Dielectrics

Part 3: dipole relaxation

Ryszard J. Barczyski, 2009 Politechnika Gdaska, Wydzia FTiMS, Katedra Fizyki Ciaa Staego Materiay dydaktyczne do uytku wewntrznego

Polarization in alternating electric field

All polarization mechanisms respond to an electrical field by shifting masses around. This means that masses must be accelerated. It takes time, so we must expect that the response to a field will depend on the frequency f of the electrical field. If the frequency is sufficiently large, no system will be able to follow. Thus we expect that there is no response to an extremely high frequency electric field. This means that for any given polarisation mechanism the dielectric permittivity will approach 1 for f -> .

Polarization in alternating electric field

Looking at the polarization mechanisms, we see that there is a fundamental difference in the dynamics of the mechanisms with regard to the response to changing forces: In the cases of electron and ionic polarization, the electrical field causes change in the distance between the charges involved. The response is a restoring force that is directly proportional to the separation distance of the dipole charges. We have an harmonic oscillator.

The characteristic property of any harmonic oscillator is the phenomena of resonance at its specific frequency.

Polarization in alternating electric field

In the case of the orientation polarization, there is no direct force that "pulls" the dipoles back to random orientation. Instead we have many statistical events and the response to the electrical field is their average result. If a driving force is present, there is an equilibrium state with a net dipole moment. If the driving force were to disappear, the ensemble of dipoles will achieve a new equilibrium (random distribution) within some characteristic time called relaxation time. We thus have to consider just the two basic situations: dipole relaxation and dipole resonance. Every specific mechanism in real materials fits one of the two cases.

Dipole relaxation
Consider what happens if the driving electrical field is suddenly switched off, after it has been constant for a long time so that an equilibrium distribution of dipoles could be obtained. We expect then that the dipoles will randomize and the total polarization will go to zero. However, that cannot happen instantaneously. A specific dipole has a certain orientation at the time the field is switched off, and it changes that orientation only by interactions with other dipoles or, in a solid, with phonons). This takes a characteristic time, roughly the time between collisions, before the dipole moment disappears.

Dipole relaxation

We are discussing statistical events so the characteristic time for a given dipole will be small for some, and large for others. But there will be an average value which we will call the relaxation time of the system. We expect a smooth change over from the polarization to zero within the relaxation time .

Dipole relaxation
All we have to assume is that the number of dipoles decaying from the oriented to the random state is proportional to the number of oriented dipoles:
dn 1 = n dt

The same model covers for example radioactive decay, cooling of any material, and the decay of the foam on top a beer (bubbles are an energetically excited state of beer because of the additional bubble surface energy :-) ).
n =n 0 e
t

Dipole relaxation

n =n 0 e

We would like to know also polarisation frequency dependence P() with = 2f - the output to a periodic harmonic input, to a field like E = Eo sint. We already know the time dependence P(t) for a switch on-off signal, and from that we can - in principle - derive P(). We thus have to employ the Fourier transform of P(t).
P = P 0 e
0 t i t

dt

where P0 is the static polarization P(=0)

Dipole relaxation
We obtain
P0 P = 1 i 0 1 0=

The P() then are the Fourier coefficients if you describe the P(t) curve by a Fourier integral (or series, with infinitesimally closely spaced frequency intervals). P() thus is the polarization response of the system if you treat it with an electrical field given by E = E0 exp (it) that contains just one frequency . However, the Fourier coefficients are complex numbers what does it that mean?

P0 P = Dipole relaxation 1 i 0 We end up with a complex polarization, but this need not bother us since we would only consider the real part of P when we are in need of real numbers. However, there is a smarter way to describe relaxation which can be generalized to all frequency dependent polarization phenomena.

We will keep our basic equation that couples polarization and field strength also for alternating fields. This requires that the susceptibility becomes frequency dependent:
P =0 E

We also include in () a possible phase shift between P() and E(), so it becomes a complex number.

Dipole relaxation
s P P 0 1 0 = = = E E 0 1 i 1 i 0 0

Where s is static suceptibility

s 1 0
2

0 =

s 0 1 0
2

We thus have the real and imaginary part of 0 ().

Dipole relaxation

1 1 0 0 Everything we did for the polarization P, may be done for the dielectric flux density D - just replace the letter "P" by "D" and "" by "" and we obtain a complex frequency dependent dielectric constant () = () + 1 with s instead of s as the static case.

0 =

s
2

s 0
2

We assumed that at very large frequencies the polarization is zero: the dipole cannot follow and () = 0. But that might be other mechanisms that still "work" at frequencies far larger than what orientation polarization can take. W have to introduce a new parameter ( >> 0) = or ( >> 0) = .

Dipole relaxation - Debye equations

s 1 0
2

' =

' '=

s 0 1 0
2

' = 0 = s ' ' = 0 = 0

' ==
Peter Debye Nobel prize in chemistry, 1936

for his contributions to our knowledge of molecul r structure through his in!estig tions on dipole moments nd on the diffr ction of "#r ys nd electrons in g ses

Dipole relaxation Debye equations

The curves always look similar, the three numbers that define a particular material (s, , and =1/0) only change the numbers on the scales. Full width at half maximum of is about 1.1 decade.

', the real part of a complex amplitude, gives the amplitude of the response that is in phase with the driving force, '', the imaginary part, gives the amplitude of the response that is phase-shifted by 90o.