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Lecture 1

Introduction into the physics of dielectrics.


ii. Electric dipole - definition.
a) Permanent dipole moment,
b) Induced dipole moment.
iii. Polarization and dielectric constant.
iv. Types of polarization
a) electron polarization,
b) atomic polarization,
c) orientation polarization,
d) ionic polarization.
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Ancient times

1745 first condensor constructed by Cunaeus and Musschenbroek


And is known under name of Leyden jar

1837 Faraday studied the insulation material,which he called the dielectric

Middle of 1860s Maxwell’s unified theory of electromagnetic phenomena

ε = n2
1887 Hertz 1847 Mossotti

1897 Drude 1879 Clausius

Lorentz-Lorentz
1912 Debye Internal field
Dipole moment
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The dynamic range of Dielectric
Spectroscopy
Dielectric spectroscopy is sensitive to relaxation processes
in an extremely wide range of characteristic times ( 10 5 - 10 -12 s)

Broadband Dielectric Spectroscopy

Time Domain Dielectric Spectroscopy

10-6 10-4 10-2 100 102 104 106 108 1010 1012
f (Hz)
Macromolecules Glass forming
Porous materials liquids
and colloids
Clusters Single droplets
and pores Water

ice

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Dielectric response in biological systems
Dielectric spectroscopy is sensitive to relaxation processes
in an extremely wide range of characteristic times ( 10 5 - 10 -11 s)
Broadband Dielectric Spectroscopy
Time Domain Dielectric Spectroscopy

10-1 0 101 102 103 104 105 106 107 108 109 1010 1011 1012 1013 1014

H
ice Cells Proteins

H3N+ — C — COO-
f (Hz)

R
Amino acids
Water
Ala Asp Arg Asn
Cys Glu Gln His
Ile Leu Lys Met
Phe Ser Thr Trp
Tyr Val
DNA, RNA
Lipids
Tissues
P
Head group
-
N+

region

α-Dispersion β - Dispersion δ - Dispersion γ - Dispersion


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ii. Electric dipole -
definition
The electric moment of a point charge relative to a fixed point
is defined as er, where r is the radius vector from the fixed
point to e. Consequently, the total dipole moment of a whole
system of charges ei relative to a fixed origin is defined as:

m = ∑ ei ri (1.1)
i

A dielectric substance can be considered as consisting of


elementary charges ei , and
∑i
ei = 0 (1.2)

if it contains no net
charge.
If the net charge of the system is zero, the electric moment is
independent of the choice of the origin: when the origin is
displaced over a distance ro, the change in m is according to
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(1.1), given by:
∆m = −∑ ei ro = −ro ∑ ei
i i
Thus ∆m equals zero when the net charge is zero.

Then m is independent of the choice of the origin. In this case


equation (1.1) can be written in another way by the
introduction of the electric centers of gravity of the positive
and the negative charges.

∑er = r ∑e = r Q
These centers are defined by the equations:
positive
i i p
positive
i p

and
∑e r
negative
i i = rn ∑e
negative
i = rn Q

in which the radius vectors from the origin to the centers are
represented by rp and rn respectively and the total positive
charge is called Q.
Thus in case of a zero net charge, equation (1.1) can be
written as: 6
m = (rp − rn )Q
The difference rp-rn is equal to the vector distance between
the centers of gravity, represented by a vector a, pointing
from the negative to the positive center ( Fig.1.1).
Thus we have:
+Q
m = aQ (1.3)
rp a
Therefore the electric moment of a
- Q system of charges with zero net
rn charge is generally called the electric
dipole moment of the system.
Figure 1.1
A simple case is a system consisting of only two point charges
+ e and - e at a distance a.
Such a system is called a (physical) electric dipole, its
moment is equal to ea, the vector a pointing from the
negative to the positive charge. 7
A mathematical abstraction derived from the finite physical
dipole is the ideal or point dipole. Its definition is as follows:
the distance a between two point charges +e and -e i.e.
replaced by a/n and the charge e by en.
The limit approached as the number n tends to infinity is the
ideal dipole. The formulae derived for ideal dipoles are
much simpler than those obtained for finite dipoles.
Many natural molecules are examples of systems with a
finite electric dipole moment (permanent dipole moment),
since in most types of molecules the centers of gravity of the
positive and negative charge distributions do not coincide.

The molecules that have such kind of


permanent dipole molecules called polar
molecules.
Apart from these permanent or intrinsic
dipole moments, a temporary induced
Fig.2 Dipole
moment of water dipole moment arises when a particle is
molecule. brought into external electric field.
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Under the influence of this field, the positive and negative
charges in the particle are moved apart: the particle is
polarized. In general, these induced dipoles can be treated
as ideal; permanent dipoles, however, may generally not be
treated as ideal when the field at molecular distances is to
be calculated.
The values of molecular dipole moments are usually
expressed in Debye units. The Debye unit, abbreviated as D,
equals 10-18 electrostatic units (e.s.u.).
The permanent dipole moments of non-symmetrical
molecules generally lie between 0.5 and 5D. It is come from
the value of the elementary charge eo that is 4.4⋅10-10 e.s.u.
and the distance s of the charge centers in the molecules
amount to about 10-9-10-8 cm.
In the case of polymers and biopolymers one can meet much
higher values of dipole moments ~ hundreds or even
thousands of Debye units. To transfer these units to CI
system one have to take into account that 1D=3.33⋅10-10
9
coulombs⋅m.
Polarizatio
n
Some electrostatic
theorems.
a) Potentials and fields due to electric charges.

According to Coulomb's experimental inverse square law,


the force between two charges e and e' with distance r is
given by: '
ee r (1.4)
F= 2
r r
Taking one of the charges, say e', as a test charge to measure
the effect of the charge e on its surroundings, we arrive at the
concept of an electric field produced by e and with a field
strength or intensity defined by:
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F
E = lim (1.5)
e' → 0 e'

The field strength due to an electric charge at a distance r is


then given by:
e r
E= 2 (1.6)
r r
in which r is expressed in cm, e in electrostatic
units and E in dynes per charge unit, i.e. the e.s.u.
of field intensity.
A simple vector-analytic calculation shows that Eq. (1.6)
leads to:
∫∫ E ⋅ dS = 4πe (1.7)

in which the integration is taken over any closed surface


around the charge e, and where dS is a surface element
having direction of the outward normal. 11
Assuming that the electric field intensity is additively built up
of the contributions of all the separate charges (principle of
superposition) Eqn. (1.7) can be extended to:

∫∫ E ⋅ dS = 4π ∑ e
i
i (1.8)

This relation will still hold for the case of the continuous
charge distribution, represented by a volume charge density
ρ or a surface charge density σ. For the case of a volume
charge density we write:

∫∫ E ⋅ dS = 4π ∫∫∫ ρ dv
V
(1.9)

or , using Gauss divergence


theorem:
divE = 4πρ (1.10)

This equation is the first Maxwell's well-known equations for


the electrostatic field in vacuum; it is generally called the
source equation. 12
The second of Maxwell's equations, necessary to derive E
uniquely for a given charge distribution, is:

curl E = 0 (1.11)

or using Stokes's theorem:

∫ E ⋅ ds = 0 (1.12)

in which the integration is taken along a closed curve of


which ds is a line element.

Stokes' theorem:

∫∫ (curlA) ⋅ dS = ∫ A ⋅ ds,
S C

where C is the contour of the surface of integration S, and


where the contour C is followed in the clock-wise sense when
looking in the direction of dS.
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From (1.12) it follows that E can be written as the gradient of
a scalar field φ, which is called the potential of the field:

E = -gradφ (1.13)

The combination of (1.10) and (1.13) leads to the famous


Poisson's equation:

div grad φ = ∇ ⋅ ∇φ = ∇ 2 φ = ∆φ = −4πρ (1.14)

In the charge-free parts of the field this reduces to the


Laplace's equation:

(1.15)
∆φ = 0

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The vector fields E and
D.
For measurement inside matter, the definition of E in
vacuum, cannot be used.
There are two different approaches to the solution of the
problem how to measure E inside matter. They are:

1. The matter can be considered as a continuum in which, by


a sort of thought experiment, virtual cavities were made.
(Kelvin, Maxwell). Inside these cavities the vacuum
definition of E can be used.
2. The molecular structure of matter considered as a
collection of point charges in vacuum forming clusters of
various types. The application here of the vacuum definition
of E leads to a so-called microscopic field (Lorentz,
Rosenfeld, Mazur, de Groot). If this microscopic field is
averaged, one obtains the macroscopic or Maxwell field E
.
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The main problem of physics of dielectrics of passing
from a microscopic description in terms of electrons, nuclei,
atoms, molecules and ions, to a macroscopic or
phenomenological description is still unresolved completely.
For the solution of this problem of how to determine the
electric field inside matter, it is also possible first to introduce
a new vector field D in such a way that for this field the
source equation will be valid.
divD = 4 πρ (1.16)

According to Maxwell matter is regarded as a continuum. To


use the definition of the field vector E, a cavity has to be
made around the point where the field is to be determined.
However, the force acting upon a test point charge in this
cavity will generally depend on the shape of the cavity,
cavity since
this force is at least partly determined by effects due to the
walls of the cavity. This is the reason that two vector fields
defined in physics of dielectrics:
The electric field strength E satisfying curlE=0, and the
dielectric displacement D, satisfying div D=4πρ. 16
The Maxwell continuum can be treated as a dipole density of
matter. Difference between the values of the field vectors
arises from differences in their sources. Both the external
charges and the dipole density of the piece of matter act as
sources of these vectors.
The external charges contribute to D and to E in the same
manner. Because of the different cavities in which the field
vectors are measured, the contribution of dipole density to D
and E are not the same. It can be shown that

D − E = 4πP (1.17)

where P called the POLARIZATION.

Generally, the polarization P depends on the electric strength


E. The electric field polarizes the dielectric.
The dependence of P on E can take several forms:

P = χE (1.18)
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The polarization proportional to the field strength. The
proportional factor χ is called the dielectric susceptibility.
D = E + 4 πP = ( 1 + 4πχ )E = εE (1.19)

in which ε is called the dielectric permittivity. It is also


called the dielectric constant, because it is independent of the
field strength. It is, however, dependent on the frequency of
applied field, the temperature, the density (or the pressure)
and the chemical composition of the system.

P = χE + ξE 2 E (1.20)

For very high field intensities the proportionality no longer


holds.→Dielectric saturation and non-linear dielectric
effects.

P = χE (1.21)

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For non-isotropic dielectrics, like most solids, liquid crystals,
the scalar susceptibility must be replaced by a tensor. Hence,
the permittivity ε must be also be replaced by a tensor:

D x = ε11E x + ε12 E y + ε13 E z


D y = ε 21E x + ε 22 E y + ε 23 E z (1.22)

D z = ε 31E x + ε 32 E y + ε 33 E z

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Types of
polarization
For isotropic systems and leaner fields in the case of static
electric fields
ε −1
P= E

The applied electric field gives rise to a dipole
density
There can be two sources of this induced dipole
moment:
Deformation
polarization
a. Electron polarization - the displacement of nuclear and
electrons in the atom under the influence of external
electric field. As electrons are very light they have a rapid
response to the field changes; they may even follow the
field at optical frequencies.
b. Atomic polarization - the displacement of atoms or atom
groups in the molecule under the influence of external electric
field. 20
Deformation
polarization

+ - +

- -
Electric Field

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Orientation
polarization:

The electric field tends to direct the permanent dipoles.

Electric field
+e

-e

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Ionic
Polarization
In ionic lattice, the positive ions are displaced in the
direction of an applied field while the negative ions are
displaced in the opposite direction, giving a resultant
(apparent)
apparent dipole moment to the whole body.
+ -
- -
+ + - -
+
- +
- - + -
+ -
+
+ + -
- +
- - + - +
+ - + +

Electric field
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Polar and Non-polar
Dielectrics
To investigate the dependence of the polarization on
molecular quantities it is convenient to assume the
polarization P to be divided into two parts: the induced
polarization Pα caused by the translation effects,
effects and the
dipole polarization Pµ caused by the orientation of the
ε −1
permanent dipoles.
E = Pα + Pµ

A non-polar dielectric is one whose molecules possess no
permanent dipole moment.

A polar dielectric is one in which the individual molecules


possess a dipole moment even in the absence of any applied
field, i.e. the center of positive charge is displaced from the
center of negative charge.
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