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ε = n2
1887 Hertz 1847 Mossotti
Lorentz-Lorentz
1912 Debye Internal field
Dipole moment
2
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)
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
3
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
m = ∑ ei ri (1.1)
i
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
5
(1.1), given by:
∆m = −∑ ei ro = −ro ∑ ei
i i
Thus ∆m equals zero when the net charge is zero.
∑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.
∫∫ 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)
curl E = 0 (1.11)
∫ E ⋅ ds = 0 (1.12)
Stokes' theorem:
∫∫ (curlA) ⋅ dS = ∫ A ⋅ ds,
S C
E = -gradφ (1.13)
(1.15)
∆φ = 0
14
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:
D − E = 4πP (1.17)
P = χE (1.18)
17
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)
P = χE + ξE 2 E (1.20)
P = χE (1.21)
18
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 z = ε 31E x + ε 32 E y + ε 33 E z
19
Types of
polarization
For isotropic systems and leaner fields in the case of static
electric fields
ε −1
P= E
4π
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
21
Orientation
polarization:
Electric field
+e
-e
22
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
23
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
4π
A non-polar dielectric is one whose molecules possess no
permanent dipole moment.