DoubleQuantum Light Scattering by Molecules

R. Bersohn, YohHan Pao, and H. L. Frisch

Citation: The Journal of Chemical Physics 45, 3184 (1966); doi: 10.1063/1.1728092
View online: http://dx.doi.org/10.1063/1.1728092
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3184

DIELEMAN,

DE

JONG,

comparison with metalloid vacancy compensation. The

dominant energy term in the latter compensation
mechanism is Hv. The value of Hv can be estimated
at about 2 eV.19 We see that the balance between
these two incorporation mechanisms can shift from
more metalloid vacancy compensation in ZnS to more
Fe-donor compensation in CdS and ZnSe. What was
found actually was that compensation by the Fe donors
increased in this direction. However, this is not evidence
of a competition with metalloid vacancy compensation,
other incorporation mechanisms still being possible at
present. Since the evidence for the self-coactivated
dissolution of the alkali metals is not yet convincing,
19 F. A. Kroger, The Chemistry of Imperfect Crystals (NorthHolland Publ. Co., Amsterdam, 1964).

THE JOURNAL OF CHEMICAL PHYSICS

AND MEIJER

it is even possible that the solubility of these metals

is largely determined by the presence of shallow donors,
i.e., they dissolve as monovalent ions, just as has been
found for the elements Cu, Ag, and Au. What remains
is an expected increase in compensation by Fe donors
from ZnS to CdS and ZnSe, because of the decreasing
ionization energy of these donors in this direction.
ACKNOWLEDGMENTS

We wish to thank Dr. C. Z. van Doorn for helpful

discussions, Dr. W. Kwestroo for the preparation of
high-purity ZnS and CdS, and the department of Dr.
N. W. H. Addink for the chemical analysis. We are
also grateful to Mr. T. S. te Velde for making available
to us some of his results.

VOLUME 45, NUMBER 9

1 NOVEMBER 1966

Double-Quantum Light Scattering by Molecules

R.

BERSOHN

Department of Chemistry, Columbia University, New York, New York

AND

YOH-HAN PAO AND H.

L.

FRISCH

Bell Telephone Laboratories, Incorporated, Murray Hill, New J ersey

(Received 19 May 1966)

Double-quantum light scattering by a system of molecules is discussed in this paper. Expressions have
been obtained for the scattered light intensity considering both the coherent and incoherent contributions.
In that coherent contributions are also considered in this treatment, it goes beyond the scope of previous
studies. It is shown that, for molecules of low symmetry, elliptically polarized light must be used in order to
determine five independent quadratic forms in the 18 symmetric components (f3i;k+{3.k;). According to the
present results, the apparent discrepancy between the observed value of l for the depolarization ratio for
eCI. and the value to be expected from theory may be due to the fact that the coherent contribution had
been neglected in previous theoretical considerations. In general, orientational correlation is essential if
there is to be appreciable contribution from coherent scattering. For macromolecules, this constitutes a
major difference between single- and double-quantum scattering, and additional information may be expected if the latter is investigated experimentally.

I. INTRODUCTION

F a system is irradiated by photons of frequency W

and scatters photons of frequency 2w, it is said
to exhibit double-quantum scattering. More generally
we call two-quantum light scattering the process in
which two quanta of frequencies WI, W2 are incident
on a system and a single quantum with frequency
W3=Wl+W2 is scattered. At low frequencies such scattering is routine and is described in terms of the nonlinear
electrical parameters of the system. On the other hand
at optical frequencies the phenomenon has only recently
been discovered. l The reason for this contrast is simply
that for a given energy density there are far more
quanta at low frequencies than at optical frequencies.

1 P. A. Franken, A. E. Hill, C. W. Peters, and G. Weinreich,

Phys. Rev. Letters 7, 118 (1961).

The possibility of nonlinear optical processes was

discussed theoretically in 1931 by Mayer. 2 Franken3
has given a review of his first nonlinear optical experiments and a phenomenological theory. The latter is
based on the observation that double-quantum scattering depends on the third-order tensor (3 in the expansion of the electric polarization of the system
(1)

or

where a and ~ are second and third order tensors, respectively. It can be inferred from this equation that
2

il

M. Goeppert-Mayer, Ann. Physik 9, 273 (1931).

p, A. Franken and J. F. Ward, Rev. Mod. Phys. 35, 23 (1963).

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LIGHT SCATTERING BY MOLECULES

in a system with a center of symmetry the polarization

vector must change sign when the electric vector reverses direction; hence fJ must vanish identically. One
would therefore expect that only crystals which lack
a center of symmetry would exhibit nonlinear effects.
Armstrong et al. 4 have analyzed these effects in detail
and have shown that coherent double-quantum scattering is to be expected in certain crystals at certain
orientations but not, in general, in fluids.
Terhune, Maker, and SavageS succeeded in observing
double-quantum scattering in such "fluids" as H 20,
CC4, CHaCN, and fused quartz. The intensities observed were so small (",10-1a of the incident intensities)
that they represent not a contradiction of the previous
theory but rather an incoherent scattering from single
molecules or small clusters of molecules. Future experiments following the pioneering work of Terhune
et at. should provide information about (1) the fJi;k
tensor of the individual molecules and (2) the structure
of liquids and dissolved macromolecules. 6
To explore these matters, we present in this paper
a derivation of expressions for the scattered light intensity, considering both the coherent and incoherent
contributions. By coherent contributions we here refer
to the cooperative scattering of neighboring molecules

+ (JJ.X1")

Oq (JJ.xa") qr (JJ.X2") rO

(Wl-Woq) ( -W2-WOr)

K=ka-kl -k2, and Ra is a vector from an arbitrary

origin to a fixed point in the scattering unit a.
Let us consider a single radiating dipole t' in classical
electromagnetic theory. If It is a unit vector from the
dipole to point of observation at a distance R, then the
field vectors are
S..,= (wNc2R)(t' xlt) xIt,

(4)

Hsc= (wNc2R) (t' xlt)

(5)

4 J. A. Armstrong, N. Bloembergen, J. Ducuing, and P. S.

Pershan, Phys. Rev. 127, 1918 (1962).
R. M. Terhune, P. D. Maker, and C. M. Savage, Phys. Rev.
Letters 14, 681 (1965).
GR. Bersohn, J. Am. Chem. Soc. 86, 3505 (1964).

3185

whose positions and orientations are correlated. It is

understood the scattering from different regions of
the liquid (whose size is of the order of the wavelength
of the light or larger) is incoherent. In that coherent
contributions7 are also considered in this treatment,
it goes beyond the theoretical treatments of Li,8
Kielich,9 Cyvin et al.,l0 and Terhune et at. 5 However, in
contrast to these previous discussions, the present
treatment is limited to elastic scattering; that is, the
scattered light is exactly at the sum frequency and the
Raman effect is neglected.
II. SCATTERING BY AN INDIVIDUAL MOLECULE

A. Tensor fJi;k
A derivation is given in Appendix A of the probability
per unit time of the scattering into a solid angle dO of
a light quantum of wave vector ka and polarization Aa
by a system of individual elements a (molecules or
segments of a larger molecule) when given intensities
of photons kl' AI, k2, A2 are incident. The derivation uses,
for the sake of clarity, a quantized radiation field but
yields (as might be expected) the same expression
previously derived by semiclassical means, viz.,

+ (I-'X2")

Oq (I-'XI") qr (JJ.X1") rO

(W2-WOq) ( -WI-WOr)

and the Poynting vector is

(6)

The corresponding quantum-mechanical expression

7 A brief summary of preliminary results of this aspect of the
present investigation was presented at the Third International
Conference on Electromagnetic Scattering, Amherst, Mass., 1965,
by H. C. Frisch.
8 L. Y. Yuan, Acta Phys. Sinica 20, 164 (1964).
G S. Kielich, Bull. Acad. Polon. Sci. 12, 53 (1964).
10 S. J. Cyvin, J. E. Rauch, and J. C. Decius, J. Chem. Phys.
43,4083 (1965).

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3186

BERSOHN, P(O, AND FRISCH

for the energy flux vector scattered by a single molecule

ex IS
Wka-klk.}iwkl

R 2dfJ

0,= 271" (~)4 (~) l(w1)I(w2)

R2 me

he

X 1fa (kaAa, k2A2, k1~q)

12hwall.

(7)

Comparing Eqs. (6) and (7) we see that the component of the induced dipole in the direction of polarization of the scattered wave is
JJ.A3=

(t)!(efNm2) [OAI (WI) OA2(W2) /Wa(WIW2) I]

Xfa (kaA3, k2A2, kIAI) ,

(8)

where we have substituted

i=I,2.

(9)

Now, by the definition of the tensor {3, we have

(10)

and hence we can establish the correspondence

(3AIA2AI = (t)1/ 2(eh 2/m 2) [1/wa(wIW2) 1/2Jfa(k3A3, k2A2, kIAI)

(11)

between the matrix element of the {3 tensor and the

scattering amplitude fa. The corresponding matrix
element for a group of molecules would be a sum over
the scattering amplitudes for the individual molecules
weighted by phase factors.

center of symmetry not all the three quantities f}oq,

t'qT, and t'rO can simultaneously be different from zero.
Therefore the tensor {3 for the unit ex vanishes and-in
the dipole approximation-harmonic scattering is impossible. The theorem depends on the existence of a
center of symmetry in the unit ex and makes no reference to the presence or absence of a center of symmetry
in the system as a whole.
Kleinman's theoremll and its limitations are also
apparent from inspection of the formulas. If the important intermediate states have energies so much
greater than the energy of the three light quanta involved that the photon frequencies can be neglected
in the denominators, the 3 ! terms of the formula become
the 3! permutations on the three indices. The tensor
{3i;k becomes symmetric in all its indices and the applied
electric fields of the light waves become equivalent
to static fields. The theorem appears to be valid for
crystals such as crystalline quartz12 and KH2P04 with
incident ruby laser light (6943 A~1.8 eV). However,
these crystals have little absorption below 7.5 eV. On
the other hand, obvious nonlinear resonance effectsl3- I5
are shown in cases where the absorption bands are
closer to the harmonic such as in CS 2, ZnS, and crystals
of benzpyrene and benzanthracene. In the absence of
a theoretical evaluation of Eq. (3), the limits of validity
of Kleinman's theorem must be determined experimentally. This is not assumed in this paper, in contrast
to the work of Cyvin, Rauch, and Decius. 1o

B. Theorems on the Tensor {3.;k

C. Estimate of the Cross Section for Double-Quantum

Scattering

Two general theorems can be established from the

tather complicated formulas of Eqs. (2) and (3). In
rhe dipole approximation which we have adopted the
individual scattering units ex are small compared to the
wavelength and only the electric dipole operator t'
occurs in the matrix elements. If the system ex has a

If we try to form the cross section from Eq. (2) according to Eq. (Al1) , we have a practical difficulty
that for a three-particle process the effective cross
sections are dependent on beam intensities. As an example, suppose we consider a single incident beam for
which WI=W2=!W3=W. Then

( 12)

A measure of the harmonic component in the scattered radiation is the ratio of the differential scattering cross
sections (12) and (AlO) , i.e.,
( h )2 1 (w) 1 ~fa(2) exp(iKRo) 12

(dO'/dfJ)harmonic e2
(dO'/dfJ).ingle

hc 471"

me'l

L:.fa(l) exp(iKRa) 12 .

(13)

The ratio SeW) of the squares of the structure factors

is dimensionless and should be of the order of magnitude of unity except at frequencies w such that 2w
is close to an absorption peak. Equation (13) can be
rewritten more simply as
0'2/0'1 =ex( 471"ao2) [I (w) /wJs(w) ,

where ex is the fine-structure constant and

(14)

ao

is the

Bohr radius. The physical meaning of this equation

is that when the incident flux lew) is so great that on
D. A. Kleinman, Phys. Rev. 126, 1977 (1962).
R. C. Miller, Phys. Rev. 131,95 (1963).
13 B. Lax, J. G. Mavroides, and D. F. Edwards, Phys. Rev.
Letters 8, 166 (1962).
14 P. D. Maker, R. M. Terhune, and C. M. Savage, Phys.
Rev. Letters 12, 507 (1964).
15 Y. H. Pao and P. M. Rentzepis, J. Chern. Phys. 43, 1281
(1965) .
11

12

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LIGHT SCATTERING BY MOLECULES

the average one photon passes through an atomic area

in the period of the light wave the harmonic ratio is
equal to the fine structure constant. Inserting the
values of the physical constants and using 6943 A as
a wavelength we have
UdCl1 =2X 10-341 (w) S(w).

(15)

Equation (15) shows that in order to observe appreciable harmonic intensity we must use a wavelength
such that Sew) is very large or an exceptionally intense
la&er beam. Contemporary technology permits peak
pulsed powers outputs in the megawatt to gigawatt
range which corresponds to l()2c1Q27 photons/sec. The
actual flux 1 (w), the number of photons per square
centimeter per second, may be increased considerably
by focusing the incident light which permits observable
intensities of the harmonic.
III. DEPOLARIZATION OF THE SCATTERED
LIGHT
A. Observable Functions of the Components of {3

Consider a small volume of the medium as a source

of dipole radiation. The induced dipole l' is by definition
(16)

Assume the initial light beam is incident along the

X axis. (These innocent looking a&sumptions restrict

3187

one to phenomena describable in terms of the 18 symmetric components (3ijk+{3ikj only as is fully explained
by Giordmaine. 16) The polarization of the light wave
will determine the actual quadratic form in the {3's
which is observed; but, as we see below, the use of
elliptically polarized light is necessary to obtain all
the observables.
The inten&ities of single-quantum scattering can be
expressed in terms of the principal molecular pol arizabilities an, a22, and a33 through the quadratic forms
(an2+a222 +(332 ) and (ana22+ana3a+a22aa3)' This can
be done by measuring the intensities of the two different
polarizations of radiation scattered at 90. No matter
what polarization properties one uses in the incident
light, and no matter at what scattering angle one looks,
one can only measure these two quadratic functions
of the polarizabilities. For double-quantum scattering
one can measure five quadratic forms in the (in general)
18 symmetric components of the polarizability (3ijk.
To prove this theorem assume that the incident light
travels in the X direction with an arbitrary polarization given by
t= to{cos~ coswtj+ sin~ cos(wt+15)kl,

(17)

where ~ and 5 are arbitrary angles. For unpolarized

light one must average the final intensities over 5. For
circular polarization one sets ~ = t1r and 5 =!1r and for
linearly polarized light ~=O. The second-harmonic
dipole moment induced by this electric vector is

l'=~: toto = ![{,Bxzz sin2~ cos2(wt+15) +,BXYY COS2~ cos2wt+(,Bxyz+{3xZY) sin~ cos~ cos(2wt+15) Ii

+ {,Byzz

sin2~

cos2 (wt+15) +,Byyy

COS2~

cos2wt+ ((3yyz+,ByZY)

sin~ cos~

cos (2wt+15) I j

+ {,BZYY COS2~ cos2wt+,Bzzz sin2~ cos2(wt+15) + ((3ZYz+,BzZY) simp co~if; cos (2wt+15) Ik]C;o2
(18)

where a static component has been subtracted.

An oscillating dipole l' will give rise to a scattered
harmonic wave at a distance R whose electric vector
is given by Eq. (4). If we take R to be arbitrary, i.e.,
(19)

of the previous vectors the new vectors are

e1 =[I/(I-Az2)1/2]( -Ayi+AXj),
e2=[I/(I-A~)1/2][ -AXAZ i-AYAzj+(1-AZ2)k],

ea=R/R=Axi+Ayj+Azk.

(21)

Then, in this basis,

then performing the cross products we have

(2W)2

1
(1-Az2)1/2 [ -JlXAY+JLY AX]e1
1

+ (l-Az

(20)

In an experiment one does not measure the magnitude

of t along three mutually perpendicular axes but along
two axes which are mutually perpendicular and perpendicular to the direction of observation, R. In terms

2)

1/2 [JlX AXAZ+JLYAY AZ-JlZ(1-AZ2) ]e2

(22)

16

J. A.

Giordrnaine, Phys. Rev. 138, A1599 (1965).

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3188

BERSOHN, PAO, AND

The two independent intensities which can be measured are

(23)
and
(24)
In these equations the subscript Av refers to a time

FRISCH

average over the period of the incident light wave

which is to be carried out first. The brackets refer to
an average over a large number of molecules. In this
latter average the cross products like J!.xJ!.y which occur
have zero average values. This is because the liquid,
unlike the individual molecules is isotropic. The averaged intensities are then

h = [(2W)4/41TC 3J[1/ (1-AZ 2) JI (.uX2)A,Ay2+ (.uy2)AVAX2},

(25)

12 = [(2w) 4/41TC3J[1/ (1- Az2) J I (Jl.X2)A,AX2AZ2+ (.uy2)A,Ay2AZ2+ (.uZ2)A, (1-A~) 21,

(26)

where

(J!.X2)A,/02=i(j3xzZ2)

sin~+i(j3xyy2)

cos41/t+i sin21/t cos2!JtfJxyz+fJxzy)2+2fJxzzfJxyy cos2c5),

(27a)

(.uy2)A,/02=i(j3YZZ2)

sin~+t.<fJyyy2)

cos41/t+i sin21/t cos2!JtfJyyz+fJyzy)2+2fJyzzfJyyy cos2c5),

(27b)

(p.z2)A,/02=i cos~(j3zyy2)+1 sin~(j3zzz2)+i sin2!Jt cos2!JtfJZyz+fJzzy)2+2fJzzzfJzyy cos2c5).

At first sight it would appear that there are
six independent variables which can be measured,
namely (j3ZZZ2), (fJXZZ2), fJxyz+fJXZY) 2), (fJxzzfJXyy),
fJZyz+fJZZY) 2), and (fJzzzfJZyy). (Terms like (j3zyy2)
and (j3 YZZ 2) are in any case the same because of the
isotropy of the solution.)
A proof that there are only five observables follows
by the method of Terhune et at.s Suppose we consider
the general expectation value (fJik!/3;mn). Because the
liquid is centrosymmetric, all six indices must be equal
in pairs or the expectation value will vanish. Here we
can write

(27c)

from which it is clear that there are five observables,

a, b, c, d, and e. A somewhat more limited, alternative
proof of the fact that there are only five observables
is obtained by considering only the incoherent contributions to the scattering as is done in the next section.
To measure all five observables it is necessary to use
not only linearly and circularly polarized light but even
elliptically polarized light as is shown by Eqs. (27),
(29), (30), (31), and (32). On the other hand from
Eqs. (25)-(32) we see that one learns nothing additional by looking in any direction but the classic 90
angle.

(fJik!/3;mn) =a[c5ijc5kmc5ln+c5ijc5knc5lmJ
+b[c5imc5kjc5In +c5 inc5kjc51m +c5imc5I,tlkn +c5inc5ljc5kmJ

l.

a TERMS:

+Cc5iic5klc5mn+d[c5ilc5lmc5jn+c5i~lnc5jm+c5ilc5kmc5inc5ilc5knc5;mJ

+e[c5 ik c5 I,tlmn +c5ilc5kjc5mn +c5 imc5k1c5;n +c5inc5klc5jmJ.

(28)
b TERMS:

This sea of Kronecker deltas is readily visualized

by means of Fig. 1 in which the various terms a through
e are represented by five classes of diagrams. From the
equation J!.'= L:ik10k01 it is clear that the indices i andj
playa different role from k and I, which accounts for
the difference between certain classes of diagrams.
If the tensor fJi;k were symmetric on all its indices
(Kleinman's theorem), then a=b and c=d=e.
Using Eq. (28) one finds that
(fJzz~)=2a+4b+c+4d+4e=2a+c+4(b+d+e),
2

(fJerzz )=2a+c,
fJxyz+fJxzy) 2+ 2fJxzzfJxyy cos2o) = 4a+ 2c cos20,

t
C TERMS:

I I
m n

L k
+

L k t

L k t
+

.N
J m n

.~n

J m

TERMS:

e TERMS:

(32)

L k t
+

.)K'

J m n

k-t

I.

J m-n

X
m n

L:-k t

L-k t

L-k t

L k t
+ ./

--......

--

L k t

L k t

L k-t

L k-t

. /
+
I + . I + . \
J m n
j-m n
J m n
J-m n
'-.-/
'---'"

./
J m-n

--

J m-n

+.\
J m

(31)

fJzZy+fJzyz)2+2fJzzzfJzyy cos21l)
=4(a+b+d) +2(c+2e) cos21l,

.Xm nI

(29)
(30)

l. k t

+ j-m
' "n

FIG. 1. Diagramatic representation of the nonvanishing components of the tensor (fJ;kl{Ji",n). Lines connect indices which
must be equal. Each of the five classes are symmetries in both
k and 1 and m and n.

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3189

LIGHT SCATTERING BY MOLECULES

TABLE

1. Expectation values of quadratic functions of f3 in space-fixed coordinates expressed as coefficients of quadratic functions
of f3 in molecule-fixed coordinates.

<f3zzz2)=2a+c+4(Hd+e)

({3xzz2)=2a+c

({3xzzf3XYY) =c

35

105

1'1

1'2

1'3

Il,

Il.

105

105

105

210

105

-1

-1

-1

210

105

70

210

-1

-1

21

84

105

-1

-1

420

210

35

35

35

35

35

-1

-1

105

35

35

35

105

35

-1

-1

-1

35

105

105

210

105

35
2

-1

105
-1

35

105

210

105

210

70

35

-4

-2

35

35

105

105

105

105

105

70

105

42

70

-4

-4

-4

-2

-1

11

-1

105

105

105

35

105

21

21

35

105

210

35

f3zyz+f3zzy)2) =4(a+b+d)

((f3xyz+f3xzy) 2 )=4a

f3.

f32

11
((3zzzf3ZYY) = c+ 2e

f3.

f3.

f31

210

42
-4

The quantities a, f31-{3., 'Yl, 'Y2, 'YI,Il., IJ, are defined in tbe text.

B. General Expressions for the Incoherent

latter are defined as follows:

Contributions to the Scattering

A component of the tensor /3 in space-fixed axes may
be written in terms of components of /3 in moleculefixed axes by the transformation

/3ikl = L L L aizPk,plr/3P'l'"

a=L/3 111
.. 2 ,
i

(34)

/31 = L /3iiJ3iiil

(35)

itj

/32 = L /3iii(/3iii+/3m) ,
(33)

p=% q=x r=zz

(36)

i.1

/33= L /3iir,

(37)

/34 = L /3iii(/3jij+/3iii) ,

(38)

i,i

where the a's are direction cosines between the old

and tr.e new axes. In evaluating products of /3's in the
space-fixed axes we must multiply two sums of this
form, As the light wave sees molecules in all orientations the incoherent contributions to the expectation
values of Eqs. (29)-(32) are obtained by averaging
the products of six direction cosines over all orientations
of the molecule-fixed axes relative to the space-fixed
axes. (The nonvanishing averaged products are tabulated by eyvin, Rauch, and Decius.l) The final resuits can be most succinctly stated in the form of the
matrix in Table 1. This matrix expresses the quadratic
functions of components of /3 which appear in Eqs.
(29)-(32) in terms of quadratic functions of components of /3 expressed in molecular fixed axes. The

i.i

/3, = L (/3iii+/3iii) 2,

(39)

i.i
1'1 =
1'2 =
1'3 =

L /3iii/3ikk,

(40)

L (/3iii+/3iii) (/3kik+/3kki) ,
i.i,k

(41)

L /3iii(/3kik+/3kki) ,

(42)

i,i,k

i.i,k

151 = L (/3iik+/3ikj)2,

(43)

i,i,k

15 2 =

L (/3iik+/3iki) (/3iik+/3iki)'

(44)

i,i,k

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3190

BERSDHN, PAD, AND FRISCH

The sums are carried out for i, j, k =X, Y, Z but

i, j, k are never to be equal to each other.
A check on the values of the coefficients in Table I
is that if one assumes the molecular tensor is totally
symmetric, the first, second, and sixth lines reduce to
identical expressions derived by Cyvin, Rauch, and
Decius. Also, addition and subtraction of various rows
confirms the expressions of the quadratic functions of
the space-fixed components of fJ in terms of the a, b,
c, d, e terms previously discussed.
C. Depolarization Ratio for Linearly Polarized Light

Inasmuch as we have shown that one does not obtain

additional information by looking in any direction
but the cla~sic 90 angle, for the case of linearly polarized light we can evaluate Egs. (25) and (26) with
Az=Ax=O, Ay=l and siny,=1. This means the incident
light travels in the X direction, is polarized in the Z
direction, and the scattered light is observed in the
Y direction. Under these conditions
Ix = [(2w) 4/47rc3J(.uX2)Av = [(2w)4/327rc3J(Bxz~),
(45)

I z = [( 2w) 4/47rc3J(.uZ2)AV = [(2w) 4/327r3J(fJzzZ2),

(46)

where Ix(z) is the intensity of light polarized in the

X (Z) orientation, and the depolarization ratio is

(47)
The general expressions of Eqs. (45) and (46) for
a molecule with no symmetry are contained in the
first two lines of Table 1. They may greatly simplified
for molecules of rather high symmetry as is shown in
Appendix B.

alter the effective magnitude of the scattering interaction. Also, there may be coherent scattering in that
the partial waves scattered by the various molecules
or segments of a given large molecule may interfere.
Finally, the observed intensity will depend on the size
of the extent of coherence between small volume elements which in turn depends on the degree of mismatch
of the indices of refraction at wand 2w.
A. Internal Fields

The effect of the polarization of the neighbors is

::ondensed into the Lorentz factor (e+ 2) /3 which is
the ratio of the local electric field to the electric field
of the light wave acting in a vacuum; e is of course the
dielectric constant at the frequency w. The intensity
of single-quantum scattering is increased by the fourth
power of [e(w) +2J/3. As pointed out by Armstrong
et al.,4 the intensity of double-quantum scattering in
which quanta WI and W2 produce the quantum W3 must
be multiplied by the square of the product
![e(wl) +2J![e(w2) +2J![e(w3) +2].
The rule is that a Lorentz factor must appear at each
vertex of the perturbation diagram to augment the
radiation field acting there.
B. Coherent and Incoherent Contributions to the
Scattering

The structure factor FJLM(K) of a group of N

scattering units can be written as the sum
N

FJLM(K) = L!JLMa (W3, W2, WI) exp(iKR a )

a=l

IV. SCATTERING BY A SYSTEM OF MOLECULES;

ORIENTATION CORRELATION

In this paper we have derived scattering probabilities

for light scattering by isolated molecules in a vacuum.
The intensity of light scattered by a real system of
many molecules is not just a multiple of the scattering
by a single molecule. In the first place internal fields

exp(iKRa).

(48)

The scattering intensity which is proportional to the

square of the structure factor equals
N

l(w3) = (167rw34jc5R2)I(wl)I(w2) i{e(wl) +2J2 t[e(w2) +2J2 t{e(w3) +2J2X 1 L fJJLM(W3, W2, WI) exp(iKRa) 12
a=1

=KN (BJLM 2),

(49)

where
N

(BJLM2) =N-l L
a=1

I fJJLM(a)

2+N-l

LL fJJLM (a) fJJLM (a')

exp[iK (Ra, -Ra)]

aa'=l

(50)
For a real fluid the sums are equivalent to averaging
over an ensemble of randomly oriented configurations.
We may characterize the two terms in this equation
as incoherent and coherent, respectively. The incoherent
terms have already been discussed in Sec. II1.B.

C. Intermolecular Correlations

In the coherent part of Eq. (50) one needs to average

over relative distances and mutual orientations of
pairs of molecules. Let g(rl' r2; Ql, Q2) be the two-

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3191

LIGHT SCATTERING BY MOLECULES

particle correlation function, i.e., p2g drldr.ylJhdQ2 is the probability of observing Molecules 1 and 2 in drldr2 at rl,
r2 with orientations in dQ ldQ2 at QI~(p=N IV, the number density). Equation (50) can then be rewritten with
r=rl-r2, r=1 rl-r21, and g(rl, r2, QI, Q2) replaced by g(r, QI, Q2)

(flJLM2) = 8~2

.BJLM2(1)dQI+P

(8~Y ~

11 f
dr

dQI

dQ2g(r, QI, 02).BJLM(1).BJLM(2) cosKr

(51)

One can write a general expansion

g(r, QI, Q2) = ! gi(r)hi(QI, Q2),

(52)

i..()

where the hi(Q I, Q2) are suitable orthogonal polynomials

in the trigonometric functions of the Euler angles designated by QI, Q2, ho=l and the gi(r) are the expansion
coefficients. The normalization of Eq. (52) is given by

(8: )2111 drdQldOg(r, QI, Q2) -lJ=p 1dr[go(r) -lJ

2

=pkTK-1,

(53)

where K is the compressibility of the fluid.

The coherent part of Eq. (51) can be written17 as
the sum of an intensity scattered as a result of the
geometry of the surface of the matter plus a scattering
from the density fluctuations. The two terms are obtained by substituting

in the second term of Eq. (51). Omitting further discussion of the surface scattering we are left with the
coherent scattering which is caused by the microscopic
inhomogeneities involving correlations in orientation
of molecules:

In Eq. (56) the summation excludes the term i=O

because there is no contribution to the incoherent scattering when g(r, QI, Q2) is replaced by go(r). The coherent part of the two-photon scattering vanishes if
there are no correlations in orientations. This is a significant difference from the case of ordinary Rayleigh
scattering. The reason is just that (averaged over all
orientations)

(.BJLM+.BJML) =0,

(58)

(aJL) = t8JL (ax.,+ayu+a .. ) .

D. Approximate Treatment of

(59)

geT, QI, Q2)

The general expansion of Eq. (52) for g(r, QI, O2)

is rather formidable and an approximate treatment is
sufficient at this early stage of consideration of the
problem. In the absence of phase transitions (liquidcrystal formation), one expects correlations in orientations to occur only between adjacent molecules in a
liquid. The range of all gi(r) is therefore small, say of
the order of the position R2 of the next-nearest peak
of go(r). In view of the absence of reliable information
on g(r, 0 1, Q2) or its expansion, one can obtain an order
of magnitude estimate by replacing the series, Eq. (52)
in hi by a single term and approximating the coefficient
gi(r) by the values

gi(r) =0
gi(r) =1

On inserting the expansion of g, Eq. (52) into Eq. (55),

we find
sinKr
27rp
drr2 - - L: gi(r) 8 i (J LM),
(56)
o
Kr i==1
where

00

00

8i(JLM)

=(8~2r

f f
dQ I

dQ2h i(01, Q2).BJLM(1).BJLM(2).

(57)

J.

Hirschfelder, C. F. Curtiss, and R. B. Bird, Molecular

Theory of Gases and Liquids (John Wiley & Sons, Inc., New York,
1954).
17

(60)

For small molecules we may replace the factor

sinKr/Kr in the integrand of Eq. (56) by unity and
with the above substitution for gi(r) the integral in
(56) becomes
(2/7r)p!-rr(R 23_R I3)8 i (JLM).

(61)

The interpretation is that RI is the distance of closest

approach of typical molecules in the liquid and that
beyond this distance the orientation of the molecules are
correlated ai> far out as the distance R 2 The quantity
!-rr(R23_R I3)p can be replaced by z, the effective
number of nearest neighbors in the fluid.
E. Application to Coo. Molecules
While otherwise a priori arbitrary, the function
h;(Q l , Q2) must be invariant under the symmetry opera-

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3192

BERSOHN, PAO, AND FRISCH

tions of the two molecules. We now consider the distribution function appropriate for molecules of symmetry Coo" The treatment holds precisely for linear
molecules without a center of symmetry and perhaps
adequately for any symmetric top. To obtain a possible form of the function hi(Ql, Q2) let us consider the
following heuristic argument. Suppose that the orienting intermolecular force were the interaction between
the static dipoles of the linear ( or symmetric-top)
molecules. The interaction energy between two such
dipoles is17

guide to the correlation function. Thus we may write

In a dilute system where the distribution function

is only determined by pair interactions, we have

COsOt2 =aXZlaXZ2+aYzlaYz2+aZZlazZ2
(65)
would have appeared. It is reasonable therefore to take
as a general form

hi(Qt,~)

=t(COS012-3 COsOt COs(2)

= t (sinOt sin02 cOS!/>t COS!/>2

+ sinOt sin02 sin!/>t sin!/>2 -

2 COsOt COs(2)

=E(aXZlaXZ2+aYzlaYz2-2azZlaZZ2)'
(64)
where E should be ""JJ.2/R t 8kT if the dipole orienting
force determined the distribution function.
The direction cosines aZ Z1 aZ Z2 appear with a different
coefficient than the sum aXZlaXZ2+aYzlaYz2' Had we
assumed that the orientation distribution was a function only of the angle 012 between the symmetry axes,
then only

h(Qt, Q2) =tt(ax Z1 aX .. +aY z1aYz2) +t2azZlaZZ2'

The form of the potential energy can thus be used as a

8 t (XZZ) =El

8 t (ZZZ) =E2

f
[8~2 f
[8~

(66)

One can now write for any molecule, regardless of

its space group, whose liquid has a distribution function of this form

dQlaXx/Jx .. (1)

dQlazz1{3 ... (1)

r ({3xZ~)ooh,

(67)

(68)

= ({3zzZ2)ooh.

Substituting the transformations

(3xzz(l) =axolazxl{3zxx+aXZlaZlIlz{3zuU+aXz13{3zzz+aXXlaZX,aZZl ({3xzx+{3xxz) +aXII,aZlI,aZZ' ((3l1zv+{3w.)
(3ZZZ( 1) = azz,3{3 ... +azZ,azX12({3zn+{3xzx+{3x"z) +az"az1I1z ((3zw+{3YZII+{3wz)

+ .. "

+. ..

(69)

(70)

(omitted terms make no contributions to the integrals) and integrating, one finds
8 z (ZZZ) = t{i{3... +I"5" ({3zu+{3xz.'+{3xxz+{3zW+{3l1Zll+{3WZ) J2,

(71)

8 t (XZZ) =tl[-h{3... +h({3zxx+{3zw) --io({3xxz+{3xzx+{3VlIZ+{3l1ZII) J2.

(72)

For linear molecules (Coov ) the only nonvanishing components16 of {3 are 13m, {3zxx = {3ZYY, and {3xzx+{3xxz = (3l1zlI+{3w;
Inspection of Table I and Eqs. (34)-(44) shows that
<ftZZ~)incoh = t{3...2+-h{3... ({3zxz+{3xzx+{3nz) +rh({3zxx+{3xzx+{3xxz) 2,

(73)

({3XZ~)inooh =-/r;{3...2+r h{3.. .f3.n--/r;{3z.. ({3x.x+{3xxz) +S\{3zn2-rh{3zxx({3xzx+{3xxz) +iK({3xzx+{3xx.)Z'

(74)

The theoretical formula, Eq. (3), for determining

the molecular quantities {3ijk is exceedingly difficult to
evaluate. Without any knowledge of their values the
formulas of Eqs. (71)-(74) are rather opaque. To interpret them we put forward some rather crude assumptions covering the electronic transitions important
in the perturbation theory.
Our assumptions are that the resonance denominators
of the perturbation theory, e.g., Eq. (3), severely limit
the important intermediate states. To determine which
components of {3 are most important we consider those

components whose transitions involve the lowest virtual

excitation energies and therefore the smallest resonance
denominators. As a concrete example consider the
linear molecule H-C=N whose optical harmonic scattering properties are assumed to be similar to those of
CHa-C=N already studied by Terhune et al,5 The
component 13m would be derived from three successive
transitions all polarized along the axis, i.e., 11"~11"*---+
1I"*/~. The transition 11"~* would be the lowest
energy transition in the molecule but that one electron
which was promoted to an antibonding 11"* state would

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LIGHT SCATTERING BY MOLECULES

nave no 7r*' state to go to except one constructed of

3fJ7r orbitals whose energy would be prohibitively high.
Therefore, we expect fJ ... to be very small; fJxx. and
its permutations would be determined by a u~*~
u*~u sequence of transitions corresponding to a nitrogen lone-pair transition to an antibonding 7r state, to
an antibonding u state, and then back to the ground
state, and therefore fJxxz, fJxzx, and flz"", would all be of
substantial size. If we crudely assume fJzzz""'O, 2fJzx::::::'
flxzx+fl",xz =fl, then

3193

we consider the transformations

fJzzz(i) =6fJazxiaZy,aZ."
flxzz (i)

= 2fl (aXXiazlliaZZ, +aXl/iaZXiaZ.. +ax .. azx,azl/') .

(80)

From the form of these transformations it is clear that

the function, Eg. (78) cannot contribute to coherent
scattering and it is therefore not considered. The
second function makes the following contributions:

(75)
(76)

and the depolarization ratio is

(77)

A check on this simplified theory would be possible

by studying the depolarization ratio in the limit when
the coherent contribution vanishes. Practically this
could be done in two ways. The harmonically generating
liquid can be mixed with a liquid composed of centrosymmetric molecules, e.g., benzene, CS 2, liquid SF6, or
liquid Xe. The depolarization ratio in the dilute limit
is, of course, the incoherent contribution. Alternatively
the pure liquid could be studied as a function of temperature; in the high-temperature limit, correlation
effects should disappear.
F. Application to Tetrahedral Molecules

For tetrahedral (Td ) molecules the only nonvanishing elements16 of the fl tensor are flX1Jz=flxzy=flyzx=
flzxy=flzyx=fl. By inspection of Eqs. (43) and (44) and
Table I, one sees that the incoherent contributions to
(flzzz'l) and (fJxzZ2) are -Hfl2 and :/r;f32, respectively.
To calculate the coherent contribution we need to
adopt a correlation function hi(flt, Q2)' Because of the
nature of the nonvanishing fliik we must use a function
which contains each of the coordinates x, y, z at least
once and symmetrically. The simplest possible functions which fulfill this requirement are
2

Ii

II (aXxiaYYiaZ .. +aXYiaYziaZX,+axz,aYx,aZYi
i=l

and
E(

i=-l

i=l

i-I

II aXXiaXlliaX .. + II aYxiaYlliaYzi+ II aZXiaZlliaZ.,).

(79)

To obtain the coherent contributions to the scattering,

(f3zzZ2)ooh = E{32 (6 (adazI/2ad) )2=rh-r;Ef32.

(82)

The depolarization ratio for tetrahedral molecules

is defined as
(f3XZZ2)
(f3zzz'l)

(flXZz'l)inooh + (f3xzZ2)ooh
(f3ZZz'l)inooh+ (f3zZz'l)coh
:/r;f32+rh-r;E{32 2+rhE
-Hf32+n\-r;Ef32 3+-hE'

(83)

This result is, from the experimental point of view,

perhaps the most significant one of this paper. The
reason is that the absolute intensity of the harmonic
scattered radiation is very difficult to measure accurately. The ratio of two intensities, the depolarization ratio is much easier to measure. For molecules of
most space groups this ratio involves a fairly large
number of independent components of fJ; it is therefore
difficult to draw much of a conclusion from the result.
But in the case of tetrahedral and D3k molecules the
ratio is independent of the values of the fJ tensor.
Terhune et al. 5 observed a depolarization ratio of "'i
for CCI4 Comparing this value with Eg. (83) we draw
the following conclusions:
(a) In CCl4 E is positive, which means that neighboring molecules tend to orient themselves so that
they are identically oriented. This is just the configuration which would cause immediately adjacent CI atoms
to avoid each other and is therefore reasonable.
(b) The orienting potential which determines E is
comparable with or greater than kT. Had it been
weaker, the depolarization ratio would have been
closer to i.
From this single datum it is perhaps unwise to draw
very broad conclusions. If the theory just given is
generally right however it would be of interest to study
the depolarization ratio in the limit when orientational
correlation disappears (d. preceding section). The
depolarization ratio in a benzene-CCI. mixture should

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3194

BERSOHN,

PAO,

1.0

AND

FRISCH

range of this stacking. For a double helix of polynucleotides a one-dimensional Ising model can be used
to describe the states of hydrogen bonding between
the bases and thus the over-all structure.
The function which we use for the segments of the
macromolecules is

0.8

0.6
Q

0.4

0.2

10

0
0

U2

FIG. 2. Angular distribution of double-quantum scattering by a

macromolecule in random-coil conformation. Abscissa u l is a
measure of differences in refractive indices as well as k vectors.
Coil dimension also enters as a parameter [Eq. (88) of text].

rather speedily approach j with decreasing mole fraction of CCl4

G. Application to Macromolecules

where K is the reciprocal of an orientation correlation

length. The explanation of this simple function is as
follows: The delta function arises from the fact that
nearby configurations are strongly correlated. The
exponential function is rigorously obtained for a onedimensional Ising model in which only nearest-neighbor
orienting forces are considered. Furthermore, in general,
it appears that the exponential decay of a correlation
function reflects the short-range character of the intermolecular forces.I s
The structure function used for macromolecules is

"N"

sinkr ij
P ()
(j =1- L...iL...i--

N2

ir'i=l

krij

(85)
,

where k= (2-n/A) sin(j and P((j) is defined by the equation

J((j) =J(OH(1+ cos2(j)P((j).

In what way can double-quantum light scattering

add to our knowledge of macromolecules? In a previous
paper one of us6 discussed this question and arrived
at the conclusion that except for the facility of being
able to look at zero angle (which is not at K =0 for
double-quantum scattering) there is no additional information available from double-quantum scattering
over single-quantum scattering. This is true if and
only if the scattering elements are oriented the same
way throughout the molecule or at least in some specific
pattern along the molecule. When this is not the case,
the coherent contribution to the scattered light for
double-quantum scattering will be different from that
of single-quantum scattering.
In solutions sufficiently dilute so that interference
occurs only between segments of the same molecule,
the function g(r, nl, n2) of Eq. (52) refers to the intersegmental pair-distribution function. The function
g(rih ni , nJ ) describes in part the structure of the
polymer, being the joint probability that two segments
separated by a distance rij have the orientation ni , nj .
Of particular interest are two types of polymers, one
being the synthetic linear polymers consisting of a chain
of N repeating units which while chemically identical
have different tacticity. By tacticity we mean that
each unit can, in principle, exist in two states of orientation. These are analogous to a one-dimensional Ising
lattice comprised of a set of spins with two possible
orientations. And the second type being the polynucleotides in which successive bases are stacked parallel to each other. The function g is a measure of the

(86)

J((j) is the intensity of scattering of (unpolarized)

radiation through an angle (j. For any assumed model
for the structure of a polymer the function P((j) can
be calculated and compared with experiment. 19 In
1.0 ........: - - - - - - - - - - - - - - - - - - - - ,

0.8

0.6
Q

0.4

0.2
10
0

FIG. 3. Angular distribution of double quantum scattering by

a thin rod. Abscissa x is a measure of differences in refractive
indices as well as k vectors [Eq. (87) of text].
18 M. E. Fisher, in
H. L. Frisch and J.
New York, 1965), p.
19 B. H. Zimm, R.
(1945) .

The Equilibrium Theory of Classical Fluids,

L. Lebowitz, Eds. (W. A. Benjamin, Inc.,
III-86.
S. Stein, and P. Doty, Polymer Bull. 1,90

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3195

LIGHT SCATTERING BY MOLECULES

kKm

particular, for a thin rod

1
PO
() = X

j2X sinwdw (sinX)2

---

IVn

(87)

X'

k'

Wo

1/10

-k'

where X =~kL, and for a random coil

(al

(88)

where U=tk2R2.
In the present problem we require a modified structure function
1
Q(O; K) =2
N

N
sinkr
2:2:
--"
exp( -Krij).
krij

(89)

k= (47r/Ao)n(w)

sin~O,

(92)

where Ao is the vacuum wavelength, 27rc/w, but that

for double-quantum scattering at a frequency 2w

12X -exp
sinw
(VW)
- - dw
0

It is perhaps worth repeating6 the point that for

single-quantum scattering at a frequency w

i>"j

For a thin rod

1
Q(k; v) =X

(h)

FIG. 4. Feynman diagrams for the scattering of a single light

quantum. In (a) the scattered quantum is emitted after the incident quantum is absorbed. In (b) the reverse is true.

k=[47r/(2Ao)](n(2w)n(w) sint9

+ a[n(w) -n(2w) ]}2)1/2.

e-' sinhv cos2X

X 1+

. 2X
sm

cotXe-2 . ]

'

(90)

where V=~KL.
For a random coil

2
Q(k;v)=-(
)1/2
7rU

In other words, to calculate k at a given scattering

angle 0, one must know the indices of refraction of the
solvent at both the incident and the scattered wavelengths.
ACKNOWLEDGMENTS

j1 (l-y)

-1-'2-

(93)

dy

xjOOo exp [-(~~+~)]{cosz-_v

SinZ}dZ,
4 uy
U 1/ 2

U 1/ 2

(91)

where v=KR/6 1/ 2 This integral can be evaluated in

terms of error functions of complex arguments but the
resulting cumbersome expression is harder to program
than the double integral above which was evaluated
directly. The numerical results for these two functions
are shown in Figs. 2 and 3, respectively.
The three values of v-O, 1, lO-for which the curves
were drawn correspond, respectively, to a correlation
length l/K which is OC), comparable with the molecular
size, and .......,lo of this size. The loss of angular correlation with distance leads to a general decrease of the
coherent contribution to the scattering. The angular
dependence becomes steeper the longer the correlation
length.
Experimentally it may be difficult to measure the
absolute intensity of the scattered light. The absolute
intensity is of interest only in the determination of the
absolute values of the /3 tensor. What is far easier to
determine is the angular dependence of the light scattering. The latter depends for single quantum scattering on the shape and characteristic size of the molecule.
For double-quantum scattering it depends on the size
and shape and on the orientation correlation length.

R. B. would like to acknowledge the support of the

U. S. Public Health Service Grant CA-07712-02 as well
as the hospitality of the Bell Telephone Laboratories
where part of this work was done. We would also like
to thank R. L. Kornegay for his able numerical computations and Paul Maker for helping to correct a
serious error.
APPENDIX A: DERIVATION OF THE TWOPHOTON SCATTERING AMPLITUDE
1. Matrix Elements of the Matter-Radiation
Interaction

Use of a quantized radiation field20 permits a simple

picture of the light-scattering phenomena on a molecular level. To make the formalism perfectly clear
we first discuss ordinary scattering. To begin with,
our system is imagined to consist of a single molecule
and an interacting radiation field enclosed within the
walls of a large box of volume V. The Hamiltonian can
be written
JC =JCmatter+JCradiation +JCinteraction ,

(A1)

where
JCinteraction =

t {_.!2.. PrA(rj) +2 e;
j=l

mjC

=JCint(l) +JC int (2).

A2(rj )}

mjC

(A2)

20 W. Heitler, Quantum Theory of Radiation (Clarendon Press,

Oxford, England, 1954).

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3196

BERSOHN, PAO, AND FRISCH

The sum over j extends over the N charged particles

of the molecule. The zeroth-order eigenfunctions of the
system (in the absence of interaction) are of the form

!/ta (fl' "', fN) I nkA, nk'A', nk"X",

).

(A3)

The occupation numbers nkA are the number of quanta

with wave vector k and polarization A present in the
box.
The scattering of photons can be described by transitions in which the material system in a state !/to absorbs the incident quantum k, is virtually excited, and

then emits the scattered quantum k' and is virtually

de-excited to its final state !/tn. Such a process may
be pictured by the Feynman diagram of Fig. 4(a).
The emission may precede the absorption in which
case the process is represented by Fig. 4(b). The probability or cross section for the scattering transition is
measured by the rate at which the amplitude for the
final state builds up in the over-all wavefunction of the
system. This amplitude is computed from time-dependent perturbation theory which in turn necessitates
the calculation of the matrix elements of x'int:

(A4a)

(A4b)
x'int(2) which contains two A operators may annihilate two quanta, create two quanta or annihilate one quantum
and create another. Here we include only the latter sort of matrix element

(A4c)
All the calculations which depend explicitly on the quantized field operators are condensed in the matrix elements (A4a), (A4b), and (A4c). Suppose that the scattering system is constructed of m units (each of which
contains na charged particles) which can be regarded as independent of each other. Within each unit the exponentials can be regarded as constants so that the matrix elements can now be written

(ASb)
(ASc)

R.. is the vector from an arbitrary origin to a fixed point in the scattering unit a. The vectors fj (for each a) extend from this fixed point to the instantaneous electron positions.

2. Ordinary Scattering Cross Sections in Terms of Structure Factors of Scattering Units

The form of the matrix elements shows that the scattering transition is accomplished by the use of x'int(1) twice
or x'lnt(2) once. Using second-order and first-order perturbation theory, we find that the transition probability
per unit time is given by
(A6)
m

where p,. is the density of final states n per unit energy per unit volume. The latter are characterized by a distribu-

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3197

tiGHT SCATTERiNG BY MOLECULES

tion in the angle 8, cp of the scattered photon of wave vector k' and polarization A' relative to the incident photon
characterized by k, A
(A7)
where dn is the solid angle within which the vector k' lies and w' is the frequency of the scattered quantum.
Substituting the appropriate matrix elements of the form of Eq. (2) we have

(AS)
where K=k'-k.
Our initial conditions correspond to nk'>" =0 and

nk>'~O.

If we use the abbreviation

(A9)

and substitute the initial conditions, our formula reduces to

(AlO)

The probability of a scattering event occurring per

unit time is just the differential scattering cross section
times the incident flux. As the incident flux is just
nk>.cjV, we can write

which means that in the sum

_ 271' 1 ~ [Xint(1) ]nq[Xint(1) ]qp[Xint(1) ]pO 12
~
~
Ii
m,p
(Eo-Eq) (Eo-Ep)

~+-O-

(A12)
du
Wn+-O
dn dnnn(cjV)'

(All)

The resulting expression for the cross section contains all ordinary one-photon scattering phenomena,
elastic and inelastic, and at all photon energies below
relativistic energies. In the next section we derive an
analogous formula for the scattering of two quanta.
3. Harmonic-Scattering Cross Sections
In single-quantum scattering there are two (2!)
Feynman diagrams corresponding to the two possible
~equences of emission and absorption. The harmonic
scattering is described by the annihilation of two incident photons of frequency WI, W2 and polarization AI, A2
with the creation of a photon with frequency Wa and
polarization As. There are six possible Feynman diagrams (d. Fig. 5) for this process corresponding to the
six different sequences of annihilation of two quanta
and creation of a third quantum. To each diagram
there corresponds a different set of matrix elements

there will be six terms. [The interaction energy JCint(2)

does not contribute to the elastic harmonic scattering
because its matrix elements are all diagonal in the
electronic energy and Xint(l), with which it would
have to be combined, has matrix elements which are
only off diagonal in the electronic energy. As we omit
discussion of the Raman effect we omit further mention of these terms.]
k3

- ~
1/10

!flo

(/Iq

(/Ir

kI

k~
1/10

k3

(/Iq

k.

"2

(/I

(110

k2

FIG. 5. FeY1l111an diagrams for elastic double-quantum scattering. Three more diagrams are obtained by permitting Wl and W2.

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3198

BERSOHN, PAO, AND

FRISCH

If we consider only the case of elastic scattering where the material system does not change its state, we set
W3=W1+W2 in Eq. (A12), use Eq. (A7) for Pn and obtain

211"
WkaXl ....k.}.2.kl}.I=~

I"7

('K 'D) {e2 ""[

(p>'.t'")oq(h.")qr(h,")rfJ
exp ~ '''~ m1i 7~ (E o-E q+fu.J1) (Eo-E r +fu.J1+fu.J2)

(h.")Oq(hl") qr(h,")rfJ
(Eo- E q +fu.J2) (Eo- E r +fu.J1+fu.J2)

(hl")Oq(h,") qr(ht)rfJ
(Eo- E q+fu.J1) (Eo- E r -fu.J2)

(h.")Oq(h3") qr(hl")rfJ
(Eo- E q+fu.J2) (Eo- E r -fu.J1)

(P).t)Oq(hl") qr(h.a)rfJ
+
(h,a)Oq(ht) qr(ht)rO
]} [2
(Eo- E q -fu.J1-fu.J2) (Eo- E r -fu.J2) (Eo- Eq-fu.J1-li(2) (Eo- E r -fu.J1)
X (211"IiC)3 (~) nkln k.(nk.+ 1) d~32V (~)3.
V
e4
k1k2k3m
Ii (211"c) 3 me2

(A13)

If we adopt the initial condition nk.=O and replace the bulky expression in the curly brackets by the dimensionless
snttering amplitude/a (2) and let (nk;c/V) =1(w.), we find
(A14)

APPENDIX B: INCOHERENT CONTRIBUTIONS FROM MOLECULES OF DIFFERENT POINT

GROUPS

The general and complex formulas of Table I and Eqs. (34)-(44) expressing the incoherent contributions to
the scattering in terms of components (3ijk in the molecular framework simplify if the molecule is symmetrical. In
the text the intensities are given for the groups Ta and Coo. In this appendix, results applicable to linearly polarized light for D 3h , C3., C2., and C3 are given. The components (3ijk have been re-expressed in terms of the com
ponents Sij where16
S;j=(3,jj for j = 1, 2, 3,
Si4 =(3i23+(3i32,
SiS = (3.13+(3i31,
S16=(3,12+(3i21 .

Individual Groups

D 3,.
/R
2)_IS 2
\/-,zzz -""{ 16,

/R 2)_2S2
\/-'x .. -TI16

Coo.
(ftm

=-ts332+-Js-S33( S31 +S15) +rh( S31+S15) 2,

(ftx .. ) = -Iss3l+As312+-hS152 -rh-S31S15+rh-S31S33 --s\S3SS15 .

Cs.

(ftm ) = t S332+-s\S162+rh ( S31 +S15) 2+-Js-S33(S31 +S15) ,

2
2
(3x .. ) = -hs3l+rl-sS162+As312 +rhS31S33 +-IS-S15 --s\S33S15
2

-m 31 15 .
S S

C2
(ft ...2) =tS332+ls-(S31+S15)2+-h(S32+S24) 2+-Is S33 (S31+ S15) +-s\S33(S32+S24) +rh(S31+S15) (S32+S24),
(ftx ..2) =-hS332+A (S312+S322) +rhS33 (S31 +S32) +-s\S31SS2+rhS152+S242 -rhS15S24

--hSSS(S24+S15) --h(SSlS15+SS2S24) -rh(S31S24+ S32S15).

Ca
<fJm2) = tSn2+tS162+tS332+rh(S31+S15) 2_-s\SnS16+-Js-S33( S31 +S15) ,
(ft:r 2) = frSn2+/rS162 +-hS332 + A S312+rh-S31S33 +-IsSI52+/sS142 --s\S15S33 - ToSalS15 +rhS31S14 .
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