Physica 69 (1973) 422-432 0 North-Holland Publishing Co.

ON THE DERIVATION OF THE

KIRKWOOD-FRtjHLICH EQUATION

P. BORDEWIJK
Gorlaeus Laboratoria der Rijksuniversiteit, Afdeling Fysische Chentie,
Leiden, Nederland

Received 29 May 1973

Synopsis
A new derivation of the Kirkwood-Frohlich equation is presented. It follows from this
derivation that within the limitation that the electric properties of the molecules are characterized
completely by a permanent dipole moment and a constant, scalar polarizability, the Kirkwood-
Frohlich equation holds rigorously for a cubic lattice. For liquids the approximation should be
made that translational fluctuations may be neglected, and that the positions are independent
of the orientations.

1. Introduction. In the evaluation of static dielectric measurements on associat-

ing liquids in terms of the electric parameters of the molecules and the specific
molecular interactions, use is often madelTs) of the so-called Kirkwood-Frohlich
equation :

(E - e,) (2E + .5,)/E (E, + 2)2 = (4xN/9kT) g$. e(l)

In this equation E is the dielectric constant of the liquid, E, is the dielectric constant
of induced polarization, Nis the number density, p is the permanent dipole moment
of the molecule in Z.MZCUO, and g is the Kirkwood correlation factor, that indicates
the degree of correlation between the permanent dipole moments of the mole-
cules :

(2)

Here 8ij is the angle between the permanent dipoles of the molecules i andj, riJ is
the distance between their centres of gravity, and V indicates the volume of the
whole dielectric. At distances where the dependence on cos Bii of the energy of the
system, averaged over the positions and orientations of all molecules except mole-
cules i andj, is dominated by the dipole-dipole interaction between the molecules

422
 ON THE DERIVATION OF THE KIRKWOOD-FROHLICH EQUATION 423

i and j, the value of x, (cos 0ij) will not change when the sphere with radius r
around the centre of gravity of molecule i is extended and the ratio V/r is kept
constant; therefore g as defined by eq. (2)accounts only for short-distance mole-
cular interactions in the liquid. Due to the correlation factor, eq. (1) differs from
the Onsager equation [ref. 6, eq. (28)]:

(E - E,) (2E + E,)/E (8, + 2)2 = (4xN/9kT)$, (3)

which is derived for the model of a liquid consisting of particles with the permanent
moment and polarizability equal to those of the molecules, in spherical cavities
with the size of the molecular volume, surrounded by a continuum with the macro-
scopic properties of the dielectric.
An expression equivalent with eq. (1) was first derived for the case of nonpolariz-
able molecules (E, = 1) by Kirkwood), who treated the sphere with radius r on a
statistical basis, and the surrounding dielectric as a continuum. Essentially, this is
the procedure used in all publications dealing with eq. (1). The correlation factor g
was introduced by Oster and Kirkwoods), who restricted themselves in the cal-
culation of this factor for water to the shell of nearest neighbours of the molecule i.
For the case of polarizable molecules, an equation corresponding to eq. (1) was
first given by Friihlich [ref. 9, eq. (8.14)]. This equation was derived by considering
the induced polarization on a macroscopic basis; the orientation polarization is
then considered to be built up from permanent dipoles with appropriate dipole
strength, in a continuum with dielectric constant E, . Although the resulting ex-
pression was used by many experimental workers in the evaluation of their measure-
ments, Friihlichs derivation was criticized in several more theoretical articles.
The main reason for this is that the derivation obscures the exact nature of the
approximations made in eq. (1). Therefore, a number of authors tried to derive
eq. (1) for the model of particles with electrical properties characterized by a per-
manent dipole ,u and a scalar polarizability 01,located at the centre of gravity of the
molecule. For the derivation of eq. (1) the approximation is then introducedlO_12)
that the fluctuations of the moment induced in a molecule by all neighbouring mole-
cules during the movements of the molecules can be neglected, and that this induced
moment has the same value as when the surroundings of the molecule can be con-
sidered as a continuum with a spherical cavity with the size of the molecular volume,
in which the molecule is located. The latter approximation is rather crude, however;
it was demonstrated by Mandel13) that for a calculation of E in this way up to linear
terms in the polarizability, not only the reduced two-particle distribution function
(that is necessary in the calculation of g) should be used, but also the reduced three-
particle distribution function.
In the following, another derivation of the Kirkwood-Friihlich equation is
presented. From this derivation it appears that the Kirkwood-Frohlich equation
holds rigorously for the case of a cubic lattice. For a liquid, the approximation
424 P. BORDEWIJK

should be made that the translational fluctuations may be neglected, and that the
positions are independent of the orientations.

2. Basic equations. An infinite dielectric with dielectric constant E is considered,

in which there is a uniform electric field E. The electric moment Mof a finite macro-
scopic sphere with volume r~in the dielectric is calculated on a molecular basis,
whereas the surrounding dielectric is treated as a continuum. The relation between
E and M is given by:

(4)

where e is the unit vector in the direction of the field E, and the index 0 indicates
E = 0. The average moment of the sphere in the direction of the field, <M * e),
can be calculated with the help of a classical, canonical ensemble:

(M-e) = jdXM .e exp (- U/kT)/J dX exp (- UIRT), (5)

where f dxindicates an integration over all configurations, and U is the total poten-
tial energy. Using (M * e). = 0, one obtains by differentiation of eq. (5):

(6)

The first term of the right-hand side of eq. (6) corresponds with the average value
of the change of the moment M on application of the field E for fixed orientations
of the molecules. Thus, in this term only the induced polarization plays a role, and
it can be obtained from the polarization of a sphere with dielectric constant F,
surrounded by a dielectric with dielectric constant a14) :

3E
V.
4X 2E + E,

Substituting this into eq. (6), and substituting the resulting expression into eq. (4),
we obtain :

(E - Egi)(2E + 1) v
= -& (M*ez)O. (8)
4X (28 + 8,)

The total potential energy U consists of an electrical part and a nonelectrical part;
for the calculation of au/LYE only the electrical part V,, should be considered. The
calculation of V,, proceeds analogously to the calculation of V,, for a sphere in
vacua, as given by Mandel and Mazur15). V,, is the energy of a system of dipoles
 ON THE DERIVATION OF THE KIRKWOOD-FROHLICH EQUATION 425

mi, consisting of a permanent part /li and an induced part pi, in a spherical cavity
in a continuum with dielectric constant E, in which in the absence of the system of
dipoles the field would be equal to the cavity field EC:

EC = [3&/(2& + l)] E. (9)

The energy V,, consists of four parts: 1) the energy V,,, necessary to enlarge the
dipoles pL to the values m, = pf + pi:

2) the energy V,,, of the dipoles in each others fields:

(11)

where Tij is the dipole-dipole interaction tensor :

Tij= (l/r:) (Y; - 3rijrij) 2 (12)

and where the factor + is incorporated to avoid counting each dipole-dipole inter-
action twice ;
3) the energy VEcnecessary to bring the system of dipoles in the electric field in the
empty cavity :

VIZ,= -EC-Cm,; (13)

I

4) the energy V, necessary to bring the system of dipoles into the reaction field in
the cavity :

where Fi,iis the tensor that accounts for the reaction field of a dipole mj at ri

R(rJ = c Ffj (ri , rj) - mj. (15)

j

Since the energy of the dipole mi in the reaction field due to mj is equal to the energy
of the dipole mj in the reaction field due to mi16), one has:

Fij (vi Vj) = Fji (VI) vi).

)
(16)

The present calculation differs from the calculation of V,, for a sphere in zxzcuo as
performed by Mandel and Mazur, only as far as the contribution V, is concerned.
426 P. BORDEWIJK

The moments mi are interrelated by:

m, = ,ui + LX EC - c Ti; - mj (17)

( j !2
where

T,; = Tij - Fij , i*j, T;j = -Fij, i=j. (18)

.
To write eq. (17) in a more manageable form, we use 3n-dimensional vectors
m, p, p, and e, and a 3n x 3n-dimensional tensor T, where n is the number of
molecules in, the sphere with volume v (n = NV). The projection of m, p, p, and e
on the 3-dimensional subspace of the ith molecule gives the 3-dimensional vectors
m,, pi, pi and e, respectively; the 3n x 3n-dimensional tensor T is composed of
n x n elements of dimension 3 x 3, equal to the tensors Tij. In the 3n-dimensional
notation, eq. (17) is written as:

m = p + a(eE, - Tsm), (19)

leading to :

m = (1 + aT)- * (p + aE,e) = m + olA . eE,, (20)

where 1 is the 3n x 3n dimensional unit tensor, and m and A are given by:

m = p - (1 + &T)-i, (21)
A = (1 + aT)-i. (22)

Here T is a symmetric tensor, as follows from the fact that Tij and Fir are sym-
metric tensors, and Tij = Tji, F,, = Fji [cJ: eqs. (12) and (16)]. It should be men-
tioned that A as defined by our eq. (22) differs by a factor l/cx from A as used by
Mandel and Mazur [ref. 15, eq. (7)].
In the 3n-dimensional formalism, the contributions to V,, are written as:

vin = (l/2&) CPi pi = (l/2%)p p, (23)

1

VE, = -Ec.xmi = -E,e*m. (25)

I

Combination of eqs. (23), (24) and (25) leads after some rearrangements to:

V,, = _tp . T . m - E,e . m + &xE:e * A * e. (26)

 ON THE DERIVATION OF THE KIRKWOOD-FROHLICH EQUATION 427

From this follows :

(27)

Substituting this result into eq. (S), we obtain:

(E ?- E,) (28 + I)2 V

=-&(M.e)(M.e)), = &<M.M),. (28)
12x.5 (2E + E,)

For the calculation of (Mm M),, we start from eq. (21):

m = p - (1 + aT)-l = p - A. (29)

From this relation follows:

my = cpi - Aij, (30)

i

where Aij is the projection of A on the product of subspaces connected with the
ith and jth molecule. Using eq. (30), we have for MO :

M=~m~=CC~i.Aii=~~i.~A,j, (31)
I i

and (M * M). is given by:

(M-M)0 = ((TPi*I$A,j) * (s~k.cAk,))* (32)

Combining this result with eq. (28), we obtain:

(E - E,) (2E + I)2 u

=~((~~*5:Ai~)(~p,~Akt))o. (33)
4TFE(2E + E,)

3. Cubic lattice. In eq. (33) the tensors Cj Aii and x1 Akl depend only on the
positions and not on the orientations of the molecules. Therefore, if the molecules
are located at fixed lattice points, so that the brackets in eq. (33) indicate averaging
over the orientations only, the elements of the tensors cj Aij and cI Akl will be
constant. For a cubic lattice, rj A,, can be calculated using the property that when
a spherical sample is brought into a uniform external field without changing the
orientation of the permanent moments, the changes of the moments will be the
same for all molecules:

-am, 1 aM
= ---. (34)
aE n aE
428 P. BORDEWIJK

The right-hand side of this equation is obtained from eq. (7), where for a lattice
the averaging is not necessary. For the calculation of the left-hand side of eq. (34),
we use eq. (20), from which follows:

dml aE,
-=- ace- A,j. (35)
aE aE I

Since in a cubic lattice for every direction of e, e,and am&YE will have the same
direction, one obtains :
.

2 4, = C-G- 1) (2E + 1)/4xN (2E + Em) Ly. (36)

J

Combining this with the Clausius-Mossotti equation for the induced polarization,
that holds exactly for a cubic lattice :

01 = [(Em - l)/km+ 2)13/4xN, (37)

one obtains :

1 Aij = (E, + 2) (2~ + 1)/3 (2~ + sm). (38)

j

In eq. (38) the scalar factor is equal to the factor for the enlargement of a polarizable
dipole by the reaction fieldl). Substitution of eq. (38) into eq. (33) followed by ap-
plication of eq. (2), which is justified since both limits are reached for the case of a
macroscopic sphere in an infinite dielectric, leads to the Kirkwood-FrShlichequa-
tion, eq. (1) :

(E - s,) (2E + E,)

&(gm f 2)2

4. Liquids. In a liquid, the tensors ~j Aij and x1 Akl will change during the
movements of the molecules. In the approximation to which the translational fluc-
tuations are negligible, we may replace & Aij and XI Akl by their average value
over all positions. Introducing the further approximation that the positions and the
orientations are independent, we may replace in eq. (33) x1 Aij with its average
value x:j xj over all positions and orientations, leading to :

(a - E,) (28 + 1) v
=$ ((TPiIjZT?;;! (~PkFX)),. (39)
4TCE(28 + E,)

The average xj ATcan be calculated from the induced polarization, in the same
 ON THE DERIVATION OF THE KIRKWOOD-FROHLICH EQUATION 429

way as for the case of a cubic lattice. Starting from eq. (7) we have:

3E
= -~((e~A~e)
o 2E + 1
3E 3E
= -a~~(e~A,j~e> =-nnole.CAlj*e.
2&+-l i J 2E + 1 J

(40)
Eq. (40) holds independently of the direction of e. From this it can be inferred that
CJ z will be equal to the unit tensor multiplied by a scalar. Thus :

CAij= (%I -
1) (2E + 1) = (8, + 2) (28 + 1)
(41)
J 47rN(2& + E,) Ly 3 (2E + E,)

where again the Clausius-Mossotti equation is used, which for liquids a1s.oholds in
the approximation to which the translational fluctuations are negligible. Comparing
eqs. (41) and (38), it appears that the eXpreSSiOn for for a liquid iS eqUd to
CJ A,J

the expression for cJ A,, for a cubic lattice. Substituting eq. (41) into eq. (39), the
Kirkwood-FrBhlich equation is obtained again.

5. Discussion. It follows from the derivation given above that, as far as the
electric properties of the molecules can be described with the help of a permanent
dipole moment ,u and a constant, isotropic polarizability o(,the Kirkwood-Friihlich
equation can be derived rigorously for a cubic lattice, and for liquids in the ap-
proximation to which both the translational fluctuations and the correlation be-
tween positions and orientations are negligible. The derivation presented here
differs from the derivation given by Friihlich in that it considers the induced polari-
zation on a molecular basis. For this reason, our derivation gives more insight into
the approximations that are involved in the Kirkwood-Frohlich equation, than
FrBhlichs derivation does.
A difference between our derivation and the derivations given by Buckingham
and by Cole is that our derivation starts from a sphere embedded in a continuum
with the macroscopic properties of the dielectric, instead of a sphere in uacuo. In
the derivations given by Buckingham and by Cole it is necessary to evaluate the ex-
pression <pi * ik& for a sphere in ~ucuo, where M is split up into three parts, i.e.,
the moment mi of the molecule i enlarged by the reaction field, the total moment of
the other molecules within a sphere that is small with respect to the macroscopic
sphere (the average value of this moment for fixed orientation of molecule i deviates
from zero due to short-range interactions), and the moment of the remainder of the
430 P. BORDEWIJK

sphere, of which the average value for fixed orientation of molecule i depends on
long-range dipole-dipole interactions. In the calculation of the moment mi , the use
of the reaction field has to be criticized, since this ignores the short-range inter-
actions. It must be preferable to calculate first the total moment of a small sphere of
macroscopic dimensions as far as it is built up from permanent moments, and
afterwards calculate the enlargement of the total moment of the molecules in the
small sphere that is directly or indirectly caused by the permanent moments of
molecules in the small sphere, including the contributions due to the reaction fields.
This is the essential point in our derivation [cJ eq. (31)].
For liquids neglecting the translational fluctuations as well as the correlation
between positions and orientations may be considered to be a good approximation,
as long as the molecules are closely packed, so that the surroundings of the mole-
cules are rather symmetric. In fact, the Clausius-Mossotti equation, that is also
based on neglecting translational fluctuations, holds rather well for liquid systems
with close packing.
It is obvious that for zero polarizability of the molecules, the Kirkwood-Friihlich
equation holds exactly. Therefore, it is interesting to investigate the deviations from
the Kirkwood-Frohlich equation as a function of the polarizability LX.To this end
we write eq. (32) with the help of a tensor Aij that indicates the deviation of Aij
from its average value Aij:

1 (c, - 1) (2.5 + 1) ngP2

=-
l%2N2 16x2 (2s + E,)~

: 2 @cc
- 1) (2E + 1)
n (Pi* (~P/c~~~))
oriv 4x (2.5 + Em)

(42)

The tensor ~4;~can be calculated with the help of eq. (22):

.4;, = Aij - A,I = [(I + OIT)-~]~~- ((1 + T)-l)ij

= Sij - OCTET
+ 01F T,kT&+ U(n3)]
[

- dij - aqj + a2 & T,,TL~+ 0(a3)

[ I
= - a (T;, - T;i;;>+ 01c (TkT;., - TikT,$) + U(a3). (43)
k
 ON THE DERIVATION OF THE KIRKWOOD-FRtiHLICH EQUATION 431

Substituting this into eq. (42), we obtain:

-- 2 (G- 1) (2E + 1)
na Pi * T /lk * T KCc~ - El
aN 4X (2e + E,) (

--
- 01; (T&% - %,T,i,J + @G2)1
>

When considering this expression, it should be taken into account that for low
values of o1the factor (Ed - 1) is proportional to a; therefore the first term of eq. (44)
is of order zero in 01for OL+ 0, the second term of order one, and the third term of
order two. Substitution of the corrected Clausius-Mossotti expression for a in the
first term of eq. (41) will lead to a correction term that is second order in OL,since
for the induced polarization the corrected Clausius-Mossotti equation is of the
form15) :

EC0 -11 4x
- - = 3 Ly[ 1 + O(a2)]. (45)
e,+2N

Thus, there is only one term of order (x, and eq. (44) can be written as:

(M-M), =
CL + 2j2 (2Ef II2 ngp2

9 (2.5 + E,)2

- 2(E;;;YF
; )na (Pi c
k
Pk T (T,', - z)) + o(Ly2),
E m
(46)
leading to :

(E - 8,) (2E + Go)

E (E, + 2)2

6 (2~ + E,) -
a (Pi c Pk * 1 (Trh - T,$> + o(a2) .
(e, + 2) (2.5 + 1) k 1 >

(47)
Clearly, when the translational fluctuations and the correlations between positions
and orientations may not be neglected, for the evaluation of the correction up to
432 P. BORDEWIJK

linear terms in the polarizability one should know the three-particle distribution
function; this result is in agreement with the results of Mandel13).
As mentioned before, for most liquids the approximation of neglecting the trans-
lational fluctuations and correlations between positions and orientations will be
appropriate. For those cases our derivation enhances the value of the Kirkwood-
Friihlich equation in the evaluation of static dielectric measurements in terms of
the correlation between the orientation of the molecules. This holds even stronger
in the case of a cubic lattice (cJ the calculations of Cobush and Hoeve18) for
cubic ice). It must be expected that the equations for the nonlinear dielectric be-
haviour of polar systems with nonzero polarizability, which are also derived with
the help of Frbhlichs model for the induced polarizationlg-*), can be shown to
depend on neglecting the translational fluctuations and the correlation between
positions and orientations in the same way as is demonstrated in this article for
the Kirkwood-Frohlich equation.

Acknowledgement. The author wishes to thank Professor M.Mandel and

Mr. A. Rip for helpful discussions.

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5) Biittcher, C. J. F., Theory of Electric Polarization, second edition, Vol. I, Elsevier (Amster-
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