Circular dichroism: A general theory based

on quantum electrodynamics
Cite as: J. Chem. Phys. 60, 3695 (1974); https://doi.org/10.1063/1.1681591
Submitted: 09 April 1973 . Published Online: 22 August 2003

E. A. Power, and T. Thirunamachandran

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J. Chem. Phys. 60, 3695 (1974); https://doi.org/10.1063/1.1681591 60, 3695

© 1974 American Institute of Physics.

Circular dichroism: A general theory based on quantum
electrodynamics
E. A. Power and T. Thirunamachandran
Departments of Mathematics and Chemistry. University College. London. England
(Received 9 April 1973)

A theory of circular dichroism is developed through a direct calculation of the absorption rates for
circularly polarized light on molecules. From this a differential rate as between left and right
circularly polarized light is calculated. This is immediately related to the experimental data on
circular dichroism. When the calculations are restricted to the dipole approximation we reproduce the
rotatory strength in the form of a differential Einstein B coefficient. Higher moments are considered
in detail and their effects analyzed for both the locked-in situation and the case of randomly oriented
molecular absorbers. A general expression is obtained for the differential absorption rate.

I. INTRODUCTION in terms of products of moments. For the locked-in

l case there are contributions from electric moments of
In a recent paper we gave a simplified theory of op-
tical rotation based on quantum electrodynamics. A di-
rect extension to account for circular dichroism needs
to go beyond the two-state model. In this paper we de-
velop a theory of circular dichroism, again from quan-
tum electrodynamics, by a direct calculation of absorp-
tion rates. 2 Circular dichroism is the phenomenon of
differential absorption as between right and left circular-
ly polarized light by an optically active medium. In
solution the phenomenon of differential absorption re-
quires that the individual absorbing units are sufficient-
ly dissymmetric so that electronic transitions to one
or more excited states are allowed by transition mo-
ments of different electrical types bu~ of opposing
parity. The simplest, and common case is when a low
excited state is accessible from the ground state by both
electric and magnetic dipole transitions. It is well
known that this demands the absence of (a) inversion
center, (b) mirror planes, and (c) rotation-reflection
axes in the molecule. In a crystalline state the sym-
metry restrictions are less stringent on the molecules
if the orientation of the crystal is fixed relative to the
incident light. One consequence of this is that circular
dichroism due to pure electric transitions of oppOSing
parity should be observable. The case of electric di-
pole-electric quadrupole interference has been con-
sidered recently by several authors. 3 The general the-
ory based on the Hamiltonian for the complete system-
molecules, radiation, and their interaction-is developed
in Sec. n. The applicability of this Hamiltonian is
briefly discussed and it is shown to reduce to the ap-
proximate Hamiltonian used in our previous paper. 1 To
deal neatly with circularly polarized light we use com-
plex wavefunctions for the electromagnetic fields in the
development of the theory. The calculation of absorp-
tion rates follows in Sec. In and is then used to obtain
a general expreSSion for the differential extinction co-
efficients which are immediately related to the experi-
mental observations on circular dichroism. The ex-
pression is applied to the case of electric and magnetic
dipoles in both the locked-in situation and for randomly
oriented molecules. This leads to a formula for the dif-
ferential Einstein B coefficient for circular dichroism.
Section IV deals with contributions from higher multi-
pole moments. The differential absorption rate is given
different parity as well as those ariSing from magnetic
multipoles. However, the pure electric contributions
vanish for randomly oriented molecules. In Sec. IV. C
the spatial averages for the higher multipoles are con-
sidered in detail. The explicit forms are found for the
first few orders of multipoles. The resulting differen-
tial rates can be expressed as a generalized rotatory
strength, where besides direct contributions from prod-
ucts of higher electric and magnetic multipoles, e. g. ,
electric quadrupole-magnetic quadrupole, 4 there are
changes in the effective electric and magnetic moments.
A surprising feature is that the contributions from the
pure magnetic moments of differing parity survive ran-
dom averaging unlike those in the electric case.
II. THEORY
In quantum electrodynamics the dynamical system,
treated in a microscopic fashion, consists of both the
molecules and the radiation field. The Hamiltonian is
H =Hmo1ecule. + Hradiatlon + H interaction • (1)
The molecular Hamiltonians are assumed to be known
and for our purpose it is sufficient to use the first-
quantized Schrodinger operators of wave mechanics.
In contrast to semiclassical theories the radiation field
is second-quantized and is described by the microscopic
transverse electric and magnetic field operators e and
b.
X=l,2
(2)
b= 6 (27TIlW)l/Z ik l( e(X)(k)[a (X)(k) e 1tor _ a().)t(k) eoltor) .
t, V
X.I,Z (3)
In Eqs. (2) and (3) a O')(k) and a().)t(k) are the annihilation
and creation operators, respectively, for a photon of
wave vector k (frequency w = kc) and polarization A,
where e().) is the unit vector normal to the plane of po-
larization; V is the quantization volume. In terms of
these fields the radiation Hamiltonian is the integral of
the energy density
3'Cradiatlon = (87T)"l(e 2 +b 2) • (4)

The Journal of Chemical Physics, Vol. 60, No.9, 1 May 1974 Copyright © 1974 American Institute of Physics 3695
3696 E. A. Power and T. Thirunamachandran: Circular dichroism

Since we are to calculate to the lowest order the rates for straightforward in Cartesian tensors. In the present
single photon absorption by independent molecules we work we use Cartesian tensors throughout.
need to know the interaction energy only up to terms
The Hamiltonian following from the density (5) can be
linear in the electric and magnetic fields. As shown
written
elsewhere,4 the appropriate interaction Hamiltonian
density is
Hlnteractlon= - ~p(~). e(R~) - ~
~ ~
mm ·b(R~) (10)
JClnteraction = - P . e - m . b, (5)
with obvious meaning of the operators p(~) and m(~).
where p and m are the electric polarization and mag-
In dipole approximation expression (10) is
netization, respectively, for the assembly of molecules.
For a particular molecule ~ with position vector R~, we
- ~ ~(~). e(R~) - ~mm· b(R~)
have the familiar multipole expansions ~ ~

Pi(r) = lli(O o(r - R~) -q ii(~) Vi o(r - R t ) as used in Ref. 1.

+tm(O Vj Vko(r - R~) _ ... (6) In this paper we use the full interaction Hamiltonian
(10). To apply this Hamiltonian to the problem of cir-
m;(r) =mi(Oo(r - R~) - ml;)(O Vj orr - R~)
cular dichroism it is convenient to introduce the com-
+mU~(~)Vj Vk orr - R~) - .... (7) plex electromagnetic field operators
In Eq. (6) ~(O is the electric dipole moment and q Ij(o, f=e+ib (11)
tm(~), tl;kl(O' ...
are the components of the electric
because the left and right circularly polarized fields
quadrupole, octupole, sedecupole, ... moments of
feLl and feR) obey the equations
molecule~. Similarly mi(~)' mW(O, mm(o, ... are
the components of the magnetic multipole moments. curl f(L)=kf(L) (12a)
The sums (6) and (7) can be formally written 5 as inte- curl feR) =- k fCR) • (12b)
grals over a parameter A as in Eqs. (8)
The convention used here concerning the sense of ro-
1 tation of the e vector is the one normally used in chem-
p(r) = - e ~ q", ( o[r - R~ - A(q", - R~)]dA, istry. Helicity states in high energy physics are de-
'" Jo fined in the opposite way. Analogously to (11) we in-
m(r) = - (e/2mc) ~{1", ( A orr - R~ - A(q", - R~)]dA (8) troduce the complex polarization field
d= p+im, (13)
+ S:Ao[r-R~-A(q,,-R~)]dAl,,}, so that the four fields are
p= i(d+d t ),
where q" and 1" are the position vectors and angular mo-
ments of the optical electrons Q! on molecule~. The m =(1/2i){d - d t ),
(14)
first few moments (referring qa to the center R~ of the
molecule ~) are e=W+tf),
b = (1/2i){f - ft).
Ili(~) = - e ~q"i'
" The interaction Hamiltonian density (5) now becomes

q ij(~) = - (e/2) 'Eq ,,/q aj , (15)

'" To calculate the absorption rate and hence the B coef-
t~;k(~) = - (e/6) ~qaiqaiqak' ficient we use the simple time-dependent perturbation
(9) theory as described by the time-ordered graph (Fig. 1).
"
A photon of wave vector k and polarization e is absorbed
mi(O = - (e/2mc) ~lai' by the molecule ~ originally in its ground state thus ex-
a
citing it to the state IE.> with energy E.. Overall, en-
m~~)(O = - (e/6mc) ~ (Z"i q ai +qai lai), ergy is, of course, conserved to within the line width so
a that

mm(~) = - (e/16mc) ~ (laiqajq ak +q aiq akla;). fick =fiw ""En-EO . (16)

" The transition rate is
It is clear from the form of these multipole moments
that they are not, in general, irreducible. That the
reducible parts may contribute to the energy density,
Eq. (5), can be seen by inspection of a typical multipole.
For example, if there is a dipole interaction - III e i
then there is also a possible interaction proportional to
-tmei = (e/6)/q/e/o It is possible to write these
multipoles as sums of irreducible components but the
theory that leads to the Hamiltonian density (5) is
(17)
where M If is the matrix element of the transition n - 0
and Pi is the initial density of states; i. e., the number
of states per unit energy interval. In terms of the in-
tensity I(erg/cm 3Hz) of the incident polarized beam the
energy in volume V for a bandwidth ~w is

J. Chem. Phys., Vol. 60, No.9, 1 May 1974

 E. A. Power and T. Thirunamachandran: Circular dichroism 3697

f(r) = '6 i(87TYiw /V)1/2[ e (L )(k) alL )(k) e itor

k

(26)
ft(r)= '0 i(87TYiW/V)1/2[e(R)(k)a(R)(k)e itor
k

we have

FIG. 1. Time-ordered graph corresponding to the matrix M:f) = - ~ (87TlZw/V)1/2 eeL) . nnO(k) (27a)
element for absorption.
MIt> = - ~ (87T1Zw/V)1/2 e (R) ·nnO(k), (27b)
In terms of Pi

IV(~w /27T) = Pi Yiw (Yi~w); (18)

n"o(k)= (Enl J deikordVIEo) (28)
so
15"O(k) = <En 1 Jd t
e ikor dV lEo) .
(19)
Thus
Hence 3

(20) w~;)= (2d/Yi 2) '6 elL)e?) .t5t>(k) Dt(k) (29a)

i .J=1

In circular dichroism the rate will depend on the helicity 3

W~:)= (27TI/Yi 2) I) elR)e?) nt>(k) Dt(k) . (29b)
of the incident photon. For a left circularly polarized i d=l
photon the absorption rate is
Thus, the transition rates are similar to their ordinary
wlf) = (IV /Yi 3W ) 1(En; 01 Hint IEo;k, e(L) 12 . (21a) electric dipole forms with D (or n) replacing the elec-
tric dipole transition moment 1-£. Clearly, in the elec-
Similarly, for a right circularly polarized photon,
tric dipole approximation for a molecule at the origin
w~:)= (IV/Yi 3w) 1 (En; 0IH int IEo;k, e(R» 2
1 , (21b)
d= j.Lo(r) (30)
where
and
(22a)
(31)
and
so that the transition rates for left and right Circularly
(22b) polarized photons are equal, both being

III. CALCULATION OF DIFFERENTIAL EINSTEIN B (32)

COEFFICIENT
The Einstein B coefficient is defined for the absorp- For a randomly oriented dipole the average is
no
tion of light by a randomly oriented molecule relative (Ilt>ilt)=t Oij j.L l2 . I (33)
to the direction of the beam by
Thus
B=r/I, (23)
(34)
where r is the averaged transition rate. The differen-
tial Einstein B coefficient may be defined as since
e(L). e(R)= eeL) .-e(L) =1 (35)
(24)

and in this section this is found by calculating IMlf)12 Hence we obtain the well-known expression for the
and IMlf)12 of Eqs. (21) which are then spatially aver- Einstein B coefficient, namely,
aged. The complex electromagnetic field operators f B= (27T/31Z 2)\ IJ.nO\2 • (36)
and ft can be expanded into creation and annihilation
operators for circularly polarized photons. In fact, f Returning to Eqs. (29) for the case where both elec-
annihilates a left-handed and creates a right-handed pho- tric dipole and magnetic dipole transitions are simul-
ton; conversely, ft annihilates a right-handed and taneously allowed, we have
creates a left-handed photon. Thus, from Eqs. (15) and d= (j.L +i m) o(r) (37)
(21),
and
Mlt>= - t (En; 01 J d t . fdVIEo;k, eeL»~ (25a)
nnO= I-£nO +i m nO (38a)
Mlf)= - t (En; 0\ J d ·ftdV\E o, k, e(R». (25b) 15no= IJ.nO - i m nO • (38b)
6
Expanding f and ft as in Eqs. (26) For a randomly oriented optically active molecule

J. Chern. Phys., Vol. 60, No.9, 1 May 1974

3698 E. A. Power and T. Thirunamachandran: Circular dichroism

nO > 1 -~J.li- t ijk

(D nOD-
i j =sOiJ 1f.L nO +zm
. nO 12 (39a) (3 l k
j
k k+tiJklm
(5 l k j k kl
k k m-'" (48)

and and
(39b) Pei=(En l-eQi(l-COSk·q)IE\
In contrast to the pure electric case, these are not equal
ik' q 0/
since m nO is imaginary. Thus, the differential B coef- =i(Qijkj-tlj~lkjkkkl+"') . (49)
ficient is
The differential absorption rate is then
B(Ll_B(Rl= (w~;l>_ (w~:l»/1, /",2)1 e i(Ll e j(Rl (P ei P oj - P 0; P ej ) . (50)
(4 17"
w(Ll
if - w (Rl
if =
= (217/3 n2 )( III nO - i m no 12 - 1 f.L nO +i m nO 12),
The next contributions in Eq. (50) after the dipole-
= - (817i/3 n2 ) f.LnO. m nO , quadrupole term (45) are the dipole-sedecupole and the
quadrupole-octupole terms. Both of these contributions
= (817/3 n2 )ImRnO , (40)
depend on the magnitude of the wave vector raised to
no the third power. In general, the 211 - 212 electric multi-
where R , the optical rotatory strength, is defined as
pole interference contribution to the differential ab-
(41)
sorption rate varies as

(51)
IV. CONTRIBUTIONS FROM HIGHER MOMENTS
A. Locked-in molecules: Electric multipole contributions B. Locked-in molecules: Electric and magnetic
multipoles
As explained in the Introduction, when the absorbing
molecules are in a fixed orientation relative to the in- It is now easy to generalize the above treatment to in-
cident light, differential absorption as between left and clude magnetic transitions. From Eqs. (29) we have
right circularly polarized photons can occur without the wi; l - w~: l= (217 /n 2)J elL le?l6~(k)i5t(k) -Dt(k)D~(k)]
admixing of magnetic transitions. If, as has been as- (52)
sumed in Sec. III, the electric dipole transition moment = (217 /n 2)J elL l ejRl[(p~ - iMro)(p'f +iM't)
is rea1 8 then the first nonvanishing electric contribution
to circular dichroism comes from interference between - (P JnO +iMjnO )(P
-nO -iM
i
-nO ) ] ,

dipole and quadrupole moments for the relevant transi- (53)

tion. The differential rate for this case is, from Eq. where, analogous to (43), the magnetization MnO is
(29), J
M nO = mnOeik.rdV. (54)
o
wlj! - wlfl= (217/n 2)1 el Ll e?lrp~ Pi - ptpf] , (42) If P and M are divided into their even and odd contri-
where for electric transition only DnO may be replaced butions, as before keeping to the case of real wave-
by functions, we have

pnO= J pnOeik.rdV. (55)

The first two terms in the multipole expansion of p and

gives, for a molecule located at the origin, (56)
P7°= (J.lf +iq'fJ kj)' (44) where
Hence (57)
eLl - W(Rl_ 2)Je(Ll e (Rl k (II nO q nO_ I1nOq~o)
Wif if - - (417i/>c
n i j I .... i 11 I""} 'I .
(45)
and

Without loss of generality we may choose the direction (58)

of the incident light k to be 3; then (45) Simplifies to are the multipole expansions of the magnetization. It
(Ll -Wif
(Rl (/,,"2)1k( J.l1nO q23-J.l2
nO nO q13'
nO) should be noted that all the electric moments are real
Wif = - 417 " (46)
whereas the magnetic ones are imaginary. Also, the
From (46) it is clear that averaging, assuming random nomenclature of odd and even is based on the normal
orientation of the molecule, gives zero differential rate assignment, namely, that a 21-pole has parity (-1)/ for
as expected. Before proceeding to include the magneti- electric transitions and (- 1)1+1 for magnetic transitions.
zation contribution we may easily generalize the pure Thus Eq. (53) becomes
electric (locked-in) case to include the higher electric
multipole moments. Analogous to (44), p may be W~j! - w:: l 2
= (41T/n )J e? l ejRl
divided into contributions from odd and even orders,
x [(P eiP oj - P DiPej - MoiMe) +MeiMo})
p = P odd + p even '" Po + P e , (47)
+i(PeiMOj-PoiMej+MoiPej-MeiPOj)] .
where
(59)

po.
. = /E
'\ n
1- eq i sin(k . q) IE \
k.q 0/
We point out that the differential absorption rate given
by (59) includes the previous contribution (50) together

J. Chem. Phys., Vol. 60, No.9, 1 May 1974

 E. A. Power and T. Thirunamachandran: Circular dichroism 3699

with an analogous magnetization term which mixes the (coscp cose cosl/! (sincp cose cos</! - sinB cos</!
odd and even multipoles. However, the additional
- sincp sinl/!) + coscp sin</!)
terms, proportional to the products of electric and mag-
netic multipoles of the same parity, are vitally impor- (- coscp cosB sim/! (- sincp cose sin</! sinB sin</!
tant: they survive the random averaging process and
- sincp cosl/!) + coscp cos</!)
are discussed in the next subsection. The k dependence
of the 211 electric multipole coupled with the 212 mag- coscp sinB sincp sinB cose
netic multi pole is again (64)
To carry out a random average of the differential ab-
(60) sorption rate (59) over all molecular orientations, we
express w (L) - W (R) as a function of (cp, 0, l/I), integrate
Since both I' s can now be unity the leading contribution with respect to cp, 0, ¢, using the appropriate Jacobian
is the dipole-dipole term, which is independent of k. and divide by the total volume 811'2, so that
(w(L)-w(R»=(81T 2 1 2u u 2v r fo fo fo (w(L)-w(R»)sinOdcpdOd¢.
C. Randomly oriented molecules (65)
Clearly, a typical angular integral will be of the form
Circular dichroism is usually observed in solution.
In order to relate such experimental data with theory we (Srr r 1 f f f Rj).R j I'R kv • •. sinBdcp dBd</!
2
(66)
need to perform a spatial average on the results ob- with (11 +12) R factors ariSing from the product of two
tained for locked-in molecules. In this section we carry moments 211 and 212. The rotational invariance of the
out this averaging for the first few multipole terms. averaged quantity (66) implies that it is a sum of iso-
First, it is necessary to specify the multipole moments tropic tensors of rank 2(11 +12)' Each summand is a
with respect to a body-fixed frame. Using greek in- product of two isotropic tensors, each of rank (l1 + I2)'
dices for the components in such a frame of reference one with latin suffices and the other with greek suffices.
we write the electric moments as By a theorem of Weyl, 9 (66) can be written as
1/2(11+12) )(1/201+12) )
(61) 'B ( II 6i112 II 6"1).2 for even (I1 +12) (67)

and the magnetic moments as

(62)

Then for the particular orientation of the molecular

frame with respect to the laboratory frame defined by
the Euler angles (cp, e, l/!) we have For the first few orders 10 we have
Il!~= (81T 2 r f Ri).sinBdcpdBd~) = 0,
1
(69)
(63) I:~:"",=(81T2r1 f Ri).Rjl'sinBdcpdBd</!=~6lj6),/.L' (70)
q '1. '2. = R,. 1,A1 R·'2 ,A2q,A1 A2
, '. m j(21j)2 = Ri1"lRj2"2 m,~21~'2 '
II;k;).l'v= (81T r f RnRjl'RkV sinBdcpdBd1J;,
~ ~ ~ ~ 2 1

where R i ). may be read off the well-known matrix (64). =t E iJk E ).l'v, (71)

Il~kl;)'l'vo= (81T
2
r 1 f Ri).Rj",RkVRlosinBdcpdBd¢
= {fs- 6 Ii 6 kl 6;..1' 6 vo - to 6ij 6kl 6;..v 6 1'0 - to 6 Ii 6 kl 6;"0 6 I'V - icr 6 ik 6 jl 6;../.L ovo +fs 0 Ik 6J1 6"v 6 ",0 - icr 0 ik 6JI 6;"0 6 I'V

-io6i/6 Jk 6).1'6 vo -io 6iI6jk6"v61'0+fs- 6/1 6 jk 6;"0 6 "'v}, (72)

Il;klm;;..I'VOv= (81T r f
2 1
Ri).RJI'RkvRloRmusinedcpdBd</!

= io [E iik E),l'v 15 1m 0 0.. +EIJI E).l'o Okm 6vv +EiJm E,,/.LV 6 kl OVO +E ikl E), v0 6 Jm 6 1''' +E ikm Ewu 6J! 61'0
+E i/m(;..ov 6Jk 61'v+ EJkl E I'v0 6 Im 6;..u+ Eikm(l'vr 6 il 6;"0+ EJ/m( I'OU 6ik 6 w +(klm (vov 6ij 6;..1'] . (73)

Using these results we evaluate the averaged differential rate given by (65). Substituting (59) into (65) we obtain
(W(L)_W(R»

= (47r /ti 2) I(el L )e jR) - eJL) e jR») f (P eiP oj +MeiM oj)sine dcp de d1J;/81T 2
+ (41Ti/ti 2 ) I(el L ) e jR) + e jL) ei(R») f (P elM oj - Poi M ej ) sinBdcpdBdl/!/81T 2 • (74)

It is easy to show that the term involving electric moments only vanishes. The value of Il +l2 in P eiP oj is odd; hence
from (68) there is a contraction of the antisymmetric tensor with a symmetric moment tensor of (61) which is neces-
sarily zero.

J. Chern. Phys., Vol. 60, No.9, 1 May 1974

3700 E. A. Power and T. Thirunamachandran: Circular dichroism

We now turn to the mixed electric and magnetic contributions in Eq. (74) and in the first instance to terms con-
taining the magnetic dipole. These terms are

- (4 7ft.'ltc2)I(L)(R)
n e i ej +e j(L)(Rl)J(
ei /lARiA - (3)
tA A A Ri A Ri ,_Ri l_ki k i +
1 2 3 1 1 2'-. 3'-, 2 3
... )
m"~ R'J."~"
sllludcpd u d1)! /87T
f) 2
(75)

~ (4 ./,,2) I( (L) j(R) (L) (R») [ 111 1(2) t(3) k k (4) ]

~- 7Tt ft ei e +e j e i /lA ", ij;A'" - A1A2A3m", i2 i3Iiji2i3;A"'A2A3'"
2
=_ 87Tli
fT2
(lJ.'m
3
_k t.m+ ... )
15 ' (76)

where tA = t~t)", is the vector formed by contraction of the octupole moment. This result can be rewritten as
eff
(87fI /fT2) Im(lJ. . m/3) , (77)
where
(78)
is an effective electric dipole moment. Equation (77) is the Rosenfeld-Condon formula with appropriate corrections
added to the lowest order electric dipole moment of the molecule.

In a similar manner we may evaluate the corrections to the magnetic dipole moment due to the higher even mag-
netic multi pole moments. Thus we obtain an effective magnetic dipole moment

(79)

The coefficients of the corrected higher moments differ for the electric and magnetic terms [Eqs. (78) and (79)]
because the electric moments are symmetric in all their indices whereas the magnetic moments have one special
index, namely, that for l. Thus we may write the averaged differential absorption rate similar to Eq. (40) but in-
cluding vector corrections from higher multipoles as

( W(L)_W(R»= 87fI Im/Jeff.meff (80)

3fT 2 ,.. .

We now turn to the leading contribution to the averaged differential absorption rate from PeiM oi term in (74).
Clearly, this term will depend on the electric and magnetic quadrupole moments and is given by

i
- (47fi/fT 2) I(e L ) ejRl +e jL) e fR») J q il kl 111 jk kksine dcp de d1)!/87T 2

= - (47Ti/fT 2)I(el L ) e jRl + e? 1 e ~R») kl kkqAO 111 ",v J RnR ",R k"R
i 10 Sinedcp de d1)!/87T
2

=- (47Ti/fT 2)I(ejL) e jR) +e?) ejR») k 1 kkqA0 111 ",,,I\jkl;A"'vo ,

2 2 (81)
=- (87Ti/fT )Ik qAo 111 ",,,(/s OA",OVO-irr owo",o-in 0).00",,,) ,

where, in the last step, we have used the transverse properties of the field, namely, e(L !Rl. k= O. The last sum-
mand in Eq. (81) gives the product of the traces of the quadrupole moments which is zero. Hence the quadrupole-
quadrupole contribution to the averaged differential absorption rate is

(82)

As in the previous paragraph, there will be contributions from higher multipoles that reduce to effective quadrupole-
quadrupole terms. The over-all rate will be like (82) with effective values for qA'" and m"'A given by
q:~f = q).", _ +k tit~" + ...
2 (83)

m~~f=111",l, _tk2111~\~,,+··· (84)

The remaining term in equation (74) involves the product of magnetic multipoles. It might have been supposed
that its contribution was zero in a manner similar to the argument for electric multipoles. This is false because the
magnetic moments, unlike the electric moments, are not necessarily symmetric in their indices. The leading con-
tribution from this term is

(4rri/fT 2 )I(elL 1 ejRl - e? 1 e \R») J 111i m ikkk Sine dcp d6d1)!/87T 2

= (4rri/fT 2)I(e lL) ejRl - ejL) e jRl) kk m). m "''' J Rn,Rj "R k " sine dcp de dljJ/8rr
2
,

= (A-i/fT 2 )I(e ~L)

"'%11 I
e(Rl
J
_ e(L
ilk
1 e ~R») k 111 m
A
I~~ 1
~ V IJ k; >"~l.1'"

= (2 7fl'/3tc2)I(
n ei(Ll e j(R) -e j(Ll ei(R»)k k€j}kml,m",,,€).,,,,,
.

=(4rr /3fT 2)I k mAm ",,,€).,,,,, • (85)

J. Chern. Phys., Vol. 60, No.9, 1 May 1974

 E. A. Power and T. Thirunamachandran: Circular dichroism
This can be written, in terms of the antisymmetric
partll of m,..v, as
(86)
where
v~ = - (k/2i)E~,..vm,..v
and v can clearly be added to the "effective" dipole mo-
ment so that the averaged differential absorption rate is
(w (L) _ W (R» = (871' /31f 2 )IIm jJ.eff . mef!
+ (47T/51f 2 )Ik 2 Im(qeff : mef!)
+"',
where the irreducible components are
/lAff = /lil) - (k/2i)E~,..vm~2j - (k 2/5)ti!),.. + ... ,
miff=m~1)-~k2m~~~+ ... ,
eff =q~,..
q).,.. (2)
- (2k/3') (3)
t EvB~mvB,.. -
1.k2t(4)
7 ~,..vv+···'
mA~f = m~~) - t k2mi~~v+'"
V. SUMMARY
By a direct calculation of the absorption rates for
radiation of given intensity and given circular polariza-
tion (either left or right) we have obtained a generalized
Rosenfeld-Condon formula for circular dichroism. For
the locked-in situation, where the molecular axes are
fixed with respect to the direction of the incident light
beam, the relevant differential absorption rate is given
by (59) in terms of the scalar products of the polariza-
tion direction of the radiation with general electric po-
larization and magnetization vectors of the absorbing
molecules. These polarization fields can be given in
terms of multipole expansions. As is known 3 the elec-
tric dipole and electric quadrupole interfere to give a
contribution to dichroism in the locked-in limit. This
is a special case of the more general pattern where mix-
tures of electric odd-electric even multipoles give rise
to dichroism as do mixed magnetic odd-magnetic even
multipoles. The mixed terms containing electric and
magnetic moments are primarily responsible for ordi-
nary circular dichroism (they survive random averag-
ing) and the leading contribution arises from the elec-
tric dipole-magnetic dipole coupling. Again, this is
the first of a series of electric-magnetic interference
effects such as quadrupole-quadrupole; there are no di-
pole-quadrupole terms. In general, the electric odd
poles (dipole, octupole, ... ) mix with the magnetic even
poles (dipole, octupole, ... ) and the electric even poles
(quadrupole, sedecupole, ... ) mix with the magnetic odd
poles (quadrupole, sedecupole, ... ). The difference in
the asSignment of the odd-even character of a particular
2'-pole as between the electric and magnetic case is due
to the axial nature of the magnetic multipoles [see the
J. Chern. Phys., Vol. 60, No.9, 1 May 1974
3701
discussion after Eq. (58)].
For a randomly oriented molecule it is not easy to
write down a general formula similar to (59) because
each moment has a different behavior under spatial ro-
tation. We have carried out this averaging for the first
(87) few terms and the result, given in Eq. (88), is a series
expressed in effective moments the first being of the
well-known form involving the dipole optical rotatory
strength Im( jJ.. m). The corrections to the Rosenfeld-
Condon formula are of two kinds. The moments them-
selves become a series involving contractions of higher
moments, similar to the general results of Kemmer 12
(88) for classical electric and magnetic multipoles. Second-
ly, there are contributions from irreducible parts of
higher moments: the quadrupole-quadrupole term being
(89) shown explicitly in equation (88). It should be noted that
both types of corrections depend on the wavelength of the
(90)
radiation as well as the nature of the molecule.
(91)
(92)
IE. A. Power and T. Thirunamachandran, J. Chem. Phys. 55,
5322 (1971).
2An earlier theoretical calculation of circular dichroism by
consideration of absorption rates was given by V. Lawetz and
D. A. Hutchinson, Can. J. Chem. 47, 576 (1969).
3y . N. Chiu, J. Chem. Phys. 52, 1042 (1970); A. D. Bucking-
ham and M. B. Dunn, J. Chem. Soc. A 1971, 1988; L. Bar-
ron, Mol. Phys. 21, 241 (1971).
4E • A. Power and S. Zienau, Philos. Trans. R. Soc. A 251,
427 (1959).
5R . G. Woolley, Proc. R. Soc. A 321, 557 (1971); M. Babiker,
E. A. Power, and T. Thirunamachandran, ibid. 332, 187
(1973).
6H. Kramers, Quantum Mechanics (North-Holland, Amsterdam,
1957).
7The dagger sign t denotes the Hermitian conjugate whereas
the bar sign as in e of D refers to the complex conjugate. The
tilde sign in f> does not refer to the complex conjugate (except
in special cases) but is defined explicitly in Eq. (28).
8Clearly, if the excited state is degenerate then the transition
moment is not necessarily real. Transitions into certain
speCified components can then show dichroism in the locked-
in limit. Even the 2Pl-1s emission along the north polar
axis in atomic hydrogen is entirely left-handed.
9H. Weyl, The Classical Groups (Princeton U. P., Princeton,
NJ, 1946), p. 53; G. F. Smith, Tensor 19, 79 (1968); H.
Jeffreys, Proc. Cambridge Philos. Soc. 73, 173 (1973).
10For even order :In) equivalent results can be found in E. B.
Wilson, J. C. Decius, and P. C. Cross, Molecular Vibra-
tions, (McGraw-Hill, New York, 1955), p. 292; S. J. Cyvin,
J. E. Rauch, and J. C. Decius, J. Chem. Phys. 43, 4083
(1965).
11It is to be noted that anti symmetry refers to the indices and
not to the ordering of operators in Eq. (9). The symmetric
part of mw contributes to optical activity through the term
given in (82).
12N. Kemmer, Quanta, edited by P. G. O. Freund,. C. J.
Goebel, and Y. Nambu (University of Chicago Press, Chicago,
1970), p. 1.