Frequency dependence of ionic conductivity of electrolyte solutions

Amalendu Chandra and Biman Bagchi

Citation: The Journal of Chemical Physics 112, 1876 (2000); doi: 10.1063/1.480751
View online: http://dx.doi.org/10.1063/1.480751
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 JOURNAL OF CHEMICAL PHYSICS VOLUME 112, NUMBER 4 22 JANUARY 2000

Frequency dependence of ionic conductivity of electrolyte solutions

Amalendu Chandraa)
Department of Chemistry, Indian Institute of Technology, Kanpur, India 208016
Biman Bagchi
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore, India 560 012
and Department of Chemistry, University of Wisconsin at Madison, Madison, Wisconsin 53706
共Received 17 June 1999; accepted 22 October 1999兲
A theory for the frequency dependence of ionic conductivity of an electrolyte solution is presented.
In this theory contributions to the conductivity from both the ion atmosphere relaxation and the
electrophoretic effects are included in a self-consistent fashion. Mode coupling theory, combined
with time-dependent density functional theory of ion atmosphere fluctuations, leads to expressions
for these two contributions at finite frequencies. These expressions need to be solved
self-consistently for the frequency dependence of the electrolyte friction and the ion conductivity at
varying ion concentrations. In the limit of low concentration, the present theory reduces exactly to
the well-known Debye–Falkenhagen 共DF兲 expression of the frequency-dependent electrolyte
friction when the non-Markovian effects in the ion atmosphere relaxation are ignored and in
addition the ions are considered to be pointlike. The present theory also reproduces the expressions
of the frequency-dependent conductivity derived by Chandra, Wei, and Patey when appropriate
limiting situations are considered. We have carried out detailed numerical solutions of the
self-consistent equations for concentrated solutions of a 1:1 electrolyte by using the expressions of
pair correlation functions given by Attard. Numerical results reveal that the frequency dependence
of the electrolyte friction at finite concentration can be quite different from that given by the DF
expression. With the increase of ion concentration, the dispersion of the friction is found to occur
at a higher frequency because of faster relaxation of the ion atmosphere. At low frequency, the real
part of the conductivity shows a small increase with frequency which can be attributed to the
well-known Debye–Falkenhagen effect. At high frequency, the conductivity decreases as expected.
The extensions of the present theory to treat frequency-dependent diffusivities of charged colloid
suspensions and conductivity of a dilute polyelectrolyte solution are discussed. © 2000 American
Institute of Physics. 关S0021-9606共00兲51103-9兴

I. INTRODUCTION limiting ionic conductance ⌳ 0 , which is determined by the

statics and dynamics of ion–solvent interactions. Significant
The dynamics of electrolyte solutions has remained a progress has been made in recent years in understanding this
central area of research in physical chemistry for a long problem. In particular, it has been pointed out that the ul-
time.1–6 Despite vigorous activity over many decades, many trafast solvation of ions observed in water and acetonitrile
fundamental problems have remained unsolved which have can play an important role in reducing the magnitude of di-
led to recurrent attempts by theoreticians to address them. electric friction on small rigid ions. This and other aspects
The motion of ions in an electrolyte solution is usually de- have been reviewed recently in Ref. 6. The second important
scribed by the specific conductivity 共␴兲 or by the equivalent problem is the concentration dependence of the ionic con-
conductance 共⌳兲 which is the specific conductivity divided ductance in the limit of small concentration, as embodied in
by the molar concentration of the salt. The best known ex- the Debye–Huckel–Onsager square root concentration law
pression for the equivalent conductance of an electrolyte so- given above. Many aspects of this law have been clarified in
lution is the Debye–Huckel–Onsager relation given by7,8 recent years and studies have been extended to higher
⌳ 共 c 兲 ⫽⌳ 0 ⫺ 共 A⫹B⌳ 0 兲 冑c, 共1兲 concentrations.9–13 However, a fully molecular theory which
is valid at high concentrations, even for the simplest case of
where ⌳(c) is the equivalent conductance of the electrolyte strong electrolytes, is yet to be developed. The third impor-
when the molar concentration of the salt is c, ⌳ 0 is the same tant problem is the motion of ions in the presence of an
at infinite dilution of the electrolyte. A and B are numerical oscillating electric field.14–20 The last one is the subject of
constants which depend on dielectric constant, viscosity, and the present article. The above-mentioned list is by no means
temperature of the solution and also on charges of the ions. exhaustive.
The problem of ion motion can be naturally divided into The motion of ions in the presence of a time-dependent
several parts. The first is the problem of understanding the electric field is traditionally described by the frequency-
dependent specific conductivity ␴共␻兲 where ␻ is the oscilla-
a兲
Electronic mail: [email protected] tion frequency of the external field. The frequency-

0021-9606/2000/112(4)/1876/11/$17.00 1876 © 2000 American Institute of Physics

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 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 Frequency dependence of ionic conductivity 1877

dependent conductivity is intimately related to the Recently Chandra, Wei, and Patey 共CWP兲19 have ad-
frequency-dependent electrolyte friction. One of the earliest dressed the problem of frequency dependence of ionic con-
studies of the frequency-dependent electrolyte friction and ductivity. These authors derived analytical expressions of
conductivity was that of Debye and Falkenhagen 共DF兲.14 ␴共␻兲 by employing a non-Markovian equation of motion of
These authors considered the dynamic effect of the relax- the self van Hove function of a tagged ion. By employing
ation of ion atmosphere on the motion of an ion. When an exactly known short and long time constraints upon the ionic
ion moves in electrolyte solution, the atmosphere cannot im- self van Hove function, these authors derived two closed-
mediately follow the motion of the central ion and becomes form expressions of the frequency-dependent conductivity
asymmetric causing a retarding effect on the motion of the 共models I and II兲. Model I depends on an expression of the
ion. At zero frequency, this relaxation effect leads to the frequency-dependent diffusion coefficient which ensures that
B⌳ 0 冑c term in Eq. 共1兲. In presence of an oscillating field, the short time dynamics up to the second frequency moment
the central ion oscillates and the ion atmosphere gets less and the long time dynamics of the self van Hove function are
time to relax and remains less asymmetric. As a result, the described correctly. The final expression of the conductivity
effects of the asymmetry of the ion atmosphere is reduced is described by a multiple Debye form19
causing a reduction of the electrolyte friction and an en- 2
1 ␳ a q ␣2 D ␣
hancement of the conductivity at low frequency. At high fre-
quency, the conductivity decreases because the ions oscillate
␴共 ␻ 兲⫽ 兺
k B T ␣ ⫽1 1⫺i ␻ D ␣ m ␣ /k B T
, 共5兲
so fast that the net ionic motion along a particular direction is
smaller than that in the presence of a static or low frequency where m ␣ is the mass of an ion of species ␣. Model II of
field. By using a diffusion equation approach for the time CWP is based on a different expression of the frequency-
dependence of ion atmosphere, Debye–Falkenhagen derived dependent diffusion coefficient which correctly describes the
the following rather unusual looking expression for the short time dynamics up to the fourth frequency moment and
frequency-dependent electrolyte friction.14 also the long time dynamics of the ionic self van Hove func-
tions. In this model, ␴共␻兲 is given by19

冋 册
1⫹ 冑q 2
␨ DF共 ␻ 兲 ⫽ ␨ DF共 0 兲 , 共2兲 1 D ␣ ⍀ ␣2 ⫺i ␻ k B T/m ␣
1⫹ 关 q 共 1⫺i ␻ ␶ atm兲兴 1/2
␴共 ␻ 兲⫽ 兺 ␳ q 2
k B T ␣ ⫽1 ␣ ␣ ⍀ ␣2 ⫺ ␻ 2 ⫺i ␻ D ␣ ⍀ ␣2 m ␣ /k B T
,
where ␨ DF(0) is the zero-frequency friction, q⫽1/2 for a 共6兲
symmetric binary electrolyte and ␶ atm is the relaxation time
where ⍀ ␣ is the Einstein frequency of an ion of species ␣.
of the ion atmosphere given by
We note that ⍀ ␣2 is proportional to the mean square force
1 acting on an ion. The results of CWP were compared with
␶ atm⫽ . 共3兲 those of molecular dynamics simulations. Their theory is ca-
共 D 1 ⫹D 2 兲 q ␬ D
2
pable of predicting the Debye–Falkenhagen effect at low
Here, D 1 and D 2 are, respectively, the self-diffusion coeffi- frequency and was found to provide a reasonable description
cients of the positive and negative ions and ␬ D is the inverse of the ionic motion at high frequency when there were no ion
Debye screening length given by pairs and tightly bound solvation shells in the solution.19
However, for many complex systems, the theory of CWP
2
4␲ was found to be inadequate which, in part, can be attributed
␬ D2 ⫽ 兺 ␳ q2 ,
⑀ k B T ␣ ⫽1 ␣ ␣
共4兲 to the absence of full self-consistent calculation of the
frequency-dependent electrolyte friction in this theory. It is
where ⑀ is the static dielectric constant of the medium, q ␣ clear that further work is needed to fully understand the ionic
and ␳ ␣ are, respectively, the charge of an ion and bulk num- conductivity at finite frequency.
ber density of species ␣, k B is Boltzmann constant, and T is More recently we have developed a self-consistent
the absolute temperature. The DF theory is valid at very low theory of the zero-frequency conductivity which describes
concentrations. For a typical 0.001 M solution of a 1:1 salt, the ionic flow when a static field is applied.12,13 The theory is
␶ atm⬃10⫺7 s and, therefore, the dispersion of the DF friction based on a combination of the mode coupling theory and the
for such a solution is predicted to occur in the megahertz or time-dependent density functional approach and included
below gigahertz region. The electrophoretic force, on the both ion atmosphere relaxation and electrophoretic effects.
other hand, responds at rates comparable to that of molecular The theory correctly goes over to the well-known Debye–
velocity correlations. The velocity correlation times in solu- Huckel–Onsager 共DHO兲 law7,8 in the limit of very low ion
tions are of the order of 0.1 ps and thus the dispersion of the concentration. In addition, it remains valid in the much
electrophoretic contribution occurs at a frequency much higher concentration regime where the DHO limiting law
higher than gigahertz. In DF theory, the frequency depen- fails completely. In the present paper, we extend the above-
dence of the electrophoretic effect is not considered. Thus, mentioned theory to investigate electrolyte friction and con-
the well-known Debye–Falkenhagen effect of increasing ductivity at finite frequencies.
conductivity with frequency arises solely from the decrease In this work, we derive self-consistent expressions for
of the friction from the ion atmosphere. Thus one immediate the frequency-dependent electrolyte friction and the conduc-
effect of the frequency dependence is the inapplicability of tivity which incorporate the details of the static and dynamic
any form like Debye–Huckel–Onsager limiting law. ion–ion correlations and also the effects of self-motion of the
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 1878 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 A. Chandra and B. Bagchi

ions. Both the ion atmosphere relaxation and the electro- q ␣q ␤

phoretic effects are calculated at finite frequency and these u ␣␤ 共 r 兲 ⫽u ␣␤
SR
共 r 兲⫹ , 共7兲
⑀r
contributions are combined to obtain the frequency-
SR
dependent friction and the conductivity. Self-consistency is where r is the distance between the two ions and u ␣␤ (r) is a
essential in this problem because the dynamics of ion atmo- spherically symmetric short-range interaction potential. This
sphere relaxation and the electrophoretic friction depend on so-called primitive model is well known in the studies of
the mobility of the ions themselves. And the mobility of ions structure and dynamics of electrolyte solutions.21 Through-
depends on the relaxation of these two effects. The above- out this paper, we label the positive ions as species 1 and the
mentioned self-consistency also demands an inherently non- negative ions as species 2. We denote the position 共r兲 and
Markovian theory for the relaxation of the ion atmosphere. It time 共t兲 dependent number density of species ␣ as ␳ ␣ (r,t)
is shown that the DF expression of the frequency-dependent and its Fourier transform ␳ ␣ (k,t) is defined by

冕
electrolyte friction can be recovered from the present micro- ⬁
scopic theory in the limit of low ion concentration when the ␳ ␣ 共 k,t 兲 ⫽ dre ik•r␳ ␣ 共 r,t 兲 . 共8兲
⫺⬁
finite sizes of the ions are ignored and the collective dynam-
ics of the ion atmosphere is described by diffusional motion. In this paper, we are interested in calculating the
Thus, the validity and the limitations of the DF friction be- frequency-dependent friction on a moving ion and the
comes clear from the present microscopic approach. The frequency-dependent conductivity of the solution. For this
present theory also reproduces the expressions of the purpose, we consider a single tagged ion of charge q s . The
frequency-dependent conductivity derived by Chandra, Wei, velocity of the tagged ion is v s (t) at time t. Its time evolution
and Patey19 when appropriate limiting situations are consid- can be described by the following generalized Langevin
ered. equation:21

冕
Numerical results show that the frequency dependence
of the electrolyte friction at finite concentration can be very ⳵ ⬁
v 共 t 兲 ⫽⫺ dt ␨ s 共 t⫺t ⬘ 兲v s 共 t ⬘ 兲 ⫹ f s 共 t 兲 , 共9兲
different from that given by the DF expression. With in- ⳵t s 0
crease of ion concentration, the dispersion of the friction is
where ␨ s (t) is the total friction acting on the single tagged
found to occur at a higher frequency because of faster relax-
ion and f s (t) is the so-called random force. The frequency-
ation of the ion atmosphere. Numerical results are also pre-
dependent friction ␨ s ( ␻ ) is defined as the Laplace transform
sented for the frequency dependence of the real and imagi-
of ␨ s (t),
nary parts of the conductivity. At low frequency, the real part
of the conductivity changes rather weakly with frequency. In
fact, the real part shows a slight increase at low frequency ␨ s共 ␻ 兲 ⫽ 冕 0
⬁
dt e i ␻ t ␨ s 共 t 兲 . 共10兲
which can be attributed to the Debye–Falkenhagen effect. At
high frequency, the conductivity decreases because the ions The self-diffusion coefficient D s ( ␻ ) is related to the
oscillate so fast that the net ionic motion along a particular friction ␨ s ( ␻ ) by the following generalized Einstein
direction is smaller than that in presence of a static or low relation:21
frequency field. The Cole–Cole plots of the conductivity re- k BT
veal a nearly Debye behavior of the conductivity dispersion D s共 ␻ 兲 ⫽ 关 ⫺i ␻ ⫹ ␨ s 共 ␻ 兲兴 ⫺1 , 共11兲
m
for very dilute solutions. As the concentration is increased,
the dispersion becomes non-Debye at low frequency due to where m s is the mass of the tagged ion. In the present work,
Debye–Falkenhagen effect. our focus will be on the calculation of the frequency-
The organization of the rest of the paper is as follows. In dependent friction ␨ s ( ␻ ) and the frequency-dependent self-
Sec. II, we present the theory and in Sec. III, we discuss the diffusion coefficient D s ( ␻ ). Once the frequency-dependent
reduction to the Debye–Falkenhagen expression. In Sec. IV, self-diffusion coefficient D s ( ␻ ) is known, the frequency-
we show how the conductivity expressions of CWP can be dependent conductivity ␴ ( ␻ ) can be calculated by using the
recovered from the present theory. We discuss the numerical following generalized Nernst-Einstein relation;19,21
results in Sec. V. Section VI concludes with a summary and 2
1
a brief discussion on the extensions of the present theory to
treat frequency-dependent diffusivities of charged colloid
␴共 ␻ 兲⫽ 兺
␳ q2 D 共 ␻ 兲,
k B T ␣ ⫽1 ␣ ␣ ␣
共12兲

suspensions and conductivity of a dilute polyelectrolyte so- where ␳ ␣ and q ␣ are defined in Sec. I. We note in this con-
lution. text that the frequency-dependent electric conductivity can,
in general, be related to the Fourier transform of the electric
II. THEORETICAL FORMULATION
current–current time correlation function.21 Since the electric
We consider an electrolyte solution consisting of posi- current is a collective dynamical quantity, its time correlation
tive and negative ions immersed in a continuum solvent of function comprises a self part that corresponds to a summa-
dielectric constant ⑀. The ions interact through a spherically tion over the velocity autocorrelation functions of the ions
symmetric short-range potential and a long-range coulombic and a cross part involving the sum of the correlation func-
interaction potential which is scaled by the value of the di- tions of the velocities of distinct ions. The generalized
electric constant. The pair potential of interaction between Nernst–Einstein relation 关Eq. 共12兲兴 includes only the self
two ions of charge q ␣ and q ␤ is given by part and thus the cross part is ignored in the present work.
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 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 Frequency dependence of ionic conductivity 1879

Although the importance of the cross part is smaller than the 1 1 1

self part, it may not be negligible at high ion concentrations. ⫽ ⫹ , 共14兲
␨ s;hyd共 ␻ 兲 ␨ s;hyd共 c⫽0 兲 ␦ ␨ s;hyd共 ␻ 兲
However, at low and moderate concentrations, the contribu-
tion of the cross part is expected to be rather small. For where ␨ s;hyd(c⫽0) is the viscous friction which also in-
example, at 0.5 M concentration of aqueous NaCl solution, cludes the additional dielectric friction contribution due to
an analysis of the simulation data of self-diffusion coeffi- the polarization current29,30 and ␦ ␨ s;hyd( ␻ ) represents the
cients and conductivity reveals that the cross term reduces electrolyte friction on the tagged ion due to coupling with the
the static conductivity by less than 5%.11 We also note that ion atmosphere current, which is commonly known as the
the solvent is considered to be a dielectric continuum in the electrophoretic effect. In the following, we calculate the fre-
present theory. At high concentrations, the molecular details quency dependence of the ion atmosphere contributions
of the ion–solvent and solvent–solvent correlations may be- ␦ ␨ s;mic( ␻ ) and ␦ ␨ s;hyd( ␻ ).
come important. Because of these approximations, the
present theory is limited to solutions of not too high concen-
A. Calculation of the time-dependent microscopic
tration. friction, ␦ ␨ s ,mic„ t …
The total friction acting on the tagged ion can be decom-
posed into two parts. The first part is due to the microscopic The time-dependent microscopic electrolyte friction,
interaction of the tagged ion with the surrounding solvent ␦ ␨ s,mic(t), is calculated by using the following Kirkwood
molecules and ions and the second part originates from the formula:23

冕
hydrodynamic coupling of the velocity of the tagged ion with 1
the current modes of the surrounding particles. Thus, the ␦ ␨ s,mic共 t 兲 ⫽ dr具 F 共 r,t 兲 F 共 r,0兲 典 , 共15兲
3k B T
total friction on the tagged ion can be written as22
where F(r,t) is the time-dependent force exerted on the
tagged ion due to its interaction with all other ions in the
1 1 1 solution. An expression for F(r,t) can be obtained from
⫽ ⫹ . 共13兲
␨ s 共 ␻ 兲 ␨ s;mic共 ␻ 兲 ␨ s;hyd共 ␻ 兲 time-dependent density functional theory and the micro-
scopic friction can be formally expressed as an integral over
the wave vector space in the following form:13,31
As discussed in Ref. 22, Eq. 共13兲 has a simple physical
interpretation. A tagged ion diffuses by two mechanisms.
The first one is by the random walk caused by its interactions ␦ ␨ s,mic共 t 兲 ⫽
k BT
3共 2 ␲ 兲3 ␣,␤ 兺 冕 dk k 2 c sa 共 k 兲 冑␳ ␣ ␳ ␤
with the surrounding solvent and ion molecules. The second
is the random walk caused by the natural currents or flows ⫻G ␣␤ 共 k,t 兲 c s ␤ 共 k 兲 F s 共 k,t 兲 , 共16兲
present in the liquid. These two contributions to diffusions where F s (k,t) is the self-dynamic structure factor of the
are additive, as they originate from two different types of tagged ion. G ␣␤ (k,t) is the ionic van Hove function defined
motions. However, the mechanisms are coupled at a dynamic by
level which, in this theory, enters nicely through self-
consistency mentioned earlier. G ␣␤ 共 k,t 兲 ⫽ 共 N ␣ N ␤ 兲 ⫺1/2具 ␳ ␣ 共 k,t 兲 ␳ ␤ 共 ⫺k,0兲 典 , 共17兲
The microscopic friction is most easily analyzed by us- where 具¯典 denotes average over an equilibrium ensemble.
ing the Kirkwood’s formula23 for friction which expresses it N ␣ and N ␤ are, respectively, the number of ions of species ␣
in terms of an integration over the force–force time correla- and ␤ in the solution. We denote G ␣␤ (k, ␻ ) as the
tion function. Since the time-dependent force on the tagged frequency-dependent van Hove function obtained by Laplace
ion has contributions from solvent density and polarization transformation of G ␣␤ (k,t). Use of time-dependent density
fluctuations and also from ion atmosphere fluctuations, one functional theory leads to the following equation for the
can decompose the total microscopic friction into a solvent frequency-dependent van Hove function:13,32
contribution ␨ s;mic(c⫽0) 24,25 which is assumed to be a con-
stant independent of ion concentration and a concentration- G ␣␤ 共 k, ␻ 兲 ⫽ 关 ⫺i ␻ ⫹D ␣ 共 ␻ 兲 k 2 兴 ⫺1 S ␣␤ 共 k 兲
dependent ion contribution ␦ ␨ s;mic( ␻ ). In the present work,
D ␣共 ␻ 兲 k 2
we calculate the frequency dependence of the ion contribu- ⫹
tion to the microscopic friction. Thus, the solvent contribu- ⫺i ␻ ⫹D ␣ 共 ␻ 兲 k 2
tion is not calculated in the present work. It determines the 2
ion diffusion at infinite dilution whose value is assumed to
be known from experiments.
⫻ 兺
␥ ⫽1
冑␳ ␣ ␳ ␥ c ␣␥ 共 k 兲 G ␥␤ 共 k, ␻ 兲 , 共18兲
The hydrodynamic contribution originates from the cou-
where the frequency-dependent diffusion coefficient D ␣ ( ␻ )
pling of the ion velocity to the relevant current modes of the
is related to friction by Eq. 共11兲. S ␣␤ (k)⫽G ␣␤ (k,t⫽0)
solution. Mode coupling theory directly provides an expres-
where S ␣␤ (k) is the partial static structure factor between
sion of the contribution of the currents of the system to the
species ␣ and ␤. S ␣␤ (k) is related to the Fourier transform of
diffusion coefficient, that is, inverse of friction.26–28 Since
the pair correlation function h ␣␤ (k) by the following rela-
the current modes of the solution consists of both the solvent
tion:
and ion currents, the hydrodynamic contribution to the total
friction can be expressed as12,13 S ␣␤ 共 k 兲 ⫽ ␦ ␣␤ ⫹ 冑␳ ␣ ␳ ␤ h ␣␤ 共 k 兲 . 共19兲
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 1880 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 A. Chandra and B. Bagchi

The four coupled equations ( ␣ , ␤ ⫽1,2) as given by Eq. ing the parameters of the model solution and we use the
共18兲 can be solved analytically to obtain the following ex- solutions of Attard33 for the ionic pair correlations which are
plicit results for the frequency dependence of the ionic van quite accurate even at high concentrations.
Hove functions:
1 B. Calculation of the hydrodynamic friction—The
G 11共 k, ␻ 兲 ⫽ 关 兵 ⫺i ␻ ⫹D 2 共 ␻ 兲 k 2 共 1⫺ ␳ 2 c 22共 k 兲兲 其
Z 共 k, ␻ 兲 electrophoretic term

⫻S 11共 k 兲 ⫹D 1 共 ␻ 兲 k 2 冑␳ 1 ␳ 2 c 12共 k 兲 S 21共 k 兲兴 , 共20兲 The ion atmosphere contribution to the hydrodynamic
friction originates from the coupling of the tagged ion veloc-
1 ity with the collective ion current of the system.12,13 A formal
G 12共 k, ␻ 兲 ⫽ 关 兵 ⫺i ␻ ⫹D 2 共 ␻ 兲 k 2 共 1⫺ ␳ 2 c 22共 k 兲兲 其
Z 共 k, ␻ 兲 expression of this friction can be derived from mode cou-
pling theory by using ␳ c (k)j(⫺k) as the relevant binary
⫻S 12共 k 兲 ⫹D 1 共 ␻ 兲 k 2 冑␳ 1 ␳ 2 c 12共 k 兲 S 22共 k 兲兴 , 共21兲 product where ␳ c (k) and j(k) are, respectively, the charge
1 density and total ion current of the solution. The hydrody-
G 21共 k, ␻ 兲 ⫽ 关 兵 ⫺i ␻ ⫹D 1 共 ␻ 兲 k 2 共 1⫺ ␳ 1 c 11共 k 兲兲 其 namic friction is then given by
Z 共 k, ␻ 兲

⫻S 21共 k 兲 ⫹D 2 共 ␻ 兲 k 2 冑␳ 1 ␳ 2 c 21共 k 兲 S 11共 k 兲兴 , 共22兲

k BT
␦ ␨ s,hyd共 ␻ 兲
⫽ 冕 0
⬁
dt e i ␻ t 兺k 兺
k
具 u 0x , ␳ c 共 k兲 j共 ⫺k兲 典
⬘
1
G 22共 k, ␻ 兲 ⫽ 关 兵 ⫺i ␻ ⫹D 1 共 ␻ 兲 k 2 共 1⫺ ␳ 1 c 11共 k 兲兲 其 ⫻ 具 ␳ 共 k兲 j共 ⫺k兲 , ␳ c 共 k兲 j共 ⫺k兲 典 ⫺1
c
Z 共 k, ␻ 兲
⫻ 具 ␳ c 共 k兲 j共 ⫺k兲 ,e iLt ␳ c 共 k⬘ 兲 j共 ⫺k⬘ 兲 典
⫻S 22共 k 兲 ⫹D 2 共 ␻ 兲 k 2 冑␳ 1 ␳ 2 c 21共 k 兲 S 12共 k 兲兴 , 共23兲
⫻ 具 ␳ c 共 k⬘ 兲 j共 ⫺k⬘ 兲 , ␳ c 共 k⬘ 兲 j共 ⫺k⬘ 兲 典 ⫺1
where
⫻ 具 ␳ c 共 k⬘ 兲 j共 ⫺k⬘ 兲 ,u 0x 典 , 共29兲
Z 共 k, ␻ 兲 ⫽⫺ ␻ 2 ⫺i ␻ ⌬ 共 k 兲关 D 1 共 ␻ 兲 k 2 S 22共 k 兲 ⫹D 2 共 ␻ 兲 k 2 S 11共 k 兲兴
where u 0x is the velocity of the tagged ion along a particular
⫹D 1 共 ␻ 兲 D 2 共 ␻ 兲 k 4 ⌬ 共 k 兲 , 共24兲 direction 共say, x兲 and e iLt is the time evolution operator. The
and vertices and the time correlation function in Eq. 共29兲 can be
evaluated to obtain the following formal expression for the
⌬ 共 k 兲 ⫽ 关 S 11共 k 兲 S 22共 k 兲 ⫺S 12共 k 兲 2 兴 ⫺1 . 共25兲 hydrodynamic friction:
In deriving Eqs. 共20兲–共25兲 we have also used the following
relation between c ␣␤ (k) and S ␣␤ (k) for a two-component
system:
k BT
⫽
1
␦ ␨ s,hyd共 ␻ 兲 3 ␲ 2 N 冕 0
⬁
dt e i ␻ t 冕 dk k 2 关 q 1 ⫹ ␳ 1 q 1 h 11共 k 兲

1⫺ ␳ 1 c 11共 k 兲 ⫽⌬ 共 k 兲 S 22 , 共26兲
⫹ ␳ 2 q 2 h 12共 k 兲兴 2 兺
␣␤
冑␳ ␣ ␳ ␤ q ␣ q ␤
冑␳ 1 ␳ 2 c 12共 k 兲 ⫽⌬ 共 k 兲 S 12共 k 兲 , 共27兲
and a similar relation between c 22(k) and S 11(k). These re- ⫻ 关 F s ␣ 共 k,t 兲 ␦ ␣␤ ⫹ 冑␳ ␣ ␳ ␤ G ␣␤
d
共 k,t 兲兴
lations can be derived from the Ornstein–Zernike equations
relating the direct and the pair correlation functions.21 We
note that the time dependence of the van Hove functions can
⫻ 冋兺 ␣␤
冑␳ ␣ ␳ ␤ q ␣ q ␤ 兵 ␦ ␣␤ ⫹ 冑␳ ␣ ␳ ␤ h ␣␤ 共 k 兲 其 册 ⫺2

be obtained through Laplace inverse transformation. The ⫻ 关 C L 共 k,t 兲 ⫹2C T 共 k,t 兲兴 , 共30兲
Laplace transform of the self-dynamic structure factor of the
tagged ion can be described by where N is the total number of ions in the solution. F s ␣ (k,t)
is the self van Hove function of an ion of species ␣, and
d
1 G ␣␤ (k,t) is the so-called distinct van Hove function between
F s 共 k, ␻ 兲 ⫽ , 共28兲 species ␣ and ␤. C L (k,t) and C T (k,t) are, respectively, the
⫺i ␻ ⫹D s 共 ␻ 兲 k 2
longitudinal and the transverse current correlation functions
where D s ( ␻ ) is the frequency-dependent self-diffusion coef- of the ions. The decay of the longitudinal current occurs at a
ficient of the tagged ion. We still require the solutions of the much faster time scale than that of the transverse current.21
static structure factors and the direct correlation functions for For nonpolar liquids, it is known that the contribution of the
the calculation of the microscopic electrolyte friction. We longitudinal current to zero and low frequency friction is
note that the direct correlation functions are related to the negligible 共less than 5%兲 compared to the transverse
static structure factors by Eqs. 共26兲 and 共27兲 and the static term.26,27 Therefore, the contribution of the longitudinal cur-
structure factors are related to the pair correlation functions rent relaxation to the hydrodynamic friction is expected to be
by Eq. 共19兲. Thus, we require the solutions of the pair cor- important only at very high frequency and we have ignored it
relation functions for the calculation of the quantities S ␣␤ (k) in the present calculations. We also note that it is the trans-
and c s ␣ (k). We need to specify the nature of the short-range verse part which leads to the Stokes–Einstein relation for
interaction between ions for this purpose. We consider the nonpolar molecules.27 For electrolytes, the transverse term
ions to be charged hard spheres with their diameters becom- leads to the electrophoretic term of Debye–Huckel.13 In the
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 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 Frequency dependence of ionic conductivity 1881

present work, we also assume a symmetric binary electrolyte phoretic term is ignored. Accordingly, we consider only the
with ions of equal size such that h 11(k)⫽h 22(k). Equation microscopic electrolyte friction as given by Eq. 共16兲 and re-
共30兲 then simplifies to write it in the following form:
k BT
⫽
2
␦ ␨ s,hyd共 ␻ 兲 3 ␲ 2 ␳ N 冕 0
⬁
dt e i ␻ t 冕 dk k 2 F s 共 k,t 兲 C T 共 k,t 兲 ␦ ␨ s,mic共 t 兲 ⫽
k BT
3共 2␲ 兲3
冕 dk k 2 关 C s 共 k 兲兴关 G 共 k,t 兲兴

⫹
2
3 ␲ 2␳ N
冕 0
⬁
dt e i ␻ t 冕 dk k 2 关 ␳ 1 G 11
d
共 k,t 兲
⫻关 C s 共 k 兲兴 † F s 共 k,t 兲 ,
where 关 C s (k) 兴 is a row matrix defined by
共34兲

⫺ ␳ 2 G 12 共31兲 关 C s 共 k 兲兴 ⫽ 关 冑␳ 1 c s1 共 k 兲 冑␳ 2 c s2 共 k 兲兴 ,
d
共 k,t 兲兴 C T 共 k,t 兲 , 共35兲
where ␳ is the total ion density of the solution. We note that and 关 C s (k) 兴 † is the transpose of 关 C s (k) 兴 . 关 G(k,t) 兴 is the
the first term on the right-hand side of Eq. 共31兲 gives the ion 2⫻2 van Hove function matrix with elements G ␣␤ (k,t),
contribution to the usual Stokes 共or viscous兲 friction and the ␣ , ␤ ⫽1,2. Clearly, 关 G(k,t) 兴 becomes the structure factor
second term represents the so-called electrophoretic friction. matrix 关 S(k) 兴 at t⫽0. We assume that the ions are point ions
In the following calculations, we will focus on the electro- and use Debye–Huckel 共DH兲 theory34 of ion–ion pair corre-
phoretic friction only because it is the most important hydro- lations. The ion–ion partial structure factor is then given by
dynamic contribution to the total ionic friction. We also note
that the relaxation of the transverse velocity correlation func- 4 ␲ q ␣ q ␤ 冑␳ ␣ ␳ ␤ 1
S ␣␤ 共 k 兲 ⫽ ␦ ␣ , ␤ ⫺ , 共36兲
tion occurs much faster than the distinct van Hove functions ⑀ k BT k ⫹␬D
2 2
so that G 11d d
(k,t) and G 12 (k,t) in Eq. 共31兲 can be approxi-
mated by their zero time values h 11(k) and h 12(k), respec- where the inverse Debye screening length ␬ D is defined by
tively. Since the transverse current does not couple with den- Eq. 共4兲. The ion–ion direct correlation function for the point
sity relaxation, its relaxation can be described quite well by ions in DH theory can be obtained by combining Eqs. 共26兲
an exponential function with a relaxation time inversely pro- and 共27兲 and 共36兲 and it is given by
portional to the shear viscosity of the medium as follows:
4 ␲ q ␣q ␤ 1
c ␣␤ 共 k 兲 ⫽⫺ . 共37兲
Nk B T ⫺ ␩ k 2 t/ ␳ m ⑀ k BT k 2
C T 共 k,t 兲 ⫽ e . 共32兲
2m
We next assume that the relaxation of the ionic van
We note that the decay of the transverse ionic current as Hove functions is described by diffusional motion. That is,
given by Eq. 共32兲 is different from that of the pure solvent in we ignore the frequency dependence of D ␣ ( ␻ ) in Eq. 共18兲
the sense that the viscosity which appears in Eq. 共32兲 is and replace it by its zero-frequency value D ␣ and solve the
concentration dependent. In the numerical calculations, how- resultant equation in the time domain to obtain
ever, the viscosity is taken as an input parameter. We next
substitute Eq. 共32兲 in Eq. 共31兲 to obtain the following simple 关 G 共 k,t 兲兴 ⫽ 关 S 共 k 兲兴 exp共 ⫺ 关 D 兴 k 2 t 关 S 共 k 兲兴 ⫺1 兲 . 共38兲
expression for the frequency-dependent electrophoretic fric- where 关D兴 is the diagonal matrix of self-diffusion coeffi-
tion: cients. When Eqs. 共36兲–共38兲 are substituted in Eq. 共34兲, the

冕 冕
k BT k BT ⬁ resultant integral over the wave vector k can be evaluated
⫽ dt e i ␻ t dk k 2 关 ␳ 1 h 11共 k 兲 analytically35 and the final result of the time-dependent mi-
␦ ␨ s,hyd共 ␻ 兲 3 ␲ 2 ␳ m 0
croscopic electrolyte friction is given by
⫺ ␳ 2 h 12共 k 兲兴 e ⫺ ␩ k
冋 册
2 t/ ␳ m
. 共33兲 q s2 ␬ D
2
e ⫺D ␬ D t
2

⫹ ␬ D e D ␬ D t 兵 ⌽ 共 冑2 ␬ D
2
␨ s,mic共 t 兲 ⫽ 2
Dt 兲 ⫺1 其 ,
We have solved Eqs. 共16兲 and 共33兲 for the microscopic 3⑀ 冑2 ␲ Dt
and the electrophoretic frictions iteratively to obtain the self- 共39兲
consistent results of the frequency-dependent electrolyte fric-
tion at varying concentrations. The results of frequency- where ⌽(x) is the error function and it is assumed that all
dependent friction are then used to calculate the frequency- ions have the same diffusion coefficient D. We note that Eq.
dependent ion diffusion and conductivity by using Eqs. 共11兲 共39兲 of time-dependent electrolyte friction becomes identical
and 共12兲, respectively. with the one derived by de Leon et al.35 when the diffusion
coefficient D in the right-hand side of Eq. 共39兲 is replaced by
D 0 , which is the value of the ion diffusion coefficient in the
III. DERIVATION OF DEBYE–FALKENHAGEN FORM limit of infinite dilution.
OF FREQUENCY-DEPENDENT FRICTION The Laplace transform of Eq. 共39兲 can be carried out
In this section we identify the limiting conditions under analytically36 to obtain the following expression of the
which the present theory reduces to the well-known Debye– frequency-dependent friction:
Falkenhagen expression 关Eq. 共2兲兴 of the frequency-dependent q s2 ␬ 1
electrolyte friction. We note that in Debye–Falkenhagen ␨ s;mic共 ␻ 兲 ⫽ . 共40兲
6⑀D 1
theory, the frequency dependence of only the ion atmosphere 1⫹ 关 1⫺i ␻ /D ␬ 兴 2 1/2
relaxation contribution is considered and that of the electro- &
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 1882 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 A. Chandra and B. Bagchi

The zero-frequency microscopic electrolyte friction is given To recover the expression of model II 关Eq. 共6兲兴, we ig-
by13 nore the hydrodynamic effects so that ␨ s (t)⫽ ␨ s;mic(t) and
we write the total friction as
q s2 ␬
␨ s;mic共 0 兲 ⫽
6⑀D
共 2⫺& 兲 ,

We next substitute Eq. 共41兲 in Eq. 共40兲 and rewrite the re-
共41兲
␨ s共 t 兲 ⫽
1
3k B T
冕 dr具 F 共 r,t 兲 F 共 r,0兲 典 , 共45兲

sultant expression of the frequency-dependent friction in the where F(r,t) is the total force 共including the solvent contri-
following form: bution兲 acting on the tagged ion at time t. Clearly, ␨ s (t⫽0)
is described by the zero-time force–force correlation
1⫹ 冑q
␨ s;mic共 ␻ 兲 ⫽ ␨ s;mic共 0 兲
1⫹ 冑q 关 1⫺i ␻ ␶ atm兴 1/2
, 共42兲
␨ s 共 t⫽0 兲 ⫽
1
3k B T
冕 dr具 F 共 r,0兲 F 共 r,0兲 典 ⫽⍀ s2 , 共46兲
where q and ␶ atm are defined in Sec. I. Equation 共42兲 is
where ⍀ s is the Einstein frequency21 of the tagged ion. We
identical to the DF expression 关Eq. 共2兲兴. Thus, it is clear from
next assume an exponential decay of ␨ s (t) so that
the above-mentioned analysis that the present microscopic
theory reduces to the DF theory in the limit of low ion con- ␨ s 共 t 兲 ⫽⍀ s2 e ⫺t/ ␶ s . 共47兲
centration when finite sizes of the ions are ignored, electro-
where relaxation time ␶ s can be eliminated in favor of the
phoretic effects are not included, and the collective dynamics
diffusion coefficient D s by using the above-described Ein-
of the ion atmosphere relaxation is described by diffusive
stein relation and the resultant expression after Laplace trans-
motion.
formation gives
It may be noted that the DF theory incorporates the cross
dynamical coupling of ions at the level of ion atmosphere ⍀ s2
relaxation 共or the ionic van Hove functions兲 and not at the ␨ s共 ␻ 兲 ⫽ . 共48兲
level of ionic velocity or current relaxation. Thus, the DF ⫺i ␻ ⫹D s m s ⍀ s2 /k B T
expression of ion atmosphere friction does not include the Equation 共48兲, on combining with Eqs. 共11兲 and 共12兲, gives
effects of the so-called current cross terms. The DF expres- Eq. 共6兲, which is the CWP model II expression for ␴共␻兲.
sion is treated as the limiting expression of ion atmosphere Thus, in this model, the frequency dependence of conductiv-
friction when current cross terms are ignored and it is shown ity originates from both the inertial and the non-Markovian
that the present microscopic theory correctly goes over to effects. We also note that although the hydrodynamic effects
this limiting expression at the limit of very low ion concen- such as electrophoretic contributions are not explicitly in-
tration. Also, the contribution of the cross correlation is ex- cluded in this model, such effects can be implicitly included
pected to be minimal at very low ion concentration where the to some extent by using proper experimental values of the
DF theory is valid. zero-frequency diffusion coefficients.

IV. DERIVATION OF THE CONDUCTIVITY V. NUMERICAL RESULTS AND DISCUSSION

EXPRESSIONS OF CHANDRA, WEI, AND PATEY
We present numerical results of the frequency depen-
In this section we describe how the CWP expressions of dence of friction and conductivity for solutions of varying
the frequency-dependent conductivity can be recovered from ion concentration. In the numerical calculations, all ions of
the present theory. To recover the expression of model I 关Eq. the solutions are assumed to be of equal diameter ␴ and
共5兲兴, we ignore the frequency dependence of ␨ s ( ␻ ) in Eq. equal mass m for simplicity. The solutions are considered to
共11兲 and replace it by the zero-frequency value ␨ s so that be of a symmetric salt such that the charge of each positive
k BT 1 Ds ion is q 1 and that of each negative ion is ⫺q 1 and ␳ 1 ⫽ ␳ 2
D s共 ␻ 兲 ⫽ ⫽ , 共43兲 and also D 1 ⫽D 2 . The solutions can be completely specified
m s ⫺i ␻ ⫹ ␨ s 1⫺i ␻ D s m s /k B T
by specifying the values of the reduced charge q 1*
where, in deriving the second equality, we have used the ⫽ 冑q 21 /k B T ␴ , the reduced ion density ␳ 1* ⫽ ␳ 1 ␴ 3 , and the
Einstein relation ␨ s ⫽k B T/D s m s . On combining Eq. 共43兲 dielectric constant ⑀. The values of ⑀ and q * 1 for all the
with the Nernst–Einstein relation 关Eq. 共12兲兴, one gets Eq. solutions are 80 and 14.1, respectively. The above-
共5兲, which is the CWP model I expression of the frequency- mentioned value of the reduced charge corresponds to the
dependent conductivity. Thus, in this limiting case, the fre- charge of a univalent ion of diameter 2.82 Å at T⫽298 K.
quency dependence of the conductivity originates entirely In the numerical calculations, the self-consistent equa-
from the inertial effects. Also, when D 1 ⫽D 2 and m 1 ⫽m 2 , tions of the microscopic and electrophoretic frictions are
the frequency dependence of the conductivity is described by solved iteratively. We first calculate the zero-frequency elec-
a simple Debye form,19 trolyte friction and the zero-frequency diffusion coefficient
␴ D. This zero-frequency diffusion coefficient is then used as
␴共 ␻ 兲⫽ , 共44兲 the initial guess for the frequency-dependent diffusion coef-
1⫺i ␻ Dm/k B T
ficient D( ␻ ) and we calculate the frequency-dependent ionic
where ␴ is the conductivity at zero frequency. We note that van Hove 关Eqs. 共20兲–共23兲兴 and self van Hove 关Eq. 共28兲兴
the simple Debye form has been used in the literature as an functions. The time dependence of these van Hove functions
empirical expression for ␴共␻兲.15 are then calculated through numerical inverse Laplace trans-
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 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 Frequency dependence of ionic conductivity 1883

FIG. 1. The frequency dependence of the 共a兲 real and 共b兲 imaginary parts of FIG. 2. The frequency dependence of the 共a兲 real and 共b兲 imaginary parts of
the microscopic electrolyte friction on an ion in a 0.01 M solution of a 1:1 the microscopic electrolyte friction on an ion in a 0.1 M solution. The
electrolyte. The solid and the dashed curves represent, respectively, the re- different curves are as in Fig. 1.
sults of the present theory and of Debye–Falkenhagen expression 关Eq. 共2兲兴.

nite dilution. In Figs. 1 and 2, the results of DF friction 关Eq.

formation. This leads to the calculation of the time- 共2兲兴 are also included for comparison. At low concentration
dependent microscopic friction ␨ s;mic(t) 关Eq. 共16兲兴, which is and at low frequency, the results of the present theory are
then numerically Laplace transformed to obtain ␨ s;mic( ␻ ). found to be quite close to the DF results. However, at high
The electrophoretic friction is calculated from Eq. 共33兲. concentration, the results of the present theory show signifi-
These two frequency-dependent frictions are then combined cant departure from the DF results, especially at high fre-
to obtain the new values of D( ␻ ) from Eq. 共11兲. The entire quency. Also, with increase of ion concentration, the disper-
process is repeated several times until convergence is sion of the electrolyte friction is found to occur at a higher
achieved. frequency because of faster relaxation of the ion atmosphere.
We decompose the frequency-dependent microscopic In Fig. 3, we have shown the frequency dependence of
electrolyte friction into its real and imaginary parts as fol- the electrophoretic term for the 0.1 M solution. The disper-
lows:
⬘ 共 ␻ 兲 ⫹i ␦ ␨ s;mic
␦ ␨ s;mic共 ␻ 兲 ⫽ ␦ ␨ s;mic ⬙ 共 ␻ 兲. 共49兲
Similar decomposition is also made for the electrophoretic
friction and the conductivity functions as these are all com-
plex quantities at finite frequencies. In Figs. 1共a兲 and 1共b兲,
we have shown the frequency dependence of the real and
imaginary parts of the microscopic electrolyte friction for
␳ 1* ⫽0.000 135. The above-mentioned value of the reduced
ion density corresponds to a 0.01 M solution for ␴ ⫽2.8 Å.
Thus, this solution corresponds to 0.01 M solution of a 1:1
electrolyte at room temperature. The corresponding results
for a 0.1 molar solution are shown in Figs. 2共a兲 and 2共b兲. The
values of the friction at different frequencies are normalized
by its zero-frequency value and the reduced frequency ␻ *
⫽ ␻␴ 2 /D. In the present calculations, we have used ␩
FIG. 3. The frequency dependence of the electrophoretic friction on an ion
⫽8.95⫻10⫺3 g cm⫺1 s⫺1, D 0 ⫽2.0⫻10⫺5 cm2 s⫺1 and m in a 0.1 M solution. The solid and the dashed curves represent, respectively,
⫽40 amu where D 0 is the ionic diffusion coefficient at infi- the real and the imaginary parts.
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 1884 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 A. Chandra and B. Bagchi

FIG. 5. The Cole–Cole plots of the frequency-dependent conductivity. The

imginary part is plotted against the real part calculated at different frequen-
cies. The dashed and the solid curves are for 0.01 and 0.1 M solutions,
respectively. The dotted curve represents the simple Debye behavior.

which connects the diffusion coefficient to the friction at

finite frequencies.
Sometimes the experimental results of the frequency-
dependent conductivity are analyzed in terms of the so-called
Cole–Cole plots where the imaginary part of the conductiv-
ity is plotted against the real part at different frequencies.
Such Cole–Cole plots for the two solutions are shown in Fig.
5. Significant non-Debye behavior is observed at higher ion
FIG. 4. The frequency dependence of the 共a兲 real and 共b兲 imaginary parts of concentration. This is not unexpected as the Debye form of
the conductivity of solutions of a 1:1 electrolyte. The dashed and the solid ␴共␻兲 关Eq. 共44兲兴 is valid only in limiting situations as dis-
curves correspond to the 0.01 and 0.1 M solutions, respectively. cussed in Sec. V and, in general, the dispersion of the con-
ductivity shows a more complex behavior.

VI. SUMMARY AND CONCLUSIONS

sion of the electrophoretic contribution is seen to occur at a
much higher frequency as one would expect. In fact, any We have presented a self-consistent theory of the
noticeable change in the electrophoretic term is found only frequency-dependent friction on a moving ion and the con-
above ␻ * ⫽103 , which corresponds to a frequency well ductivity of electrolyte solutions. The theory is based on a
above the gigahertz region. The dispersion of the solvent combination of the mode coupling theory and time-
contribution to the ionic friction, which is assumed to be a dependent density functional approach and it incorporates
constant in the present calculations, is also expected to occur the details of the static and dynamic ion–ion correlations and
in this frequency domain. The solvent contribution, being a also the effects of self-motion of the ions. Both the ion at-
larger effect, may dominate the dispersion of the total ionic mosphere relaxation and the electrophoretic effects are in-
friction at such high frequencies. cluded which are now frequency dependent and the results of
The results of the frequency dependence of real and the two effects are combined to obtain the frequency-
imaginary parts of the ion conductivity are shown in Figs. dependent electrolyte friction and the conductivity. It is
4共a兲 and 4共b兲 for the 0.01 and 0.1 M solutions. The ionic shown that the present theory correctly reduces to the well-
charges are the same as in Fig. 1. The real part shows a slight known Debye–Falkenhagen expression of the frequency-
increase at low frequency and then it decreases at high fre- dependent electrolyte friction in the limit of very low ion
quency as one would expect. The initial increase at low fre- concentration. It is also shown how the expressions of the
quency can be attributed to the Debye–Falkenhagen effect. It frequency-dependent conductivity derived earlier by Chan-
is seen that the primary dispersion of the conductivity occurs dra, Wei, and Patey19 can be recovered from the present
at a much higher frequency than that of the microscopic elec- theory. Numerical results are obtained for the real and imagi-
trolyte friction. The dispersion of the microscopic electrolyte nary parts of the friction and the conductivity at various fre-
friction is primarily determined by the inverse relaxation quencies. It is found that at high concentration the frequency
time of the ion atmosphere. The frequency dependence of the dependence of the friction can be quite different from that
conductivity, on the other hand, is determined by the given by the Debye–Falkenhagen expression. With increase
frequency-dependent diffusion coefficient D( ␻ ). The pri- of concentration, the dispersion of the electrolyte friction is
mary dispersion of D( ␻ ) occurs at a much higher frequency found to occur at a higher frequency because of faster relax-
than that of the electrolyte friction because of the presence of ation of the ion atmosphere. The real part of the conductivity
⫺i ␻ term in the generalized Einstein relation 关Eq. 共11兲兴 is found to change rather weakly at low frequency. In fact, at
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 J. Chem. Phys., Vol. 112, No. 4, 22 January 2000 Frequency dependence of ionic conductivity 1885

low concentration, a slight increase of the real part of the

conductivity is observed at low frequency which can be at- F, 共 r,t 兲 ⫽k B Tⵜ 冕 dr ⬘ c ic 共 r⫺r⬘ 兲 ␦ ␳ c 共 r⬘ ,t 兲
tributed to the so-called Debye–Falkenhagen effect. The dis-
persion of the conductivity is found to occur at a much
higher frequency than that of the ion atmosphere friction.
⫹k B Tⵜ 冕 dr ⬘ c i j 共 r⫺r⬘ 兲 ␦ ␳ j 共 r⬘ ,t 兲 , 共50兲
Also, significant non-Debye behavior is observed in the where c ci (r,t) is the colloid-ion direct correlation function,
Cole–Cole plots of the conductivity of concentrated solu- ␦ ␳ c (r⬘ ,t) is the density fluctuation of the colloids, c i j is the
tions. ion–ion direct correlation function, and ␦ ␳ j (r⬘ ,t) is the fluc-
The theory of the frequency-dependent conductivity de- tuation in the density of ion type j. Equation 共50兲 naturally
veloped here can be used to study the dynamics of many leads to an expression for the friction which depends on the
interesting chemical phenomena such as solvation dynamic structure factor of the colloids. A similar expression
dynamics,37–40 dielectric relaxation,5,41,42 and chemical reac- can be written for the friction on the colloids which would
tions in electrolyte solutions.43–46 In all these chemical prob- involve the dynamic structure factor of the ions. These equa-
lems, the motion of ions in response to a time-dependent tions need to be solved self-consistently. While this method
electric field or to a changing charge distribution inside the is well-known, one can carry out such detailed calculations
solution plays an important role and the theory developed now with the availability of the desired pair and direct cor-
here can be applied or generalized to study such problems. relation functions. In this context, we note the work of Leon
Also, in the present theory, the solvent is considered to be a et al.35 where similar equations have been derived for the
dielectric continuum. Thus, although the present theory in- time-dependent friction on a charged colloidal particle from
corporates the static and dynamic ion–ion correlations and an approach of contracted description through generalized
the screening effects, the molecular details of the ion– Langevin equation.48 The resultant equations were, however,
solvent and solvent–solvent correlations are missing. Also, solved without incorporating the inherent self-consistency
since the conductivity is calculated by using the generalized required in the problem. It would certainly be worthwhile to
Nernst–Einstein relation 关Eq. 共12兲兴, the dynamical cross cor- carry out full self-consistent calculations of the frequency-
relations between velocities of distinct ions or the collective dependent friction on such charged macroparticles. Work in
effects in the current–current correlation are not included in these areas is in progress.
the present theory. Because of these approximations, the
present theory is limited to solutions of not too high concen- ACKNOWLEDGMENTS
tration 共say, less than 0.1 M兲. In fact, recent computer simu-
The research reported here was supported in part by
lations have shown that for highly concentrated solutions, the
grants from the Council of Scientific and Industrial Research
dynamic ion–solvent correlations and the cross velocity cor-
共CSIR兲, Department of Science and Technology 共DST兲.
relations are responsible for much of the complex behavior
Government of India and Indian National Science Academy.
of the conductivity at finite frequencies.19 Thus, it would
certainly be worthwhile to generalize the present self-
consistent theory to include the molecularity of the solvent
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