J. Phys. C : Solid State Phys. 18 (1985) 3829-3836.

Printed in Great Britain

Debye and non-Debye relaxation

R M Hill and L A Dissado

The Dielectrics Group. Chelsea College, University of London, Pulton Place. London SW6
5PR, UK

Received 8 November 1984, in final form 14 January 1985

Abstract. Debye relaxation behaviour is unique in the sense that all memory of excitation is
instantaneously lost. It is shown that the presence of higher-frequency relaxations for
components of the same dipole degrades this property by extended the memory into the
timescale of relaxation, thus giving a non-Debye behaviour which can be expected to occur
in all practical dielectric materials. In this case it is not possible, as has been suggested. that
knowledge of the polarisation or of the depolarisation current at a single time is sufficient,
alone. to define the relaxation behaviour of the system for all subsequent times. Furthermore
the Guo and Guo experiment is shown to be incapable of discriminating between this picture
of sequential relaxation and the alternative possibility of an ensemble of independent
relaxations.

1. Introduction

Recently Guo and Guo (1982, 1983) and Calderwood (1982, 1983) have discussed
some of the consequences of non-Debye relaxation and have pointed out an essential
difference between Debye relaxation (Debye 1912) and the alternative models that have
been proposed. In particular the Curie-von Schwiedler depolarisation characteristic
(Curie 1889. von Schwiedler 1907)
j ( t ) x t-’ O S S S l (1)
has been criticised by Calderwood as leading to the possibility of two different forms for
current decay from a single polarisation state, when the polarisation state is defined
purely in terms of the magnitude of the polarisation. Notwithstanding these comments,
the experimental observation of the fractional power-law decay of the polarisation
current, j ( t ) = dP(t)/dt, where P(r) is the polarisation, has been well substantiated in
real materials (Kliem and Arlt (1982), Jonscher (1983) and references therein), although
in the past the current range over which the decay could be followed was limited by slow
and relatively insensitive detectors.
The conventional explanation of the non-Debye nature of the Curie-von Schweidler
depolarisation characteristic is that there exist in the materials studied a number of
relaxation processes, each of the Debye form but with their relaxation times, t, dis-
tributed in such a manner that the summation over the individual non-interacting
processes gives the characteristic indicated in equation (1). It has been pointed out by
Guo and Guo (1982,1983) and by Hill and Jonscher (1983) that the use of a distribution
of Debye-like relaxation elements to describe the experimentally observed response is

0022-3719/85/193829 + 08 $02.25 01985 The Institute of Physics 3829

 R M Hill and L A Dissado

no more than a mathematical transformation of the measured response, unless the

resulting distribution can be related to some other distributed property of the system.
Indeed unless the distribution can be observed by means other than the relaxation of
the system it is not a useful description of the system.
In principle all spectral or temporal relaxation functions can be described in terms
of suitable distributions of exponentially decaying elements (Gross 1968) which are not
even necessarily unique. We have chosen the term ‘exponentially decaying’ here to
emphasise that the algebraic analysis is expressed as a weighted sum of exponentials
which has often been taken to imply a distribution of Debye relaxations. Thus the
physical origin of the distribution is imputed to lie in an ensemble of non-interacting
dipoles to each of which is assigned a relaxation time determined by its particular local
environment. In this picture the environment of a dipole remains unaffected by the
relaxation process, and the total relaxation is obtained by summing in parallel the
individual contributions. If all dipoles are identical the Debye model is completely
recovered. An entirely different approach has been adopted by the present authors
(Dissado 1982, Dissado and Hill 1983). In this picture dipoles interact with their environ-
ment, which may include other dipoles, to give a finite-sized cluster with an effective
dipole which has many components corresponding to differing amounts of correlation
within the cluster. Relaxation proceeds sequentially (i.e. in series) as the slower com-
ponents displace in the environment of the already relaxed faster components. In this
picture, therefore, relaxation takes place on a continuously changing potential surface
(Dissado and Hill 1983, Dissado et a1 1985). Recently Palmer et a1 (1984) have shown
that such a hierarchical approach can be expressed as a distribution of exponential
decays which can lead to the Kohlrausch (1847) function exp[ - ( t / t ) p J ] , more commonly
attributed in dielectrics to Williams and Watts (1970). In the short-time region, t Q t,
this function asymptotically approaches the Curie-von Schwiedler Law of equation (1)
as derived by Dissado and Hill (( 1983) and references therein).
In summary then we can distinguish two physical categories of relaxation. namely
the ideal Debye case (Ia) and the ideal distribution (Ib), in which contributions from an
ensemble occur in parallel, and (11) the cluster approach containing sequential (series)
developments in which events over a range of timescales interact (Kawasaki 1976).
In the following we will adopt a simple construction containing just two exponential
relaxations in order to differentiate between these two alternative systems in a discussion
of the consequences of non-Debye relaxation. Although this construction may be easily
envisaged for case Ib, in case I1 it can best be thought to refer to a system of non-
interacting flexible molecules such as, for example, cyclohexanol in which the molecular
dipole has more than one component. It is possible to regard such a construction as a
sub-category IIb of class 11, but we can expect it to be physically unrealisable in con-
densed-phase materials because of the inevitability of intermolecular interactions (Shab-
lakh et a1 1983). However, although the range and continuity of the timescales in this
case are insufficient to give the Curie-von Schwiedler law, we show that this construction
is sufficient to give fundamentally non-Debye behaviour. It is also shown that Calder-
wood’s definition of the polarisation state applies only to the ideal Debye case (Ia).

2. Debye relaxation

We take as a starting point for examination of the Debye relaxation the condition
that the rate of change of the polarisation should be proportional to the polarisation, so
 Debye and non-Debye relaxation 3831

that
dP(t)/dt = - P ( t ) / t t>O
where r , as stated earlier, is a constant which is the relaxation time of the polarisation.
The time development of the polarisation is then given by
P(t) = Po(l - e-"T) (3a)
and
P(t) = Po e-' (3b)
under conditions of charge and discharge respectively. The rate of change of the polar-
isation is the current that flows in the external circuit and is given by

j ( t ) = Pot-' e-r'T (4)

where the positive and negative signs refer to charge and discharge conditions
respectively.
If the sample is polarised to some intermediate value of polarisation P , ( < P o ) ,which
can be expressed as Po exp( - t d / t ) , and the discharge is delayed from time zero until the
time t d ,the subsequent current flowing in the external circuit will be given by
j(t a t d )= - P,, exp( - t,/r) exp[ - ( t - f d ) / r ] T - l = - Pot-, (5)
which is exactly the original decay of equation (4). In this Debye case, case Ia, as
Calderwood (1982,1983) has made clear, the form of the relaxation in the time domain
can be defined completely by knowledge of the initial polarisation.
Guo and Guo (1982, 1983) have considered an interesting corollary to this time
development. Initially a sample is taken in the zero-polarisation state and polarised with
a field Eo. During polarisation. at a time t,, the field is reversed to -Eo. When the
subsequent polarisation becomes zero, at a time r2, the field is set to zero and the
time development of the polarisation or current observed. Simple algebra gives the
subsequent polarisation and current as zero for the Debye case considered here.
The observation of this behaviour in a material that was known to exhibit Debye
properties would give a critical test for the principle of superposition which is fun-
damental both in equation (5) and in the Guo and Guo experiment. It should be noted,
however, that the essential feature is the use of the principle of superposition in
the separation of the delayed response into the product of the initial decay function,
exp(-t/t), and a constant scaling factor which is itself a simple function of the delay
time. In principle if this separation can be matched by any other decay process then an
equivalent result to that given by the Guo and Guo experiment could be established.

3. Non-Debye relaxation

As discussed in the introduction the commonly accepted model for non-Debye behaviour
is that of a distribution of relaxation times under the conditions of class Ib. Making the
conventional assumptions that the individual responses from the elemental sub-systems
are in parallel and hence directly additive the external current is given by

j(t) = - Po lox g ( t ) r - ' e-'/T d t

3832 R M Hill and L A Dissado

under discharge conditions. We define a polarisation Pd such that

Pd = lox
dZ> exp( - td/t) (7)

assuming that the integration can be carried out. The discharge current when the
discharge of the polarisation P d is delayed until the time td is given by

j(t 3 t d ) = Po
IoX g( t)eXp( - t d / t ) d t
/ox
g ( t ) t - ' eXp[ - ( t - t d ) / Z ] d t (8)

which, by inspection, can only equal the current of equation (6) when& t)is a &function
in t,thereby recovering the case considered in the previous section.
The inequality can be seen more clearly by considering the simplest distribution, that
of two independent Debye relaxation processes. We let the processes be of equal strength
and of relaxation times t1 and t 2 .In this, trivial, case equation (8) becomes
j ( t 3 t d ) = ( ~ , / 4 ) [ t ; ' e-f'rl(I + e f d r )+ t;' e-' T * ( ~ + e-'d ')I (9)
where t - l = z;' - t;' .
It is obvious that the relaxation current is strongly dependent on the parameters that
characterise the distribution, and that even in this trivial case the initial polarisation is
not sufficient to define the state of the system.
Alternatively we can consider the Guo and Guo experiment with this distribution.
It is simple to show that the polarisation becomes zero at the time t2 which is the solution
of
\ox g ( t ) e-'*/r(2e'l/r - 1) d t = 1. (10)

However because t i s distributed t2cannot be defined in terms of t l and t,as in the simple
Debye case, and as a consequence neither the polarisation nor the external current will
remain zero for times greater than t 2 .
It can be seen, then, that the Guo and Guo experiment can only distinguish Debye
relaxation, case Ia, from the other relaxation models. In particular it cannot differentiate
between the parallel relaxation of class Ib and the correlated (series) forms of class 11,
as has been implied by Kliem and Arlt (1984).

4. Memory function

The non-equivalence between the Debye and non-Debye behaviour has been ascribed
to the presence of memory in the latter case (Calderwood 1983, Guo and Guo 1983).
The memory function for relaxation. K ( t ) ,is commonly defined (see, for example, Ferry
(1970)) through the integral relationship
d PO> =
-
dt
- IorK(t - x ) P ( x )dx

where x is a dummy variable in units of time. For a linear system inclusion of a field term
followed by a one-sided Fourier transformation gives the spectral response of the
memory function, in terms of susceptibility, as
K ( w ) = t - ' ( x ( O ) / x ( w ) ) - iw (12)
 Debye and non-Debye relaxation 3833

where w is the radian frequency. Inverse Fourier transformation of equation (12), when
it exists, then gives the time dependence of the memory function.
For the Debye case the zero-frequency normalised reciprocal susceptibility response
function is (1 + iwt) and hence K ( w ) has the constant value t-'. On carrying out the
inverse transformation the memory function in time is obtained as a b-function at time
zero of magnitude t-'. Hence, on the timescale of the relaxation, there is no memory.
In general when the spectral shape functions are more complex the inverse trans-
formations of their reciprocals are not simple. It is however instructive to examine a
number of cases for which the memory function in time can be determined. Perfect
resonance gives a constant, and positive, memory function for all times greater than zero
with a magnitude that is the square of the resonant frequency. An exponentially damped
resonance gives both a 6-function at time zero, of magnitude equal to the reciprocal of
the damping time, and a positive exponential decay term with relaxation time equal to
the damping time and magnitude, as in the perfect resonance case, given by the square
of the resonant frequency. These characteristics, and that of the Debye case, are listed
in table 1.
Here, however, we are interested in more than one process of relaxation. In order
to examine the problem fully it would be necessary to consider, in detail, the coupling
that takes place between the processes. As this requires extensive knowledge of the
particular system we prefer to approach the problem in a different manner. First consider
two Debye processes, A and B. Under the conditions applying to case Ib the dipoles in
each subset A and B relax independently of each other and of the dipoles in the other
subset. Hence equation (11)has to be written as

and

which lead immediately to

K*(t) = t i 1 b(0) KB(t) = tglb(0).
Because of the required condition of non-interaction these subset currents exist inde-
pendently of each other as do the A and B processes within the sample. Memory
functions have to be defined separately for each subset current and the total external
current is given by their parallel addition.
Relaxation case IIb, however, is more interesting and can be taken as a simple
model of cooperative or series relaxation. Here we will consider only two relaxation
components and we may, if we wish, take one of these as being anoverdampedresonance
and the other an orientational realignment, the essential feature being that the timescales
of the relaxations should be different. In general the two components will have differing
magnitudes, a and b, but exclusion of interactions with other dipoles within the system
allows us to adopt the simplest case of two exponentially damped relaxations with
relaxation times t, and tb,respectively. Because each component is part of the total
relaxation of the same dipole it is necessary to define a single memory function for the
response of the system by applying equation (11) to the total polarisation with the
effective relaxation time, t,being taken as the mean relaxation time.
3834 R M Hill and L A Dissado

z
 Debye and non-Debye relaxation 3835

Straightforward but tedious algebra then gives the two-term memory function listed
in full in table 1 which has the characteristic b-function at time zero and a negative-
amplitude exponential decay term. It can be seen that if either a or b is zero, or if tuis
equal to t b , the exponential term disappears and we are left with the b-function of the
Debye case. Of more interest, however, is the case when one of the relaxation times is
greatly in excess of the other. Letting t b %tu yields

K ( t ) = t;iL3(0) - ( b / a t u t b exp[
) - ( a + b)t/at,]. (15)

That is the b-function magnitude is given by the faster process and the relaxation time
of the exponential decay is of the order of the relaxation time of the slower process. We
can consider that the fast process corresponds to the fast relaxation (and resonance)
processes that lead to the ‘infinite-frequency’ permittivity being greater than unity and
that the slower process is the relaxation that is being observed. Hence in any real material
for which E , is greater than unity there will always be memory on the timescale of
relaxation when there is more than one component in a sequential route to relaxation.
Essentially there is an exchange of energy between the relaxing components and this
exchange is a decaying function of time, but on the timescale of the slowest relaxation.
Derivation of the memory function has therefore shown that even for the simple
distribution of a pair of exponential relaxations a fundamental difference exists between
an ensemble of independent relaxations and a sequential relaxation of components of
the same dipole. In this latter case the memory has extended from the zero-time timescale
into the relaxation timescale. Therefore if relaxation is to be described correctly in
terms of the initial polarisation it must include the response due to the ‘instantaneous’
processes. Experimentally, of course, these responses are seldom seen on the timescale
of the relaxation; their neglect will however lead to erroneous conclusions concerning
the polarisation and the decay current in addition to an incorrect approach to zero time
(Williams 1972).
A detailed examination of the cluster model identifying the relationships between
the Curie-von Schwiedler law and the presence of a non-zero memory on the relaxation
timescale has been completed (Dissado et a1 1985) and there is every reason to assume
that the hierarchical model of Palmer et a1 (1984) will show the same feature.

5. Conclusions

Debye relaxation, as conventionally discussed, is unique in having a memory function

that is a zero-time &function. The forcing of experimental data into a distribution
of independently relaxing species leads to a diagonal array of equivalent &function
responses. This is a consequence of the independence of the relaxations of the species
comprising the ensemble, in a parallel construct. It has been shown, however, that the
Guo and Guo experiment is a useful technique for differentiating the single Debye
relaxation from all other forms of relaxation. Only for the Debye case is the state of
relaxation completely defined by the polarisation.
Series relaxation, formally considered here in terms of a sequential two-component
model leads to a single memory function which is non-zero, and decaying, on the
timescale of the relaxation process itself. The success of the cluster model of relaxation,
and to a more limited extent of the Kohlrausch/Williams and Watts model, lies in the
construction of a continuum of timescales from the very short up to the effective
3836 R M Hill and L A Dissado

relaxation time. It is expected that this will lead to a non-zero memoryover the timescale
of relaxation.
In all cases but that of Debye the Guo and Guo experiment will give a finite polar-
isation and relaxation current after the field has been returned to zero, and hence
this experiment cannot differentiate directly between the commonly accepted parallel
distribution of relaxation times and the sequential or series picture.

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