3.2.

3 Ionic Polarization

Consider a simple ionic crystal, e.g. NaCl.

The lattice can be considered to consist of Na+ - Cl– dipoles as shown below.
Each Na+ - Cl– pair is a natural
dipole, no matter how you pair up
two atoms.
The polarization of a given
volume, however, is exactly zero
because for every dipole moment
there is a neighboring one with
exactly the same magnitude, but
opposite sign.
Note that the dipoles can not
rotate; their direction is fixed.

In an electric field, the ions feel forces in opposite directions. For a field acting as
shown, the lattice distorts a little bit (hugely exaggerated in the drawing)

The Na+ ions moved a bit to

the right, the Cl– ions to the
left.
The dipole moments between
adjacent NaCl - pairs in field
direction are now different and
there is a net dipole moment in
a finite volume now.

From the picture it can be seen that it is sufficient to consider one dipole in field
direction. We have the following situation:

1
 Shown is the situation where the distance between the ions increases by d; the
symmetrical situation, where the distance decreases by d, is obvious. How large is d?
That is easy to calculate:
The force F1 increasing the distance is given by

F1 = q · E

With q = net charge of the ion.

The restoring force F2 comes from the binding force, it is given as the derivative of
the binding potential. Assuming a linear relation between binding force and deviation
from the equilibrium distance l, which is a good approximation for d << l, we can write

F2 = kIP · d

With kIP being the "spring constant" of the bond. kIP can be calculated from the bond
structure, it may also be expressed in terms of other constants that are directly related to
the shape of the interatomic potential, e.g. the modulus of elasticity or Youngs modulus.
If we do that we simply find

kIP = Y · d0

With Y = Youngs Modulus, and d0 = equilibrium distance between atoms.

From force equilibrium. i.e. F1 – F2 = 0, we immediately obtain the following

relations:

2
 Equilibrium distance d

q·E
d =
Y · d0

Induced dipole moment µ (on top of the existing one)

q2 · E
µ =
Y · d0

Polarization P
N·q2·E
P =
Y · d0

Of course, this is only a very rough approximation for an idealized material and just
for the case of increasing the distance. Adding up the various moments - some larger,
some smaller - will introduce a factor 2 or so; but here we only go for the principle

For real ionic crystals we also may have to consider:

More complicated geometries (e.g. CaF2, with ions carrying different amount of
charge).
This example was deliberatly chosen: The dielectric constant of CaF2 is of paramount
interest to the semiconductor industry of the 21st century, because CaF2 is pretty
much the only usable material with an index of refraction n (which is directly tied to
the DK via εr = n2) that can be used for making lenses for lithography machines
enabling dimensions of about 0,1 µm.

If the field is not parallel to a major axis of the crystal (this is automatically the case
in polycrystals), you have to look at the components of µ in the field direction and
average over the ensemble.

Still, the basic effects is the same and ionic polarization can lead to respectable
dielectric constants εr or susceptibilities χ.

3
3.2.4 Orientation Polarization

In the case of orientation polarization we have a material with built-in dipoles that
are independent of each other, i.e. they can rotate freely - in sharp contrast to ionic
polarization.
The prime example is liquid water, where every water molecule is a little dipole that
can have any orientation with respect to the other molecules. Moreover, the orientation
changes all the time because the molecules moves! Orientation polarization for dielectric
dipoles thus is pretty much limited to liquids - but we will encounter it in a major way
again for magnetic dipoles.
A two-dimensional "piece of water" may - very graphically - look somewhat like the
picture below that captures one particular moment in time. It is like a snapshot with a
very, very short exposure time. A few nanoseconds later the same piece of water may
look totally different in detail, but pretty much the same in general.
In a three-dimensional piece of water the blue and red circles would not have to be in
the same plane; but that is easy to imagine and difficut to draw.

Shown is a bunch of water molecules that form natural dipoles because the negatively
charged oxygen atom and the two positively charged H - atoms have different centers of
charge. Each molecule carries a dipole moment which can be drawn as a vector of
constant length. If we only draw a vector denoting the dipole moment, we get - in two
dimensions - a picture like this:

4
 Again, remember that both pictures are "snap shots" that only appear unblurred for
very small exposure times, say picoseconds, because the dipoles wiggle, rotate, and move
around rather fast, and that in three dimensions the vectors would also point out of the
drawing plane.

The total dipole moment is the vector sum of the individual dipole moments.
For dipoles oriented at random, at any given moment this
looks like the picture below if we draw all vectors from a
common origin: The sum of all dipole moments will be
zero, if the dipoles are randomly oriented.
We can see this most easily if we have all dipoles start at the
same origin. The picture, of course, is two-dimensional and
crossly simplified. There would be a lot more (like 10 20)
dipoles for any appreciable amount of water - you really
will average them to zero pretty well.

If we now introduce a field E, the dipoles would have a tendency to turn into the field
because that would lower their energy.
If you have problems with this statement, just imagine the electrostatic interaction,
which will always try to move the positive pole of the dipole towards the negative pole of
the field, and vice versa for the negative pole - the dipole would align itself exactly along
a field line of the external field for minimum energy.
Naively, we would then expect a perfect orientation into the field and a concomitantly
large polarization because that would lead to the minimum of the dipole energy.
Well, water does have a pretty large DK of 81, so there is obviously some orientation
into the field, but it is easy (not really) to show (in an exercise) that this DK is several
orders of magnitude too small for fully oriented dipole moments at some normal field

5
strengths. In reality, the orientation into the field direction will be counteracted by
random collisions with other dipoles, and this process is energized by the thermal energy
"kT" contained in the water.
Again, the dipoles are not sitting still, but moving around and rotating all the time -
because they contain thermal energy and thus also some entropy.
Whenever two molecules collide, their new orientation is random - all memory of an
orientation that they might have had in the electrical field is lost. This is analogous to
what happens to electrons carrying an electrical current in an electrical field.
The electrical field only induces a little bit of average orientation in field direction -
most of the time an individual dipole points in all kinds of directions. This is the simple
truth even so some (undergraduate) text books show pictures to the contrary. The "real"
picture (in the sense of a snapshot with a very short exposure time) looks like this:
 If you are not familiar with the basics of thermodynamics, you have a problem at this
point.

We obviously need to calculate the free enthalpy G = U – TS to see what kind of

average orientation will result in a given field. Note that we use U, the common symbol
for the (internal) energy instead of H, the common symbol for the enthalpy, because U
and H are practically identical for solids and liquids anyway.
Moreover, a mix up with the magnetic field strength usually designated by H, too,
would be unavoidable otherwise. (The possible mix-up between internal energy U and
voltage U is not quite so dangerous in this context).

The internal energy of a dipole is clearly a function of its orientation with respect to
the field. It must be minimal, when the dipole is aligned with the field and the dipole
moment has the same direction as the electrical field, and maximal if the direction is
reversed.
This is the easy part: The energy U(δ) of a dipole with dipole moment µ in a field E
as a function of the angle δ between the dipole moment direction and the field direction.
From basic electrostatics we have have

U(δ) = – µ · E = – |µ| · |E| · cos δ

The minimum energy U thus would occur

for δ = 0o, i.e. for perfect alignment in
proper field direction (note the minus
sign!); the maximum energy for δ = 180o,
i.e. for alignment the wrong way around.
That was for two dimensions - now we
must look at this in three dimensions.

In 3D we see that all dipoles with the same angle δ between their axis and the field
still have the same energy - and this means now all dipoles on a cone with opening angle
2δ around the field axis if we consider possible orientations out of the plane of drawing.
In order to obtain the total internal energy Utotal of a bunch of dipoles having all
kinds of angles δ with the field axis, we will have to sum up all cones.
This means we take the number of dipoles N(δ) having a particular orientation δ
times the energy belonging to that δ, and integrate the resulting function over δ from 0o to
180o. This is something that we could do - if we would know N(δ).

7
 However, just calcuating Utotal will not be of much use. We also must consider the
entropy term – TS, because we do not want to calculate the total internal energy Utotal,
but the total free enthalpy G = Utotal – TS.
We need to consider that term as a function of all possible angle distributions and
then see for which distribution we can minimize G.

But what is the entropy S(N(δ)) of an ensemble of dipoles containing N(δ) members at
the angle δ as a function of the many possible distribution N(δ)? Not an easy question to
answer from just looking at the dipoles.

Fortunately, we do not have to calculate

S explicitly!
We know a formula for the distribution of (classical) particles on available energy
levels that automatically gives the minimum of the free enthalpy!
We have a classical system where a number of independent particles (the dipoles) can
occupy a number of energy levels (between Umin and Umax) as defined by δ = 0o or δ =
180o, respectively.
Basic thermodynamics asserts that in equilibrium, the distribution of the particles on
the available energy levels is given by the proper distribution function which is defined in
such a way that it always gives the minimum of the free enthalpy.
Since we deal with classical particles in this approach, we have to use the Boltzmann
distribution. We obtain for N(U) = number of dipoles with the energy U

U(δ)
N(U) = A · exp –
kT

With a constant A that has yet to be determined.

This Boltzmann distribution equation gives us the number of dipoles with a certain
angle relative to the field direction, i.e. the number of dipoles that have their tips on a
circle with an opening angle 2δ relative to the field directions as shown below.

8
 We are, however, only interested in the component of the dipole moment parallel to
the field. For this we look at the solid angle increment dΩ defined on the unit sphere as
the segment between δ and δ + dδ
The number of dipoles lying in the cone
angle increment defined by δ and δ+ ∆δ
is the same as the number of dipoles
with tips ending on the surface of the
unit sphere in the incremental angle dΩ.
It is given by
N(U(δ)) · dΩ.
Note that dΩ is a measure of an
incremental area; a kind of ribbon once
around the unit sphere.
The sum of the components µF of the
dipole moments in field direction is then
.

µF = (N · dΩ) · (µ · cos δ)

If you are not familiar with spherical coordinates, this (and what we will do with it),
looks a bit like magic. Since we do not want to learn Math in this lecture, the essentials to
spherical coordinates are explained in detail in a basic module.

The average dipole moment, which is what we want to calculate, will now be obtained
by summing up the contributions from all the dΩs

9
 π
⌠
N(U(δ)) · µ · cosδ · dΩ
⌡
0
<µF> =
π
⌠
N(U(δ)) · dΩ
⌡
0

And the integrals have to be taken from the "top" of the sphere to the "bottom" , i.e.
from 0 to π.

dΩ and δ are of course closely related, we simply have

dΩ = 2π · sinδ · dδ

Putting everything together, we obtain a pretty horrifying integral for µF that runs
from 0 to π

π
µ · E · cosδ
⌠
µ · sinδ · cosδ · exp · dδ
⌡ kT
0
<µF> =
π
µ · E · cosδ
⌠
sinδ · exp · dδ
⌡ kT
0

One advantage is that we got rid of the undetermined constant A. The integral, being a
determined integral, is now simply a number depending on the parameters of the system,
i.e. the temperature T, the dipole moment µ and the field strength E.
The problem has been reduced to a mathematical exercise in solving integrals.

Since we are not interested at doing math, we just show the general direction toward a
solution:

10
 Use the substitutions

µ·E
β =
kT

x = cos δ

The integral reduces to

–1
⌠
µ· x · exp (β · x) · dx
⌡
+1
<µF> =
–1
⌠
exp (β · x) · dx
⌡
+1

The final result after quite a bit of fiddling around is

<µF> = µ · L(β)

With L(β) = Langevin function, named after Paul Langevin, and defined as

1
L(β) = coth (β) –
β

µ·E
β =
kT
y = coth x

The "coth" is the hyperbolic cotangent, defined as coth x = (ex + e–x)/(ex – e–x) =
1/tanh x

11
 L(β) is a tricky function, because the coth x part looks pretty much like a hyperbola,
from which the real hyperbola 1/x is subtracted. What's left is almost nothing - L(x)
values are between 0 and 1

The polarization (always on average, too) is accordingly

P = N · <µ>

This is a definite result, but it does not help much. We need to discuss the
mathematical construct "Langevin function L(β)" to get some idea of what we obtained.
We look at the graph in general units and in units of the dipole moment and electrical
field (in red).
Since β is
proportional to the
field strength E, we
see that the dipole
moment and the
polarization
increases
monotonically with
E, eventually
saturating and giving
<µF> = µ which is
what we must expect.

The question is, what range of β values is accessible for real materials. i.e. how close
to the saturation limit can we get?

For that we look at some simple approximations.

If we develop L(β) into a series (consult a math textbook), we get

β β3 2 β5
L(β) = – + – .....
3 45 945

For large values of β we have L(β) ≈ 1, while for small values of β (β < 1), the
Langevin function can be approximated by .

L(β) ≈ 1/3 · β

12
 The slope thus is 1/3 for β → 0
For "normal" circumstances, we always have β << 1 (see below), and we obtain as
final result for the induced dipole moment the Langevin - Debye equation

µ2 · E
<µF> =
3kT

N · µ2 ·E
<P> =
3kT

These equations will be rather good approximation for small values of µ and E and/or
large values of T. For very large fields and very small temperatures the average dipole
moment would be equal to the built in dipole moment, i.e. all dipoles would be strictly
parallel to the field. This is, however, not observed in "normal" ranges of fields and
temperatures

Lets see that in an example. We take

E = 108 V/cm which is about the highest field strength imaginable before we have
electrical breakdown,
µ = 10–2 9 Asm, which is a large dipole moment for a strongly polarized molecule, e.g. for
HCl, and
T = 300 K.
This gives us
β = 0,24 - the approximation is still valid.

At T = 30 K, however, we have β = 2,4 and now we must think twice:

1. The approximation would no longer be good. But
2. We no longer would have liquid HCl (or H2O, or liquid whatever with a dipole
moment), but solid HCl (or whatever) , and we now look at ionic polarization and no
longer at orientation polarization!

You may now feel that this was a rather useless exercise - after all, who is interested
in the DK of liquids? But consider: This treatment is not restricted to electric dipoles. It is
valid for all kinds of dipoles that can rotate freely, in particular for the magnetic dipoles
in paramagnetic materials responding to a magnetic field.
Again, you may react with stating "Who is interested in paramagnets? Not an
electrical engineer!" Right - but the path to ferromagnets, which definitely are of interest,
starts exactly where orientation polarization ends; you cannot avoid it.

13
 It is important to be aware of the basic condition that we made at the beginning: there
is no interaction between the dipoles! This will not be true in general.
Two water molecules coming in close contact will of course "feel" each other and
they may have preferred orientations of their dipole moments relative to each other. In
this case we will have to modify the calculations; the above equations may no longer be a
good approximation.
On the other hand, if there is a strong interaction, we automatically have some
bonding and obtain a solid - ice in the case of water. The dipoles most likely cannot
orientate themselves freely; we have a different situation (usually ionic polarization).
There are, however, some solids where dipoles exist that can rotate to some extent - we
will get very special effects, e.g. "ferroelectricity".

14
3.2.5 Summary and Generalization

For all three cases of polarization mechanisms, we had a linear relationship between
the electrical field and the dipole moment (for fields that are not excessively large):

Electronic polarization Ionic polarization Orientation polarization

q2 µ2
µIP = ·E µop = · E
µEP = 4π · ε0 · R3 · E kIP 3kT

It seems on a first glance that we have justified the "law" P = χ · E.

However, that is not quite true at this point. In the "law" given by equation above, E
refers to the external field, i.e. to the field that would be present in our capacitor without a
material inside
We have Eex = U / d for our plate capacitor held at a voltage U and a spacing between
the plates of d.
On the other hand, the induced dipole moment that we calculated, always referred to
the field at the place of the dipole, i.e. the local field Eloc. And if you think about it, you
should at least feel a bit uneasy in assuming that the two fields are identical. We will see
about this in the next paragraph.

Here we can only define a factor that relates µ and Eloc; it is called the polarizability
α. It is rarely used with a number attached, but if you run across it, be careful if ε0 is
included or not; in other words what kind of unit system is used.
We now can reformulate the three equations on top of this paragraph into one
equation

µ = α · Eloc

15
 The polarizability α is a material parameter which depends on the polarization
mechanism: For our three paradigmatic cases they are are given by

αEP = 4π · ε0 · R3

q2
αIP =
kIP

µ2
αOP =
3kT

This does not add anything new but emphasizes the proportionality to E.

So we almost answered our first basic question about dielectrics - but for a full answer
we need a relation between the local field and the external field. This, unfortunately, is
not a particularly easy problem
One reason for this is: Whenever we talk about electrical fields, we always have a
certain scale in mind - without necessarily being aware of this. Consider: In a metal, as
we learn from electrostatics, there is no field at all, but that is only true if we do not look
too closely. If we look on an atomic scale, there are tremendous fields between the
nucleus and the electrons. At a somewhat larger scale, however, they disappear or
perfectly balance each other (e.g. in ionic crystals) to give no field on somewhat larger
dimensions.
The scale we need here, however, is the atomic scale. In the electronic polarization
mechanism, we actually "looked" inside the atom - so we shouldn't just stay on a "rough"
scale and neglect the fine details.

Nevertheless, that is what we are going to do in the next paragraph: Neglect the
details. The approach may not be beyond reproach, but it works and gives simple
relations.

16
3.2.6 Local Field and Clausius - Mosotti Equation

"Particles", i.e. atoms or molecules in a liquid or solid are basking in electrical fields -
the external field that we apply from the outside is not necessarily all they "see" in terms
of fields.
First, of course, there is a tremendous electrical field inside any atom. We have after
all, positive charges and negative charges separated by a distance roughly given by the
diameter of the atom.
Second, we have fields between atoms, quite evident for ionic crystals, but also
possible for other cases of bonding.

All these fields average to zero, however, if you look at the materials at a scale
somewhat larger than the atomic scale. Only then do we have a field-free interior as we
always assume in electrical engineering ("no electrical field can penetrate a metal").

Here, however, we are looking at the effect an external field has on atoms and
molecules, and it would be preposterous to assume that what an atom "sees" as local
electrical field is identical to what we apply from the outside.
Since all our equations obtained so far always concerned the local electrical field -
even if we did not point that out in detail before - we now must find a relation between
the external field and the local field, if we want to use the insights we gained for
understanding the behavior of dielectrics on a macroscopic scale.

We define the local field Eloc to be the field felt by one particle (mostly an atom) of
the material at its position (x,y,z).
Since the superposition principal for fields always holds, we may express Eloc as a
superposition of the external field Eex and some field Emat introduced by the surrounding
material. We thus have

Eloc = Eex + Emat

All electrical fields can, in principle, be calculated from looking at the charge
distribution ρ(x, y, z) in the material, and then solving the Poisson equation (which you
should know). The Poisson equation couples the charge distribution and the potential
V(x, y, z) as follows:

ρ(x, y, z)
∆V = –
ε · ε0

17
 ∂2 V ∂2 V ∂2 V
∆ = Delta +
operator = +
∂x2 ∂y2 ∂z2

The electrical field then is just the (negative) gradient of the potential; E = – ∇V.

Doing this is pretty tricky, however. We can obtain usable results in a good
approximation in a much simpler way, by using the time-honored Lorentz approach or
the Lorentz model.
In this approach we decompose the total field into four components.
For doing this, we imagine that we remove a small sphere containing a few 10 atoms
from the material. We want to know the local field in the center of this sphere while it is
still in the material; this is the local field Emat we are after. We define that field by the
force it exerts on a charge at the center of the sphere that acts as a "probe".

The essential trick is to calculate the field produced from the atoms inside the sphere
and the field inside the now empty sphere in the material. The total local field then is
simple the sum of both.
Like always, we do not consider the charge of the "probe" in computing the field that
it probes. The cut-out sphere thus must not contain the charge we use as the field probe!
The cut-out material, in general, could produce an electrical field at its center since it
is composed of charges. This is the 1st component of the field, Enear which takes into
account the contributions of the atoms or ions inside the sphere. We will consider that
field in an approximation where we average over the volume of the small sphere. To
make things cleare, we look at an ionic crystal where we definitely have charges in our
sphere.

Enear, however, is not the only field that acts on our probe. We must include the field
that all the other atoms of the crystal produce in the hollow sphere left after we cut out
some material. This field now fills the "empty" void left by taking out our sphere.
This field is called EL (the "L" stands for Lorentz); it compensates for the cut-out part
- and that provides our 2nd component.

Now we only have to add the "macroscopic" fields from 1. the polarization of the
material and 2. the external field that causes everything:
The field Epol is induced by the macroscopic polarization (i.e. by area charges equal
to the polarization); it is the 3rd component
The external field Eex = U/d from the applied voltage at our capacitor which supplies
the 4th component.

In a visualization, this looks like this:

18
 The blue "sphere" cuts through the lattice (this is hard to draw). The yellow "point" is
where we consider the local field; we have to omit the contribution of the charged atom
there. We now have

Eloc = Eex + Epol + EL + Enear

How large are those fields? We know the external field and also the field from the
polarization (always assuming that the material completely fills the space inside the
capacitor).

U P
Eex = Epol = –
d ε0

We do not know the other two fields, and it is not all that easy to find out how large
they are. The results one obtains, however, are quite simple:
Lorentz showed that Enear = 0 for isotropic materials, which is easy to imagine. Thus
for cubic crystals (or polycrystals, or amorphous materials), we only have to calculate EL.

EL needs some thought. It is, however, a standard problem from electrostatics in a

slightly different form.
In the standard problem one calculates the field in a materials with a DK given by εr
that does not fill a rectangular capacitor totally, but is in the shape of an ellipsoid
including the extreme cases of a pure sphere, a thin plate or a thin needle. The result is
always

NP · P
Eellipse =
εr · εo

19
 In words: The field inside a dielectric in the shape of an ellipsoid (of any shape
whatsoever) that is put between the parallel plates of a typical capacitor arrangement, is
whatever it would be if the dielectric fills the space between the plates completely times a
number NP, the value of which depends on the geometry.
NP is the so-called depolarization factor, a pure number, that only depends on the
shape of the ellipsoid. For the extreme cases of the ellipsoid we have fixed and well-
known depolarization factors:
• Thin plate: N = 1
• Needle: N = 0
• Sphere: N = 1/3

Our case consists of having a sphere with εr = 1. We thus obtain

P
EL =
3εo

We have now all components and obtain

U P P
Eloc = – +
d ε0 3εo

U/d – P/ε0 is just the field we would use in the Maxwell equations, we call it E0. It is
the homogeneous field averaged over the whole volume of the homogeneous material
The local field finally becomes

P
Eloc = E0 +
3εo

This seems a bit odd? How can the local field be different from the average field?

This is one of the tougher questions one can ask. The answer, not extremely
satisfying, comes from the basic fact that all dipoles contribute to E0, whereas for the
local field you discount the effect of one charge - the charge you use for probing the
field (the field of which must not be added to the rest!).
If you feel somewhat uneasy about this, you are perfectly right. What we are
excluding here is the action of a charge on itself. While we may do that because that
was one way of defining electrical fields (the other one is Maxwells equation defining
a field as directly resulting from charges), we can not so easily do away with the
energy contained in the field of a single charge. And if we look at this, the whole

20
 theory of electromagnetism blows up! If the charge is a point charge, we get infinite
energy, and if it is not a point charge, we get other major contradictions.

Not that it matters in everyday aspects - it is more like a philosophical aspect. If you
want to know more about this, read chapter 28 in the "Feynman lectures, Vol. 2"
But do not get confused now! The relation given above is perfectly valid for everyday
circumstances and ordinary matter. Don't worry - be happy that a relatively complex
issue has such a simple final formula!

We now can relate the macroscopic and microscopic parameters. With the old
relations and the new equation we have a grand total of:

µ = α · Eloc

P = N · α · Eloc

P
Eloc = Eo +
3εo

From this we obtain quite easily

P
⎛ ⎞
P = N · α · Eo +
⎝ ⎠
3εo
N · α · Eo
P =
1–N·
α/3εo

With N = density of dipoles

Using the definition of P

P = εo · χ · E = εo · (εr – 1) · E

and inserting it into the equations above gives as final result the connection between
the polarizability α ( the microscopic quantity) and the relative dielectric constant εr (the
macroscopic quantity):

21
 N·α εr – 1
=
3 ε0 εr + 2

χ
=
χ+3

This is the Clausius - Mosotti equation, it relates the microscopic quantity α on the
left hand side to the macroscopic quantity εr (or, if you like that better, χ = εr – 1) on the
right hand side of the equation. This has two far reaching consequences

You must also see this in an historical context: With the Clausius-Mosotti equation the
dielectric properties of materials were essentially reduced to known electrical properties.
There was nothing mysterious anymore about the relative dielectric constant. The next
logical step now would be to apply quantum theory to dielectric properties
We now can calculate (at least in principle) the dielectric constants of all
materials, because we know how to calculate α.
We have an instrument to measure microscopic properties like the polarizability
α, by measuring macroscopic properties like the dielectric constant and
converting the numbers with the Clausius-Mosotti equation.

22