar liquid crystal 407
where Ec and rc are the energy and radius of the core. The radial and
angular components of the force of interaction between two edge
dislocations are
Db1b2
fr = 2n(\-v)r'
/« TTrV s i n 2 a '
2n(\— v)r
where v is Poisson's ratio.
Transverse edge dislocations
The dislocation line is now normal to n. Let it be along the x axis, so that
the only component of the displacement that needs to be considered is u y.
Minimization of the free energy yields
dy2 33
dz* '
which is exactly of the same form as that for edge dislocations in smectic A
(see §5.4.2). The solution is
b b
Screw dislocations
Let the dislocation line be along x. The relevant component of the
displacement is therefore ux, and the equation of equilibrium becomes
X 1^ X
33
8/ ~ 8z4 '
408 6. Disco tic liquid crystals
(a) (b)
o° o S o °o
Oo>o O nO°
o
o o oo
° o o oo oo
0 o o oo o oo ooo
o ooo o o o oo
o o oo
(c)
Fig. 6.4.4. Disclinations in the columnar phase: (a) and (b) —n/3 and n/3
longitudinal wedge disclinations about the sixfold axis L6; (c) and (d) n transverse
wedge disclinations about the binary axes T2 and 62 respectively; (e) —n transverse
wedge disclination leading to the formation of walls; (/) two n disclinations at right
angles to each other, one about T2 and the other about 92. (Bouligand.(61))
which is again of the same form as the equation for an edge dislocation in
smectic A. The solution is
b b
uxx = 7 + —
4 An
Fig. 6.4.5. Photograph indicating the presence of two n disclinations at right angles
to each other as depicted in fig. 6.4.4 (/). (Oswald.(64))
6.4.2 Disclinations
Longitudinal wedge disclinations are the standard crystal disclinations in
a hexagonal lattice. The rotation vector is L 6 or L3 or L2, parallel to the
columns. Two examples of such defects are shown in figs. 6.4.4 (a) and (b).
The lattice gets compressed near a positive disclination and stretched near
a negative one. Generally, most of these disclinations have prohibitively
large energies, and hence they occur as unlike pairs at the core of a
dislocation.
In transverse wedge disclinations the rotation vector is 62 or T2, normal
to n. Examples of ± n disclinations are shown in figs. 6.4.4(c), (d) and (e).
Two transverse wedge disclinations may occur in association as shown
in fig. 6.4.4 (/). The angle between the rotation axis may be 90°, 60° or 30°.
Such defects have been observed experimentally. (64) Fig. 6.4.5 presents a
photograph which may be interpreted as arising from two n disclinations
410 6. Discotic liquid crystals
(a)
Fig. 6.4.6. Developable domains in the columnar phase, (a) The developable
surface is degenerated into a straight line S common to the planes P. The columnar
axes C form coaxial circles about S. (b) The developable surface D is a cylinder. The
columns (or the layers in the case of smectic A) are a set of parallel and equispaced
involutes of a circle, (c) A Reimann surface generated by half-tangents to a helix.
The columns are normal to the half-tangents. (Bouligand.(61))
parallel to the glass slides and at right angles to each other as depicted in
fig. 6.4.4 (/).
The symmetry of the columnar phase also permits the occurrence of
twist disclinations in the hexagonal lattice and of hybrids consisting of a
twist disclination in the hexagonal lattice and a wedge disclination in the
director field. According to Bouligand these defects are not likely to exist.
(i) If the developable surface degenerates into a straight line, then the
columns form a set of coaxial circles around this line (fig. 6.4.6(a)).
The line need not necessarily be a twofold axis, 02 or 7L The structure
of this defect is similar to the 2n disclinations of smectics.
(ii) If the developable surface is a cylinder, then the columns are along the
involutes of a circle in any plane normal to the axis of the cylinder (fig.
6.4.6 (b)). This defect is similar to a disclination of unit strength. It is
seen that this is an obvious generalization of the solutions for smectic
A. Structures similar to this have been observed by Oswald.
(iii) If the developable surface is a Reimann surface generated by half-
tangents to a helix, then the columns are normal to the half-tangents
and are involutes of the helix (fig. 6.4.6 (c)). This defect has the
features of a dislocation and a disclination, and can therefore be
described as a dispiration.
(a) (b)
Fig. 6.5.2. Flow alignment of the director in nematic liquid crystals, (a) For rod-
shaped molecules the alignment angle 9 with respect to the flow direction lies
between 0° and 45°, while (b) for disc-shaped molecules it lies between —90° and
-45° (or equivalent^ between 90° and 135°).
where 60 lies between 0° and 45° with respect to the flow direction (fig.
6.5.2(a)). In practice 00 is usually a small angle. In certain nematics, it is
found that //3 > 0 at temperatures close to the nematic-smectic A transition
point. Under these circumstances there is no equilibrium value of #0, and
in the absence of an orienting effect due to the walls or a strong external
field, the flow becomes unstable.(76)
It has been suggested that in the N n phase, the disc-like shape of the
molecule may have a significant effect on ju2 and //3.(77'78) The stable
orientation of the director under planar shear will now be as shown in fig.
6.5.2(b). Thus it can be argued that both ju2 and jus should be positive, and
the flow alignment angle 60 should lie between —45° and —90°. It then
follows that when ju2 < 0, the director tumbles and the flow becomes
414 6. Discotic liquid crystals
Fig. 6.6.1. Two examples of molecules which exhibit the biaxial nematic phase:
(a) (bis-1 -(/?-n-decylbiphenyl)-3-(/?-ethoxyphenyl) propane-1,3-dionatocopper
(H))<8i,82) (hereafter referred to as complex A); (b) l,12-te(pentakis((4-pentyl-
phenyl)ethynyl)pheny loxy)dodecane.(83)
Fig. 6.6.2. Conoscopic figure demonstrating the biaxiality of the nematic phase of
complex A. (8284)
(i) H (ii) H
\ T I . I . I . I . i , i . i . i , i . i . i . i i i
-12 - 6 0 6 12 - 2 4 - 1 8 - 1 2 - 6 0 6 12 18 24
(a) 26 (deg)
(i) (ii)
H
Fig. 6.6.3. Raw microdensitometer scans of the X-ray intensity plotted against
diffracting angle (26) for magnetically aligned nematic samples: (a) the uniaxial
nematic phase of 80CB at 77 °C; (b) the biaxial nematic phase of complex A at
168.5 °C, (i) meridional scan (parallel to / / ) , (ii) equatorial scan (perpendicular to
H). M represents the diffraction peaks from the mylar film which covered the
windows of the sample holder and heater assembly. (8586)
(a) (b)
Fig. 6.6.4. Schematic diagram of the molecular order in (a) the uniaxial nematic
phase and (b) the biaxial nematic phase.
Toulouse(118) describes a s ' topological rigidity'. These and other ideas have
yet to be investigated experimentally. The availability of the N b phase in
simple thermotropic systems is likely to make it conveniently possible to
test some of these predictions.
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128 D. Coates and G. W. Gray, Mol. Cryst. Liquid CrySt., 24, 163 (1973).
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Chapter 5
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5 A. Tardieu and J. Billard, / . de Physique Colloq., 37, C3-79 (1976).
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7 W. L. McMillan, Phys. Rev., A 4, 1238 (1971).
8 J. G. Kirkwood and E. Monroe, / . Chem. Phys., 9, 514 (1941).
9 K. Kobayashi, Mol. Cryst. Liquid Cryst., 13, 137 (1971).
10 R. B. Griffiths, Phys. Rev., B 7, 545 (1973).
11 W. L. McMillan, Phys. Rev., A 6, 936 (1972).
12 R. G. Priest, Mol. Cryst. Liquid Cryst., 37, 101 (1976).
13 F. T. Lee, H. T. Tan, Y. M. Shih and C. W. Woo, Phys. Rev. Lett., 31, 1117
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14 L. Senbetu and C. W. Woo, Phys. Rev., A 17, 1529 (1978).
15 M. D. Lipkin and D. W. Oxtoby, / . Chem. Phys., 79, 1939 (1983).
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18 A. Kloczkowki and J. Stecki, Mol. Phys., 55, 689 (1985).
19 D. A. Badalyan, Sov. Phys. Crystallogr. 27, 10 (1982).
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24 P. G. de Gennes, / . de Physique, 30, C4-65 (1969).
25 L. D. Landau and E. M. Lifshitz, Statistical Physics, Part I, 3rd edn,
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26 R. Schaetzing and J. D. Litster, Advances in Liquid Crystals, Vol. 4 (ed.
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438 References: Chapter 5
Chapter 6
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4 S. Chandrasekhar, Advances in Liquid Crystals, Vol. 5 (ed. G. H. Brown), p.
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5 S. Chandrasekhar, Phil. Trans. Roy. Soc, London, A309, 93 (1983).
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7 C. Destrade, P. Foucher, H. Gasparoux, N. H. Tinh, A. M. Levelut and J.
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8 A. J. Leadbetter, in Thermotropic Liquid Crystals, Critical Reports on
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9 S. Chandrasekhar and G. S. Ranganath, Rep. Prog, in Physics, 53, 57 (1990)
10 A more or less complete bibliography on the subject up to 1984 has been
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11 B. Kohne and K. Praefcke, Chimia, 41, 196 (1987).
12 B. Kohne and K. Praefcke, Angew. Chem., 96, 70 (1984).
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15 C. Destrade, M. C. Bernaud, H. Gasparoux, A. M. Levelut and N. H. Tinh,
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References: Chapter 6 447
16 N. H. Tinh, H. Gasparoux and C. Destrade, Mol. Cryst. Liquid Cryst., 68,
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19 A. M. Giroud-Godquin, M. M. Gauthier, G. Sigoud, F. Hardouin and
M. F. Achard, Mol. Cryst. Liquid Cryst., 132, 35 (1986).
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20 C. Piechocki, J. Simon, A. Skoulios, D. Guillon and P. Weber, / . Am. Chem.
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21 F. C. Frank and S. Chandrasekhar, / . de Physique, 41, 1285 (1980).
22 D. H. Van Winkle and N. A. Clark, Phys. Rev. Lett., 48, 1407 (1982).
23 C. R. Safinya, K. S. Liang, W. A. Varady, N. A. Clark, and G. Andersson
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24 C. R. Safinya, N. A. Clark, K. S. Liang, W. A. Warady and L. Y. Chiang,
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25 E. Fontes, P. A. Heiney, M. Ohba, J. N. Haseltine and A. B. Smith, Phys.
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26 E. Fontes, P. A. Heiney and W. H. De Jeu, Phys. Rev. Lett., 61, 1202 (1988).
27 D. Goldfarb, Z. Luz and H. Zimmermann, J. de Physique, 42, 1303 (1981).
28 A. M. Levelut, P. Oswald, A. Ghanem and J. Malthete, J. de Physique, 45,
745 (1984).
See also, A. M. Levelut, / . de Physique Lettres, 40, L 81 (1979).
29 J. Malthete and A. Collet, Nouv. J. Chem., 9, 151 (1985).
30 A. M. Levelut, J. Malthete and A. Collet, J. de Physique, 47, 351 (1986).
31 H. Zimmerman, R. Poupko, Z. Luz and J. Billard, Z. Naturforsch., 40a, 149
(1985).
32 Lin Lei, Wuli (in Chinese) 11, 171 (1982).
33 J. M. Lehn, J. Malthete and A. M. Levelut, / . Chem. Soc. Chem. Commun.,
1794 (1985).
34 C. Destrade, N. H. Tinh, J. Malthete and J. Jacques, Phys. Lett., 79A, 189
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Cryst. Lett., 64, 233 (1981).
35 A. M. Giroud-Godquin and J. Billard, Mol. Cryst. Liquid Cryst., 66, 147
(1981).
36 K. Ohta, H. Muroki, A. Takagi, K. I. Hatada, H. Ema, I. Yamamoto and
K. Matsuzaki, Mol. Cryst. Liquid Cryst., 140, 131 (1986).
37 A. C. Ribeiro, A. F. Martins and A. M. Giroud-Godquin, Mol. Cryst.
Liquid Cryst. Lett., 5, 133 (1988).
38 S. Chandrasekhar, Plenary Lecture, X International Liquid Crystals
Conference, York, 15-21 July 1984; Mol. Cryst. Liquid Cryst., 124, 1 (1985).
39 J. Malthete, A. M. Levelut and N. H. Tinh, / . de Physique Lettres, 46, L-875
(1985).
40 N. H. Tinh, C. Destrade, A. M. Levelut and J. Malthete, / . de Physique, 41,
553 (1986).
41 E. I. Kats, Sov. Phys. JETP, 48, 916 (1978).
42 G. E. Feldkamp, M. A. Handschy and N. A. Clark, Phys. Lett. 85A, 359
(1981).
448 References: Chapter 6
451
452 Index
cholesteryl nonanoate: equations, 97-8; thermal instability
blue phases, 16 201-5; twisted nematic and
Borrmann effect, 236 supertwisted nematic devices 106-15;
critical divergence of pitch, 349 viscosity coefficients, 92-3
molecular structure, 16 of smectic A:
transitions, 16 breakdown of conventional
Clausius-Clapeyron equation, 27 hydrodynamics, 325; damping rate of
conductivity: undulation mode, 322; elastic free
electrical, 177, 181 energy density, 310; energetics of
thermal, 202-5 defects, 327-39; fluctuations, 317-19;
consistency relation light scattering, 317-19; mechanical
Chang, 72 instability, 314—16; Peierls-Landau
Krieger-James, 72 instability 312-14; permeation, 321;
Maier-Saupe, 44 ultrasonic propagation, 323-5;
continuum theory viscosity coefficients, 321
of cholesterics: of smectic C:
coefficients of thermal conductivity, elastic free energy density, 367;
260; distortion by external fields, fluctuations, 367; light scattering, 367
277-88; elastic free energy density, 97, convection
284-5; energetics of defects, 248-58; oscillatory, 205
flow along the helical axis stationary, 202-5
(permeation), 270-3; flow normal to critical end point, 355
the helical axis, 274-6; critical point, 353
thermomechanical coupling, 258-67; curvature elasticity, see elastic constants
torque induced by electric field 4-cyanobenzylidene-4/-octyloxyaniline, see
(electromechanical coupling), 264-7; CBOOA
torque induced by heat flux (the cyanobiphenyls (4/-n-alkyl-4-
Lehmann rotation phenomenon), cyanobiphenyl) nCB
262-3; viscosity coefficients, 260 5CB (pentyl compound):
of columnar liquid crystals: antiparallel local order, 80;
acoustic wave propagation, 401-2; applications, 110; dielectric anisotropy
elastic free energy density, 397; 79; molecular structure, 15; surface
energetics of defects, 402-8; tension, 81; transitions, 15; X-ray
fluctuations, 398; light scattering, 400; studies, 79
mechanical instabilities, 400-1; 6CB:
Peierls-Landau instability, 398; X-ray electric and magnetic birefringence, 66
scattering, 399 7CB:
of nematics (including discotic applications, 110; X-ray studies, 79
nematics): 8CB:
backflow and kickback effects, 162-7; critical exponents associated with the
distortions due to external fields, smectic A-nematic transition, 347;
98-117; elastic free energy density, 57, molecular structure, 15; transitions, 15
97, 116; electrohydrodynamic 9CB:
instabilities, 177-95; energetics of critical exponents associated with the
defects, 117-44; Ericksen-Leslie smectic A-nematic transition, 347
equations, 85-94; flexoelectricity, 12CB:
205-12; flow properties, 144-59, surface-induced smectic order in the
413-14; Freedericksz effect, static isotropic phase, 84; X-ray specular
theory, 98-106; Freedericksz effect, reflectivity from free surface, 84
dynamics of, 161-7; hydrodynamic 80CB (octyloxycompound):
instabilities, 155-7, 195-201,413-14; critical exponents associated with the
light scattering, 162-77; smectic A-nematic transition, 347;
Oseen-Zocher-Frank elasticity P—T diagram, 356; reentrant
equations, 94-7; Parodi's relation, 94; behaviour at elevated pressures, 356;
periodic distortions in highly surface-induced smectic order in
anisotropic media, 113-15; reflexion nematic phase, 83; X-ray specular
of shear waves, 159-61; summary of reflectivity from free surface, 83
Index 453
cybotactic groups, 2, 4, 83 discotic liquid crystals
columnar structures, 10, 390
Darwin's theory of X-ray diffraction, see columnar phases of conical, macrocyclic,
optical properties of cholesterics phasmidic molecules, 393—4
defects discotic lamellar phase, 9, 394, 397
in cholesterics: discotic nematic, 10, 393, 411-14
X (chi)-edge disclinations, 252; / (chi)- disc-shaped molecules, 389
screw disclinations, 249-51; extension of McMillan's model to
disclination pairs, 250-1; dislocations, discotics, 394-7
254-8; edge dislocations, 254-7; high resolution X-ray studies on freely
fingerprint textures, 254-6; suspended strands, 389-93
Grandjean-Cano pattern, 257-8; ordering of the cores and chains, 390-2
lattice disclinations, 252^4; reentrant behaviour, 394
pincements, 254-6; screw dislocations, structure and classification of
254 mesophases, 8-10, 388-93
in columnar liquid crystals, 402-11 twisted nematic (or cholesteric), 393
developable domains, 409—11; see also continuum theory, defects,
disclinations, 408-9; dislocations, discotic nematics, discotic polymers
403-8; longitudinal dislocations, discotic, nematics, 10, 390, 393, 411-14
406-7; longitudinal wedge diamagnetic anisotropy, 412
disclinations, 408; screw dislocations, dielectric anisotropy, 412-13
408; transverse dislocations, 407; director, 390, 412
transverse wedge disclinations, 408 Frank (elastic) constants, 413
in nematics: hydrodynamical properties, 413-14
angular forces between disclinations, optical anisotropy, 412
140-3; Brochard-Leger walls, 136; discotic polymers, 10-12
consequences of elastic anisotropy, columnar nematic, 11-12
139—43; core structure, 143—4; director columnar phase, 11-12
field in the neighbourhood of, 119-20; sanidic nematic, 11-12
disclination loops, 127-8; energies and dispersion forces, 41-2
interactions, 120-2; Helfrich walls, donors and acceptors, 12, 358
135; non-singular structures, 123-6; Dupin cyclides, 329, see focal conic
schlieren textures in discotic nematics, textures
412; singular points, 129-30; solitons, dynamic scattering, 178, 288, see also
137-9; threads and schlieren textures, applications
7, 117; twist disclinations, 126-8;
umbilics, 136-7; wedge disclinations, elastic constants
117-28 nematics:
in smectic A: critical divergence of, 3 4 2 ^ ;
disclinations, 328-9; edge dislocations, dependence on order parameter,
333-7; energies and interactions, 59-60; experimental determination of
335-7; focal conic textures, 327-33; splay, twist and bend (or Frank)
screw dislocations, 338 constants, 98-106, 172; permanent
in smectic C: splay and twist, 96, 117
core structure 3 7 3 ^ ; disclinations in smectic A:
the odirector field, 368-9; edge critical divergence of twist, bend and
dislocations, 369-70; toric domains, layer compressibility constants, 343,
329 348; experimental determination of
dielectric anisotropy, theory of, 51-7, 76-8 layer compressibility, 315, 322
dielectric dispersion, 56 electric birefringence (Kerr effect), 55,
4,4'-di-n-alkoxyazoxybenzenes 63-6
dielectric dispersion, 56 electric field induced distortions
odd-even effect, 48-51 cholesterics:
structure, 50 Carr-Helfrich instability, 286-7;
see also PAA, PAP conduction and dielectric regimes,
director, definition of, 85-6 288; square grid pattern, 282, 286-8;
disclinations, see defects storage mode, 288
454 Index
magnetoclinic effect, 371-2 molecular flexibility, 37, 41, 48-52; see also
Maier-Saupe theory of nematics, 38-51, end chains
70-1 molecular statistical theories:
applications cholesterics, 298
binary mixtures, 51; dependence of discotics, 394-7
elastic constants on the order nematics, 17-61, 71-80
parameter, 57-60; dielectric smectic A, 302-9
anisotropy, 51-6; odd-even effect, smectic C, 364
47-51 monotropic transition, 14, 16, 379
extension of the theory multicritical point, nematic-smectic
to cholesterics, 298; to discotics, A-smectic C (NAC), 374-8
394-7; to smectic A (McMillan's Chen-Lubensky model, 375-8
model), 302-9 high resolution X-ray calorimetric and
limitations of the theory, 47-9, 70-71 light scattering studies, 378
Mauguin-Oseen-de Vries model, 237^41 topology of phase diagram in the
MBBA temperature-concentration and
backflow effects, 165 pressure-temperature planes, 374, 376
disclination patterns, 122
electrohydrodynamic distortions, 180, near neighbour correlations
183^ antiparallel (or antiferroelectric)
flexoelectric coefficients, 207-9 correlation, 75-8
flow birefringence, 71 Bethe approximation, 71
heats of transition, 26 correlation lacking a centre of inversion,
light scattering studies 289
in nematic phase, 60; in the isotropic Krieger-James approximation, 72-3
phase, 67-8 short range order parameter, 75
magnetic birefringence, 64 nematic-isotropic transition
mixtures with cholesterics, dependence of Bethe approximation, 71-80
pitch on composition, 298 effect of pressure, 27-30, 46-7
molecular orientation at free surface, Landau-de Gennes model, 61-3
83 latent heat, 15-16,26,47
oblique rolls in electrohydrodynamic Maier-Saupe theory, 38-48
patterns, 211 molecular statistical theories, 17^8
roll instability threshold, 198 pressure-induced mesomorphism, 28-30
thermal instability, 202, 205 short range order effects, 61-70
torque in a rotating magnetic field, 148 volume change, 26, 45
transverse pressure and secondary flow, nematic liquid crystals, 1-3, 8-10
158 nematics as solvents, 39, 146
viscosity (or Leslie) coefficients, 155 nuclear magnetic resonance (NMR)
volume change at transition, 26 studies, 39, 61, 308-9, 392
McMillan's model of smectic A, 302-9
melting of odd-even effect, 48-51
inert gas crystals, Lennard-Jones and Onsager's reciprocal relations, 69, 94
Devonshire model, 17-19 Onsager's theory of dielectric polarization,
molecular crystals, Pople-Karasz model, 52
19-27 Onsager's theory of the hard rod fluid, 31
mesomorphic groups, Hermann's optical properties of cholesterics
classification, 8 absorbing systems, 220-2, 232-6
mesomorphism, thermotropic and analogy with Darwin's dynamical theory
lyotropic, 1 of X-ray diffraction, 222-232
metallomesogens, 389, 414 Borrmann effect, 232-6
4-methoxybenzylidene-4/-butylaniline, see equivalence of the continuum and
MBBA dynamical theories, 241-5
Miesowicz's viscosity coefficients, 144-5, exact solution of the wave equation: the
155 Mauguin-Oseen-de Vries model,
miscibility criterion, 300 237^1
molecular field, 38 oblique incidence, 245-7
Index 457
propagation along the helical axis, PAA
213^5 comparison of properties with hard rod
propagation normal to the helical axis, and hybrid model calculations, 37,
247-8 60
rotatory power, reflectivity and circular dielectric constants, 53
dichroism as functions of wavelength, dielectric dispersion, 56
pitch and sample thickness, 217-20, dipole moment, 55
227-32, 239^1 electrohydrodynamic distortions, 178
optical textures flow birefringence, 69-71
cholesterics: heat of transition and volume change,
droplets with a /-line of strength 2, 26
442; fingerprint texture, 255-6; Leslie coefficients, 150
Grandjean-Cano pattern, 258; helical light scattering studies, 59, 66-8, 83, 172,
configurations of disclination pairs, 176
143, 249-51 lines of constant order parameter vs. In V
columnar liquid crystals: and In T, 46
texture showing two orthogonal n magnetic and electric birefringence, 62-5
disclinations, 410 Miesowicz coefficients, 146
nematics: molar volume at the transition, 44
disclination loops, 127-8; schlieren molecular orientation at the free surface,
textures {structures a noyaux), 6, 30, 83
117-20, 365, 412; singular points, molecular structure, 15
129-32; threads, 7-8; umbilics, orientational order parameter, 27, 40
136-8 PAA -I- cholesteryl nonanoate, Borrmann
smectic A: effect in, 236;
batonnets, 30, 333; fan-shaped and Poiseuille flow, 150-3
polygonal textures, 9, 331; focal conic P-T diagram and other pressure studies,
textures, 9, 30, 327-33; stepped drop 28,46
(goutte a gradins), 332, toric domains, surface tension, 81
329 torque in a rotating magnetic field
smectic C: (Tsvetkov's experiment), 148
edge dislocations, 370; toric domains, transitions, 15
329 twist elastic constant, 104
order parameter see also 4,4/-di-n-alkoxyazoxybenzenes
complex order parameter PAP
smectic A, 340; smectic C, 370 heat of transition and volume change,
orientational order parameter 26
curves, 40, 45, 75, 77, 303-5, 308-9; light scattering studies, 59
definition, 38—41; experimental Miesowicz coefficients, 146,
determination of <P2>, 39-^0, 308-9; orientational order parameter, 27
<.P4> from polarized Raman studies, twist elastic constant, 104
48-9; short range order parameter, see also 4,4/-di-n-alkoxyazoxybenzenes
74—5, 77; variation near an interface, Parodi's relation, 93, 98
82,211 penetration depth, 314, 322, 342, 398
positional order parameter in melting phase diagrams, 28-9, 291, 295, 306, 353-6,
theory, 23-4 376, 397
translational order parameter planar structure, see homogeneous
amplitude of one-dimensional density orientation
wave (smectic A), 303-5, 307, 340; plastic crystals, 22
density wave in two dimensions Poiseuille flow, 148-52, 157-9, 268-9,
(columnar phase), 395 270-3
orientation distribution function in MBBA polymorphism in
derived from Raman studies, 49 smectic A, 350-2
Oseen's equation of motion for the smectic C, 364-5
director, 87 thermotropics, 14-16
Oseen-Zocker-Frank elasticity equations, pressure studies, 27-9, 46-7, 297, 356, 372,
94-7 374-6
458 Index
pretransition effects in the vicinity of molecular models, 357
cholesteric-isotropic transition: multiple reentrance, 357
anomalous optical rotation in the rotational transitions in crystals, 19
isotropic phase, 289-93;
coherence lengths, 293 second sound, 324-6, 402, 404
nematic-isotropic transition: shear flow, 69, 152-7, 195-201, 274-7, 383
Bethe approximation, 71-80; shear waves, reflexion of, 159-61
coherence length, 68; flow short-range order, see near neighbour
birefringence, 69-71; Landau-de correlations, pretransition effects
Gennes model, 61-3; light scattering smectic A, 6, 301, 341
studies, 66-8; magnetic and electric absence of true long range translational
birefringence, 63-6; see also near order, 321
neighbour correlations high resolution X-ray scattering studies,
smectic A-cholesteric transition: 313-14
analogy with the behaviour of a polymorphic forms of smectic A and
superconductor in a magnetic field, transitions between them, 351-5,
348-9; critical divergence of the pitch, see also under continuum theory, defects,
349-50 optical textures
smectic A-nematic transition: smectic A* or the twist grain boundary
critical divergence of twist and bend phase:
elastic constants, 343; critical example of a compound which shows
divergence of viscosity coefficients, this phase, 359
345; critical exponents, 347; high structure of smectic A*, 359
resolution X-ray, light scattering, X-ray and optical studies, 359-60
specific heat and other studies, 347; smectic A-nematic transition:
Landau-Ginsburg description, 341-2; complex order parameter, 340
longitudinal and transverse coherence influence of twist and bend distortions
lengths, 343 on the transition, 358-9
smectic C-nematic transition: McMillan's molecular model, 302-9
Chen-Lubensky model, 374—8; critical phenomenological theory, 340-1
divergence of the splay, twist and bend review of theoretical situation and its
constants, 378 comparison with experiment, 347
smectic C-smectic A transition: tricritical point, 309, 341
Landau mean field description, 370-2; see also under pretransition effects
transition induced by layer smectic C:
compression, 372; variation of tilt molecular models, 364
angle, specific heat, magnetoclinic optical biaxiality, 363
effect near the transition, 370-2 polymorphic forms in polar systems, 365
smectic C*-smectic A transition: structure and symmetry, 362
critical variation of the frequencies, temperature dependence of tilt angle 363
dielectric strengths and viscosities tilt and bond orientational order, 3 6 3 ^
associated with the soft mode and see also under continuum theory, defects,
Goldstone mode, 384; generalized textures
Landau theory, 386; temperature smectic C-smectic A transition:
dependence of tilt angle, polarization, complex order parameter and the helium
pitch, electroclinic effect, dielectric analogy, 370
constant, 381-3 Landau mean field theory, 370-1
see also under pretransition effects
Raman scattering studies, determination of smectic C*:
the orientational order parameter applications
<^4>, 48-9 optical modulators, 386-7; surface
reentrant phenomenon: stabilized ferroelectric LCDs, 386-7;
in binary mixtures of polar compounds, tunable colour filters, 386-7
355 description of the structure and the
in discotics, 394 origin of ferroelectricity, 378-80
in non-polar materials, 358 director modes, the soft mode and the
in pure polar compounds at elevated Goldston mode, 382
pressures, 356 electric field effects, 380
Index 459