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Curvature and Uctuations: 8.1 Fluctuations of Interfaces and Capillary Waves
Curvature and Uctuations: 8.1 Fluctuations of Interfaces and Capillary Waves
Curvature and Uctuations: 8.1 Fluctuations of Interfaces and Capillary Waves
where d2 A is the element of area of the interface, and γ is the surface tension for
a planar interface, calculated e.g. using the theory of section 7.3. The ‘energy’ in
equation (8.1), also known as a ‘capillary Hamiltonian’ is actually a free energy,
as indicated by the presence of the surface tension γ , which depends on thermo-
dynamic parameters like the temperature. This effective Hamiltonian therefore
includes fluctuations of short (molecular) wavelength, which are embedded in
the definition of γ . The total free energy of the system is obtained by integrat-
ing the Boltzmann weight exp(−Hcap /kB T ) over a phase space defined by the
possible positions of the interface.
The calculation can be carried out if one restricts the phase space inte-
gration to those configurations that deviate only weakly from the planar con-
figuration. As discussed in section 6.2, such interfaces can be described by
a function h(x, y), and the element of area is d A = dxdy 1 + h 2x + h 2y
2
213
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214 Curvature and fluctuations
where R = (x, y) and q = (qx , q y ) are two-dimensional vectors. With this nota-
tion, the capillary Hamiltonian can be rewritten (up to an extensive constant γ A)
as
γ 2
Hcap = q |h(q)|2 (8.3)
2L 2 q
and the partition function is expressed as an integral over the complex Fourier
components h(q)
γ
Q= d h(q) exp −
2
q2 |h(q)|2 (8.4)
q
2kB T L 2 q
The sum over wavevectors can be transformed into an integral, using the identity,
valid for large systems,
1 1
= d2 q (8.7)
L2 q (2π)2
The lower bound in the integral is qmin = 2π/L, determined by the system size.
The upper bound can be taken to be qmax = 2π/ξ , where ξ is the interfacial width
(see section 7.3) below which the coarse-grained description does not hold any
more. Equation (8.6) then yields
qmax
kB T 2πqdq kB T L
|h(R)|2 = = ln (8.8)
4π2 γ qmin q2 2πγ ξ
Equation (8.8) indicates that the effective width of the interface, when the fluctua-
tions are included, is actually a divergent quantity. The average width, as measured
by equation (8.8), increases logarithmically with system size. Although such a
divergence may seem alarming at first sight, there are several reasons why it is
not very important in practice. The first one is related to the weakness of the
logarithmic divergence. A simple numerical application shows that even for an
interface of one square kilometer, the width defined by (8.8) would not exceed
a few nanometres. The second reason is that gravity will actually introduce a
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8.2 Membranes and curvature moduli 215
Exercise: The liquid and the vapour have different densities. If ρ is the mass
density difference, show that for a gravity field g along the z axis, the gravitational
energy of the curved interface can be expressed as
gρ
dx dy h(x, y)2 (8.9)
2
Show next that
2kB T L 2
|h(q)|2 = (8.10)
γ (q 2 + −2 )
√
where = γ /gρ is the capillary length, i.e. the length scale above which
gravity effects become dominant over capillary ones.
Deduce from (8.10) that for L
kB T
|h(R)|2 = ln (8.11)
2πγ ξ
so that the interfacial width due to fluctuations is not divergent.
The surface fluctuations described in this section are usually termed capillary
waves, in reference to their dynamical behaviour. A fluctuation of the interface
with wavevector q is a collective mode in the sense discussed in section 11.5,
with a dispersion relation that can be computed from hydrodynamics 1 . These
collective modes have been studied in light-scattering experiments 2 similar to
the neutron-scattering experiments described in section 11.6.
1See e.g. L. Landau and E. Lifshitz, Hydrodynamics, Pergamon Press, Oxford, 1959.
2J. Charvolin, J-F. Joanny and J. Zinn-Justin (eds.), Liquids at Interfaces, North Holland,
Amsterdam, 1990.
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216 Curvature and fluctuations
of the membranes contained in the system. Under these conditions, it turns out
that the interfacial tension associated with the membranes is effectively zero.
This somewhat surprising result can be understood as follows. The number of
surfactant molecules per unit area in a membrane, , is a free parameter, which
will adjust in such a way as to minimize the free energy of the system. If f (, T )
is the free energy per unit area of a membrane with surface density , one has at
equilibrium,
∂ f (, T )
=0 (8.12)
∂
Increasing the membrane area at fixed number of molecules is equivalent to
modifying . Equation (8.12) indicates that the free energy cost of this operation,
which defines the surface tension of the membrane, actually vanishes.
When the surface tension vanishes, the surface free energy is dominated by
terms that involve higher order contributions in terms of the deviation from a
planar shape. These deviations are characterized by the curvatures of the surface,
defined in section 6.2. The lowest order contributions from these curvatures to
the free energy can be written in the generic form
1
where g is the genus of the surface, i.e. the number of holes in the surface: g = 0
for a sphere, g = 1 for a torus. The equality (8.14) stems from the fact that the
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8.3 Fluctuations of membranes 217
where, as in section 8.1, we have used equation (6.13) for H , and the Fourier
representation of the function h(x, y) for a system of size L × L. The term
involving the Gaussian curvature has been ignored, since we are interested in
fluctuations that affect only the shape of the membrane, leaving its topology
unchanged.
As in section 8.1, the free energy (8.15) will be considered as an effec-
tive Hamiltonian for the long wavelength fluctuations, assuming all contribu-
tions from short-range correlations have been lumped into the definition of
the curvature moduli. As for the area fluctuations described by the capillary
Hamiltonian (8.3), the statistics of the membrane fluctuations described by the
Hamiltonian (8.15) is Gaussian and one may write, in analogy with equations
(8.4), (8.5), and (8.6)
2kB T L 2
|h(q)|2 = (8.16)
κq 4
and
2
kB T −4 kB T L
|h(R)|2 = q (8.17)
κ L2 q πκ 2π
where the lower cut-off q = 2π/L has once again been used. Equation (8.17)
shows that the fluctuations have a very strong effect on the position of the mem-
brane. The uncertainty in the vertical coordinate is proportional to the in-plane
dimension. A membrane is a much ‘softer’ and strongly fluctuating object than
an interface with non-zero surface tension. Clearly this makes the description
as a weakly undulated interface questionable for large membranes. In order to
estimate the length scale at which fluctuations become dominant, we compute
the average deviation of the normal to the membrane from the z direction. The
normal N(x, y) has coordinates (h x , h y , 1) (see section 6.2) so that the mean
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218 Curvature and fluctuations
where the large q cut-off, determined by the membrane width, is equal to 2π/ξ .
From equation (8.18) we deduce that the membrane will appreciably deviate from
the x y plane as soon as its dimension exceeds the persistence length
2πκ
ξp = ξ exp (8.19)
kB T
In order to compute the free energy of a given membrane, we will assume that it
can be divided into blocks of lateral size L d × L d , each block being unaffected by
the interactions between membranes. The free energy of a block can be computed
from the curvature free energy (8.15). For simplicity, we satisfy ourselves with
an order of magnitude estimate, replacing (∇2 h) in equation (8.15) by d/L 2d .
Within this rough approximation, the free energy of a block is
2
d
F(L d , d) κ L 2d (8.21)
L 2d
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Further reading 219
and the total free energy for a membrane of size L × L is obtained by adding the
contributions from different blocks of size L d × L d as
(kB T )2
F(L , d) L 2 (8.22)
κd 2
This free energy corresponds to a repulsive interaction between the membranes,
that varies as the inverse square of their distance. When combined with the other
types of interactions listed above, this interaction will determine the periodicity
of the lamellar stack.
Further reading
Again the best references are Safran’s Statistical Thermodynamic of Interfaces (Chapter 6) and
the proceedings of the Les Houches summer school, Liquids at Interfaces (see chapter 7).
In the latter see in particular the lectures by W. Helfrich and by J. Meunier.
P.M. Chaikin and T.C. Lubensky, Principles of Condensed Matter Physics, Cambridge
University Press, Cambridge, 1995, has a long discussion of membranes and generally
speaking of fluctuating interfaces.
The book edited by R. Lipowsky and E. Sackmann, Structure and Dynamics of Membranes,
volume 1, Handbook of Biological Physics, Elsevier, Amsterdam, 1995, contains many
interesting and recent experimental contributions.
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