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Denis Andrienko
International Max Planck Research School
Modelling of soft matter
1115 September 2006, Bad Marienberg
September 14, 2006
Contents
1 What is a liquid crystal 2
1.1 Nematics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.2 Cholesterics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 Smectics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
1.4 Columnar phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.5 Lyotropic liquid crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2 Long and shortrange ordering 7
2.1 Order tensor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.2 Director . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3 Phenomenological descriptions 10
3.1 Landaude Gennes free energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.2 FrankOseen free energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
4 Nematicisotropic phase transition 14
4.1 Landau theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
4.2 MaierSaupe theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
4.3 Onsager theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
5 Response to external ﬁelds 18
5.1 Frederiks transition in nematics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
6 Optical properties 20
6.1 Nematics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
6.2 Cholesterics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
7 Defects 23
8 Computer simulation of liquid crystals 24
9 Applications 27
1
Literature
Many excellent books/reviews have been published covering various aspects of liquid crystals. Among
them:
1. The bible on liqud crystals: P. G. de Gennes and J. Prost “The Physics of Liquid Crystals”, Ref. [1].
2. Excellent review of basic properties (many topics below are taken from this review): M. J. Stephen,
J. P. Straley “Physics of liquid crystals”, Ref. [2].
3. Symmetries, hydrodynamics, theory: P. M. Chaikin and T. C. Lubensky “Principles of Condensed
Matter Physics”, Ref. [3].
4. Defects: O. D. Lavrentovich and M. Kleman, “Defects and Topology of Cholesteric Liquid Crys
tals”, Ref. [4]; Oleg Lavrentovich “Defects in Liquid Crystals: Computer Simulations, Theory and
Experiments”, Ref. [5].
5. Optics: IamChoon Khoo, ShinTson Wu, “Optics and Nonlinear Optics of Liquid Crystals”,
Ref. [6].
6. Textures: Ingo Dierking “Textures of Liquid Crystals”, Ref. [7].
7. Simulations: Michael P. Allen and Dominic J. Tildesley “Computer simulation of liquids”, Ref. [8].
8. Phenomenological theories: Epifanio G. Virga “Variational Theories for Liquid Crystals”, Ref. [9].
Finally, the pdf ﬁle of the lecture notes can be downloaded from
http://www.mpipmainz.mpg.de:/
~
andrienk/lectures/IMPRS/liquid_crystals.pdf.
1 What is a liquid crystal
There is always a reason behind everything and this principle does not exclude naming conventions in
physics. Hence, to understand what is a “liquid crystal” we need to clarify why would one give such a
name to a substance.
At ﬁrst, the notion “liquid crystal” seems to be absurd. It, however, suggests that it is an intermediate
state of a matter, in between the liquid and the crystal. It must possess some typical properties of a
liquid (e. g. ﬂuidity, inability to support shear, formation and coalescence of droplets) as well as some
crystalline properties (anisotropy in optical, electrical, and magnetic properties, periodic arrangement of
molecules in one spatial direction, etc.).
Certain structural features are often found in molecules forming liquid crystal phases, and they may
be summarized as follows:
1. The molecules have anisotropic shape (e. g. are elongated). Liquid crystallinity is more likely to
occur if the molecules have ﬂat segments, e. g. benzene rings.
2. A fairly good rigid backbone containing double bonds deﬁnes the long axis of the molecule.
3. The existence of strong dipoles and easily polarizable groups in the molecule seems important.
4. The groups attached to the extremities of the molecules are generally of lesser importance.
2
Figure 1: The arrangement of molecules in liquid crystal phases. (a) The nematic phase. The molecules
tend to have the same alignment but their positions are not correlated. (b) The cholesteric phase. The
molecules tend to have the same alignment which varies regularly through the medium with a periodicity
distance p/2. The positions of the molecules are not correlated. (c) smectic A phase. The molecules tend
to lie in the planes with no conﬁgurational order within the planes and to be oriented perpendicular to
the planes.
1.1 Nematics
The nematic phase is characterized by longrange orientational order, i. e. the long axes of the molecules
tend to align along a preferred direction. The locally preferred direction may vary throughout the medium,
although in the unstrained nematic it does not. Much of the interesting phenomenology of liquid crystals
involves the geometry and dynamics of the preferred axis, which is deﬁned by a vector n(r) giving its
local orientation. This vector is called a director. Since its magnitude has no signiﬁcance, it is taken to
be unity.
There is no longrange order in the positions of the centers of mass of the molecules of a nematic,
but a certain amount of shortrange order may exist as in ordinary liquids. The molecules appear to be
able to rotate about their long axes and also there seems to be no preferential arrangement of the two
ends of the molecules if they diﬀer. Hence the sign of the director is of no physical signiﬁcance, n = −n.
Optically a nematic behaves as a uniaxial material with a center of symmetry. A simpliﬁed picture of
the relative arrangement of the molecules in the nematic phase is shown in Fig. (1a). The long planar
molecules are symbolized by ellipses.
Figure 2: (a) Schlieren texture of a nematic ﬁlm with surface point defects (boojums). (b) Thin nematic
ﬁlm on isotropic surface: 1dimensional periodicity. Photos courtesy of Oleg Lavrentovich http://www.
lci.kent.edu/ALCOM/oleg.html. (c) Nematic threadlike texture. After these textures the nematic
phase was named, as “nematic” comes from the Greek word for “thread”. Photo courtesy of Ingo
Dierking.
On optical examination of a nematic, one rarely sees the idealized equilibrium conﬁguration. Some
very prominent structural perturbation appear as threads from which nematics take their name (Greek
3
“νηµα” means thread). These threads are analogous to dislocations in solids and have been termed
disclinations by Frank.
Several typical textures of nematics are shown in Fig. (2). The ﬁrst one is a schlieren texture of a
nematic ﬁlm. This picture was taken under a polarization microscope with polarizer and analyzer crossed.
From every point defect emerge four dark brushes. For these directions the director is parallel either to
the polarizer or to the analyzer. The colors are newton colors of thin ﬁlms and depend on the thickness
of the sample. Point defects can only exist in pairs. One can see two types of boojums with “opposite
sign of topological charge”; one type with yellow and red brushes, the other kind not that colorful. The
diﬀerence in appearance is due to diﬀerent core structures for these defects of diﬀerent “charge”.
The second texture is a thin ﬁlm on isotropic surface. Here the periodic stripe structure is a spectacular
consequence of the conﬁned nature of the ﬁlm. It is a result of the competition between elastic inner
forces and surface anchoring forces. The surface anchoring forces want to align the liquid crystals parallel
to the bottom surface and perpendicular to the top surface of the ﬁlm. The elastic forces work against
the resulting “vertical” distortions of the director ﬁeld. When the ﬁlm is suﬃciently thin, the lowest
energy state is surprisingly archived by “horizontal” director deformations in the plane of the ﬁlm. The
current picture shows a 1dimensional periodic pattern.
Many compounds are known to form nematic mesophase. A few typical examples are sketched in
Fig. (3). From a steric point of view, molecules are rigid rods with the breadth to width ratio from 3:1
to 20:1.
Figure 3: Typical compounds forming nematic mesophases: (PAA) pazoxyanisole. From a rough steric
point of view, this is a rigid rod of length ∼ 20
˚
A and width ∼ 5
˚
A. The nematic state is found at high
temperatures (between 116
0
C and 135
0
C at atmospheric pressure). (MMBA) N(pmethoxybenzylidene)
pbutylaniline. The nematic state is found at room temperatures (between 20
0
C to 47
0
C). Lacks chemical
stability. (5CB) 4pentyl4’cyanobiphenyl. The nematic state is found at room temperatures (between
24
0
C and 35
0
C).
1.2 Cholesterics
The cholesteric phase is like the nematic phase in having longrange orientation order and no longrange
order in positions of the centers of mass of molecules. It diﬀers from the nematic phase in that the director
varies in direction throughout the medium in a regular way. The conﬁguration is precisely what one would
obtain by twisting about the x axis a nematic initially aligned along the y axis. In any plane perpendicular
to the twist axis the long axes of the molecules tend to align along a single preferred direction in this
4
plane, but in a series of equidistant parallel planes, the preferred direction rotates through a ﬁxed angle,
as illustrated in Fig. (1b).
The secondary structure of the cholesteric is characterized by the distance measured along the twist
axis over which the director rotates through a full circle. This distance is called the pitch of the cholesteric.
The periodicity length of the cholesteric is actually only half this distance since n and −n are indistin
guishable.
A nematic liquid crystal is just a cholesteric of inﬁnite pitch, and is not really an independent case.
In particular, there is no phase transition between nematic and cholesteric phases in a given material,
and nematic liquid crystals doped with enantiomorphic materials become cholesterics of long (but ﬁnite)
pitch. The molecules forming this phase are always optically active, i. e. they have distinct right and
lefthanded forms.
Figure 4: (a) Cholesteric ﬁngerprint texture. The line pattern is due to the helical structure of the
cholesteric phase, with the helical axis in the plane of the substrate. Photo courtesy of Ingo Dierking. (b)
A shortpitch cholesteric liquid crystal in Grandjean or standing helix texture, viewed between crossed
polarizers. The bright colors are due to the diﬀerence in rotatory power arising from domains with
diﬀerent cholesteric pitch occuring on rapid cooling close to the smectic A* phase where the pitch strongly
diverges with decreasing temperature. Photo courtesy of Per Rudqvist. (c) Longrange orientation of
cholesteric liquid crystalline DNA mesophases occurs at magnetic ﬁeld strengths exceeding 2 Tesla. The
image presented above illustrates this longrange order in DNA solutions approaching 300 milligrams per
milliliter. Parallel lines denoting the periodicity of the cholesteric mesophase appear at approximately
45degrees from the axis of the image boundaries.
The pitch of the common cholesterics is of the order of several hundreds nanometers, and thus com
parable with the wavelength of visible light. The spiral arrangement is responsible for the characteristic
colors of cholesterics in reﬂection (through Bragg reﬂection by the periodic structure) and their very large
rotatory power. The pitch can be quite sensitive to temperature, ﬂow, chemical composition, and applied
magnetic or electric ﬁeld. Typical cholesteric textures are shown in Fig. (4).
1.3 Smectics
The important feature of the smectic phase, which distinguishes it from the nematic, is its stratiﬁcation.
The molecules are arranged in layers and exhibit some correlations in their positions in addition to the
orientational ordering. A number of diﬀerent classes of smectics have been recognized. In smectic A
phase the molecules are aligned perpendicular to the layers, with no longrange crystalline order within
a layer (see Fig. (1c)). The layers can slide freely over one another. In the smectic C phase the preferred
axis is not perpendicular to the layers, so that the phase has biaxial symmetry. In smectic B phase there
is hexagonal crystalline order within the layers.
In general a smectic, when placed between glass slides, does not assume the simple form of Fig. (1c).
The layers, preserving their thickness, become distorted and can slide over one another in order to adjust
to the surface conditions. The optical properties (focal conic texture) of the smectic state arise from
these distortions of the layers. Typical textures formed by smectics are shown in Fig. (5).
5
Figure 5: (a,b) Focalconic fan texture of a chiral smectic A liquid crystal (courtesy of Chandrasekhar
S., Krishna Prasad and Gita Nair) (c) Focalconic fan texture of a chiral smectic C liquid crystal. More
images are available here: http://www.chem.warwick.ac.uk/jpr/lq/liqcry.html
A number of substances exhibit nematic (or cholesteric) and smectic phases. The general rule appears
to be that the lower temperature phases have a greater degree of crystalline order. Examples are: (i) the
nematic phase always occurs at at a higher temperature than the smectic phase; (ii) the smectic phases
occur in the order A → C → B as the temperature decreases.
1.4 Columnar phases
Figure 6: (a) hexagonal columnar phase Col
h
(with typical spherulitic texture); (b) Rectangular phase
of a discotic liquid crystal (c) hexagonal columnar liquidcrystalline phase.
Figure 7: Typical discotics: derivative of a hexabenzocoronene and 2,3,6,7,10,11
hexakishexyloxytriphenylene. K(70K) → Col
h
(100K) → I.
Diskshaped mesogens can orient themselves in a layerlike fashion known as the discotic nematic
phase. If the disks pack into stacks, the phase is called a discotic columnar. The columns themselves
6
Figure 8: (1) Columnar phase formed by the discshaped molecules and the most common arrangements
of columns in twodimensional lattices: (a) hexagonal, (b) rectangular, and (c) herringbone. (2,3) MD
simulation results: snapshot of the hexabenzocoronene system with the C
12
side chains. Aromatic cores
are highlighted. Both top and side views are shown. T = 400 K, P = 0.1 MPa.
may be organized into rectangular or hexagonal arrays, see Fig. (8). Chiral discotic phases, similar to
the chiral nematic phase, are also known.
The columnar phase is a class of liquidcrystalline phases in which molecules assemble into cylindrical
structures to act as mesogens. Originally, these kinds of liquid crystals were called discotic liquid crystals
because the columnar structures are composed of ﬂatshaped discotic molecules stacked onedimensionally.
Since recent ﬁndings provide a number of columnar liquid crystals consisting of nondiscoid mesogens, it
is more common now to classify this state of matter and compounds with these properties as columnar
liquid crystals.
Columnar liquid crystals are grouped by their structural order and the ways of packing of the columns.
Nematic columnar liquid crystals have no longrange order and are less organized than other columnar
liquid crystals. Other columnar phases with longrange order are classiﬁed by their twodimensional
lattices: hexagonal, tetragonal, rectangular, and oblique phases.
The discotic nematic phase includes nematic liquid crystals composed of ﬂatshaped discotic molecules
without longrange order. In this phase, molecules do not form speciﬁc columnar assemblies but only
ﬂoat with their short axes in parallel to the director (a unit vector which deﬁnes the liquidcrystalline
alignment and order).
1.5 Lyotropic liquid crystals
Liquid crystals which are obtained by melting a crystalline solid are called thermotropic. Liquid crys
talline behavior is also found in certain colloidal solutions, such as aqueous solutions of tobacco mosaic
virus and certain polymers. This class of liquid crystals is called lyotropic. For this class concentration
(and secondarily temperature) is the important controllable parameter, rather then temperature (and
secondarily pressure) as in the thermotropic phase. Most of the theories outlined below is equally valid
for either class, although we will generally have a thermotropic liquid crystal in mind.
2 Long and shortrange ordering
2.1 Order tensor
We will ﬁrst try to characterize a nematic mesophase. Suppose that the molecules composing a nematic
are rigid and rodlike in shape. Then we can introduce a unit vector u
(i)
along the axis of ith molecule
which describes its orientation. Since liquid crystals possess a center of symmetry, the average of u
(i)
vanishes. It is thus not possible to introduce a vector order parameter for a liquid crystals analogous to
7
Figure 9: Orientation of mesogens in a nematic phase. A unit vector u
(i)
along the axis of ith molecule
describes its orientation. The director n shows the average alignment.
the magnetization in a ferromagnet, and it is necessary to consider higher harmonics (i. e. tensors). A
natural order parameter to describe the ordering in nematics (or cholesteric) is the second rank tensor
S
αβ
(r) =
1
N
¸
i
u
(i)
α
u
(i)
β
−
1
3
δ
αβ
(1)
when the sum is over all the N molecules in a small but macroscopic volume located at the point r;
indexes α, β = (x, y, z).
Properties of the order parameter tensor
1. S
αβ
is a symmetric tensor
S
αβ
= S
βα
, (2)
since u
(i)
α
u
(i)
β
= u
(i)
β
u
(i)
α
and δ
αβ
= δ
βα
.
2. It is traceless
TrS
αβ
=
¸
α=(x,y,z)
S
αα
=
1
N
¸
i
¸
(u
(i)
x
)
2
+ (u
(i)
y
)
2
+ (u
(i)
z
)
2
−
1
3
3
= 1 −1 = 0, (3)
since u is a unit vector.
3. Two previous properties (symmetries) reduce the number of independent components (3 by 3 ma
trix) from 9 to 5.
4. In the isotropic phase S
iso
αβ
= 0.
To prove this, let us transform everything to the spherical coordinate system (in the isotropic phase
all directions are equivalent  spherical coordinates allow simple formulation of this fact)
u
x
= sin θ cos φ (4)
u
y
= sin θ sin φ
u
z
= cos θ
Then
S
αβ
=
2π
0
dφ
π
0
sin θdθP(θ, φ)
u
α
u
β
−
1
3
δ
αβ
, (5)
where P(θ, φ) is the probability to ﬁnd a molecule with the orientation given by the angles θ, φ.
8
It is clear that in the isotropic phase P
iso
is a constant. Normalization conditions require that
P
iso
(θ, φ) =
1
4π
. Indeed,
2
2π
0
dφ
π/2
0
sin θdθ = 4π. (6)
Note that the integration over θ is from 0 to π/2, but we double the value of the integral to
compensate for the conventional integration from 0 to π in spherical coordinates. This is due the
fact the u and −u are indistinguishable (for unpolar molecules), but we nevertheless describe their
orientations using vectors, for which the opposite directions are of course distinguishable.
It is easy to see that in the isotropic phase the cross terms S
xy
= S
yz
= S
xz
= 0 because of the
integration over φ (periodic function integrated over its full period). Let us consider one of the
diagonal components, for example S
zz
S
zz
= 2
2π
0
dφ
π/2
0
sin θdθP(θ, φ)
cos
2
θ −
1
3
= (7)
4πP
iso
1
0
cos
2
θ −
1
3
d(cos θ) =
2
3
π (x
3
−x)
1
0
= 0.
In a similar fashion one can show that the other two diagonal components are also equal to zero.
5. In a perfectly aligned nematic (with the molecules along the z axis), prolate geometry
S
prolate
=
¸
−1/3 0 0
0 −1/3 0
0 0 2/3
¸
. (8)
To prove this it is suﬃcient to calculate only the S
zz
component:
S
zz
= u
z
u
z
−1/3 = 1 −1/3 = 2/3. (9)
Keeping in mind that S is symmetric and traceless we obtain (8).
6. In a perfectly aligned oblate geometry (u
z
= 0)
S
oblate
=
¸
1/6 0 0
0 1/6 0
0 0 −1/3
¸
. (10)
These properties tell us that S
αβ
is a very good candidate for the order parameter of our system.
It equals to zero in the isotropic phase, it is sensitive to the direction of the average orientation of the
molecules as well as to the molecular distribution of the molecules around the their average orientation.
It is indeed often used to describe “diﬃcult” situations, which include presence of defects, melting of
parts of the system, i. e. where the order parameter is a function of spatial coordinates (in the defect
core region, at the nematicisotropic interface, etc.).
2.2 Director
In the previous section we showed that the order tensor is a suitable candidate for an order parameter of a
nematic mesophase. It is, however, rather inconvenient to use since it lacks clear physical interpretation.
Indeed, in some special cases we can ﬁnd a more convenient representation, especially in those systems
where the degree of ordering is not changing and therefore only the average orientation of the molecules
is of interest.
In general, any symmetric secondorder tensor has 3 real eigenvalues and three corresponding orthog
onal eigenvectors. (Recall gyration tensor or mass and inertia tensor). Since this tensor is a symmetric
9
3 × 3 matrix, a Cartesian coordinate system can be found in which it is diagonal with the diagonal
elements
2
3
S, −
1
3
S +B, −
1
3
S −B (principal moments in case of a gyration tensor). Here the eigenvalues
are ordered such as S has the biggest aboslute value. The corresponding eigenvector is called a director,
n(r). B is a biaxiality of the molecular distribution.
For a uniaxial nematic phase (molecular distribution function has an axial symmetry) two smaller
eigenvalues are equal (B = 0) and the order tensor reads
S
αβ
= S
n
α
n
β
−
1
3
δ
αβ
(11)
where n
α
are the components of n in a laboratory (ﬁxed) coordinate system.
If we choose n along the z axis of the coordinate system, the three nonzero components of S are
S
zz
=
2
3
S, S
xx
= S
yy
= −
1
2
S. (12)
The scalar quantity S is a measure of the degree of alignment of molecules. Quantitatively, if P(θ) sin θdθ
is the fraction of molecules whose axes make angles between θ and θ +dθ with the preferred direction
S =
π
0
1 −
3
2
sin
2
θ
P(θ)dθ. (13)
In the isotropic phase S = 0, and in the nematic (cholesteric) phase 0 < S < 1. The limit S = 1
corresponds to perfect alignment of all the molecules and, of course, can never be realized in practice. If
we compare Eq. (11) to two previous cases of ideal prolate and oblate molecular distributions, we will
see that negative values of S correspond to a pancakelike (oblate) molecular distribution, positive values
describe prolatelike distributions, and isotropic liquid has S = 0. In general, it can be shown that the
scalar order parameter S changes in the range from −1/2 to 1 (from perfect oblate to perfect prolate
geometry via isotropic phase).
The most important classes of liquid crystals belong to the uniaxial case (the smectic C is a typical
counter example). The order parameter for all such systems can be characterized by a magnitude S and
a direction n, where the latter is the principal axis of the order parameter tensor.
The theoretical development depends merely upon the existence of n and is by no means restricted
to the case of rigid symmetric molecules.
3 Phenomenological descriptions
3.1 Landaude Gennes free energy
Once the appropriate order parameter of the system is identiﬁed (here the order tensor S
αβ
) we can
assume, in a spirit of Landau theories, that the free energy density g(P, T, S
αβ
) is an analytic function of
the order parameter tensor S
αβ
. To the extent that S
αβ
is a small parameter, we may expand g in power
series. In particular this expansion is supposed to work well near the transition temperature. Since the
free energy must be invariant under rigid rotations, all terms of the expansion must be scalar functions
of the tensor S
αβ
. The most general such expansion has the form
g = g
i
+
1
2
AS
αβ
S
αβ
−
1
3
BS
αβ
S
βγ
S
γα
+
1
4
CS
αβ
S
αβ
S
γδ
S
γδ
(14)
correct to fourth order in S
αβ
. Here g
i
is the free energy density of the isotropic phase. There is just one
distinct invariant of the order 2,3, and 4, as shown: other forms (such as S
αβ
S
βγ
S
γδ
S
δα
) can be reduced
for uniaxial crystals to one of the forms given when consideration is taken of the fact that the trace S
αα
vanishes.
10
The coeﬃcients A, B, and C are in general functions of P and T. Typical to Landautype theories,
this model equation of state predicts a phase transition near the temperature where A vanishes. It is
normally assumed that A has the form
A = A
(T −T
∗
) . (15)
The transition temperature itself will prove to be somewhat above T
∗
(see Sec. 4.1). The coeﬃcients B
and C need have no particular properties near T
∗
; we will regard them as constants.
If we consider a nematic liquid crystal in which the order parameter is slowly varying in space, the
free energy will also contain terms which depend on the gradient of the order parameter. These terms
must be scalars and consistent with the symmetry of a nematic. If we conﬁne ourselves to terms O(S
2
),
the most general form for the inhomogeneous part of the free energy density is
g
e
=
1
2
L
1
∂S
ij
∂x
k
∂S
ij
∂x
k
+
1
2
L
2
∂S
ij
∂x
j
∂S
ik
∂x
k
(16)
We will refer to the constants L
1
and L
2
as elastic constants. In the OseenFrank curvature elasticity
theory (see Sec. 3.2) it will be shown that there are three independent constants for nematics in contrast
to just two here. Evidently it is necessary to retain higher terms in the expansion in S.
The constants L
1
and L
2
are related to FrankOseen elastic constants by K
11
= K
33
= 9Q
2
b
(L
1
+
L
2
/2)/2 and K
22
= 9Q
2
b
L
1
/2 and S
b
is the bulk nematic order parameter.
Typical values for a nematic compound 5CB [10]: A
= 0.044 × 10
6
J/m
3
K, B = 0.816 × 10
6
J/m
3
,
C = 0.45 × 10
6
J/m
3
, L
1
= 6 × 10
−12
J/m, L
2
= 12 × 10
−12
J/m T
∗
= 307 K. The nematicisotropic
transition temperature for 5CB is T
NI
= 308.5 K.
3.2 FrankOseen free energy
We have learned that in a given microscopic region of a liquid crystal there is deﬁnitive preferred axis
along which the molecules orient themselves (the director). Globally, the orientation of the liquid crystal
is then characterized by a vector ﬁeld, which we denote as a “director ﬁled”. The question we would like
to address here is: how much energy will it take to deform the director ﬁled?
We will refer to the deformation of relative orientations away from equilibrium position as curvature
strains. The restoring forces which arise to oppose these deformations we will call curvature stresses or
torques. If these changes in molecular orientation vary slowly in space relative to the molecular distance
scale, we will be able to describe the response of the liquid crystal with a version of a continuum elastic
theory.
We will assume that the curvature stresses are proportional to the curvature strains when these are
suﬃciently small; or, equivalently, that the free energy density is a quadratic function of the curvature
strains in which the analog of elastic moduli appear as coeﬃcients.
We consider a uniaxial liquid crystal and let n(r) be a unit vector giving the direction of the preferred
orientation at the point r. As we discussed before, the sign of this vector has no physical signiﬁcance.
Once n is deﬁned at some point we assume that it varies slowly from point to point. At r we introduce
a local righthanded Cartesian coordinate system x, y, z with z parallel to n. The x and y axis can
be chosen arbitrarily because the liquid crystal is uniaxial. Referred to this coordinate system, the six
components of curvature at this point are deﬁned as
splay s
1
=
∂n
x
∂x
, s
2
=
∂n
y
∂y
(17)
twist t
1
= −
∂n
y
∂x
, t
2
=
∂n
x
∂y
(18)
bend b
1
=
∂n
x
∂z
, b
2
=
∂n
y
∂z
(19)
11
Figure 10: The three distinct curvature strains of a liquid crystal: (a) splay, (b) twist, and (c) bend.
These three curvature strains can also be deﬁned by expanding n(r) in a Taylor series in powers of
x, y, z measured from the origin
n
x
(r) = s
1
x +t
2
y +b
1
z +O(r
2
), (20)
n
y
(r) = −t
1
x +s
2
y +b
2
z +O(r
2
), (21)
n
z
(r) = 1 +O(r
2
). (22)
We now postulate that the Gibbs free energy density g of a liquid crystal, relative to its free energy
density in the state of uniform orientation can be expanded in terms of six curvature strains
g =
6
¸
i=1
k
i
a
i
+
1
2
6
¸
i,j=1
k
ij
a
i
a
j
(23)
where the k
i
and k
ij
= k
ji
are the curvature elastic constants and for convenience in notation we have
put a
1
= s
1
, a
2
= t
2
, a
3
= b
1
, a
4
= −t
1
, a
5
= s
2
, a
6
= b
2
.
Because the crystal is uniaxial, a rotation about z will make no change in the physical description
of the substance, and consequently the free energy density g should be invariant under such rotations.
By consideration of a few special cases (such as rotations of
1
2
π and
1
4
π about z), it is readily shown
that there are only two independent moduli k
i
, and that of the thirtysix k
ij
, only ﬁve are independent.
The general expression for the free energy density, written in terms of a set of eight independent moduli,
becomes
g = k
1
(s
1
+s
2
) +k
2
(t
1
+t
2
) +
1
2
k
11
(s
1
+s
2
)
2
1
2
+k
22
(t
1
+t
2
)
2
(24)
+
1
2
k
33
(b
2
1
+b
2
2
) +k
12
(s
1
+s
2
)(t
1
+t
2
) −(k
22
+k
24
)(s
1
s
2
+t
1
t
2
).
The last term can be written
s
1
s
2
+t
1
t
2
=
∂n
x
∂x
∂n
y
∂y
−
∂n
y
∂x
∂n
x
∂y
=
∂
∂x
n
x
∂n
y
∂y
−
∂
∂y
n
x
∂n
y
∂x
(25)
and consequently it will contribute only to to surface energies. Thus we can omit the last term in
considerations involving the properties of the bulk liquid crystal.
In the presence of further symmetries g can have still simpler forms
1. If the molecules are nonpolar or, if polar, are distributed with equal probability in the two directions,
then the choice of the sign of n is arbitrary. We have chosen a righthanded coordinate system in
which z is positive in the direction of n. A reversal of n which retains the chirality of the coordinate
system generates the transformation
n → −n, x → x, y → −y, z → −z. (26)
Invariance of the free energy under this transformation requires
k
1
= k
12
= 0 (nonpolar). (27)
If k
1
= 0, the equilibrium state has ﬁnite splay.
12
2. In the absence of enantiomorphism (chiral molecules which have diﬀerent mirror images) g should
be invariant under reﬂections under reﬂections in plane containing the z axis, such as the transfor
mation
x → x, y → −y, z → z. (28)
This introduces the constraints
k
2
= k
12
= 0 (mirror symmetry). (29)
If k
2
= 0 then the equilibrium state has ﬁnite twist.
In summary, k
1
vanishes in the absence of polarity, k
2
in the absence of enantiomorphy, and k
12
vanishes unless both polarity and enantiomorphy occur together.
It is convenient to deﬁne
s
0
= −
k
1
k
11
t
0
= −
k
2
k
22
(30)
and to add constants to g
g = g +
1
2
k
11
s
2
0
+
1
2
k
22
t
2
0
(31)
=
1
2
k
11
(s
1
+s
2
−s
0
)
2
1
2
+k
22
(t
1
+t
2
−t
0
)
2
+
1
2
k
33
(b
2
1
+b
2
2
) +k
12
(s
1
+s
2
)(t
1
+t
2
) −(k
22
+k
24
)(s
1
+s
2
)(t
1
+t
2
).
so that now evident that s
0
and t
0
are the splay and twist of the state which minimizes the free energy 
the equilibrium state. Thus the cholesteric phase is characterized by t
0
= 0.
The free energy density can be written in a vector notation. We note that
s
1
+s
2
=
∂n
x
∂x
+
∂n
y
∂y
= ∇· n, (32)
−(t
1
+t
2
) =
∂n
y
∂x
−
∂n
x
∂y
= n · (∇×n), (33)
b
2
1
+b
2
2
=
∂n
x
∂z
2
+
∂n
y
∂z
2
= (n · ∇n)
2
(34)
which may be substituted back to the expression for the free energy to give
g =
1
2
k
11
(∇· n −s
0
)
2
+
1
2
k
22
(n · curl n +t
0
)
2
+
1
2
k
33
(n ×curl n)
2
−k
12
(∇· n)(∇· curl n) (35)
This is the famous FrankOseen elastic free energy density for nematics and cholesterics.
Brieﬂy about the meaning of diﬀerent symbols:
div n = ∇· n =
∂
∂x
n
x
+
∂
∂y
n
y
+
∂
∂z
n
z
curl n = ∇×n =
i j k
∂
∂x
∂
∂y
∂
∂z
n
x
n
y
n
z
= i
∂
∂y
n
z
−
∂
∂z
n
y
+j
∂
∂z
n
x
−
∂
∂x
n
z
+k
∂
∂x
n
y
−
∂
∂y
n
x
For the purpose of qualitative calculations it is sometimes useful to consider a nonpolar, nonena
tiomorphic liquid crystal whose bend, splay, and twist constants are equal (oneconstant approximation).
The free energy density for this theoretician’s substance is
g =
1
2
k
(∇· n)
2
+ (∇×n)
2
. (36)
13
Equations for the director can be obtained by minimization of the free energy
V
gdr with an additional
constraint n
2
= 1 and have the following form
−k
11
∇(∇· n) +k
22
{A[∇×n] + [∇×(An)]} +k
33
{[[∇×n] ×B] + [∇×[B ×n]]} +µn = 0,
where A = n · [∇× n], B = [n ×[∇×n]], µ is an unknown Lagrange multiplier which must be found
from the condition n
2
= 1.
4 Nematicisotropic phase transition
In this section we will apply existing theories to describe the isotropic to nematic phase transition. We
consider thermotropic liquid crystals, where temperature is the parameter driving the transition.
4.1 Landau theory
In Sec. 2.2 we derived that in a uniaxial liquid crystal the order parameter S
αβ
takes the form
S
αβ
= S
n
α
n
β
−
1
3
δ
αβ
(37)
Substituting this into Eq. (14) we obtain
g = g
i
+
1
3
AS
2
−
2
27
BS
3
+
1
9
CS
4
. (38)
The equilibrium value of S is that which gives the minimum value for the free energy. The dependence
of g
i
on S for several choices of T is shown in Fig. (11). There is a discontinuous phase transition at a
temperature T
c
slightly above T
∗
. The source of this ﬁrstorder phase transition lies in the presence of
the oddorder powers of S in the expansion; the existence of these terms is in turn due to the fact that
the sign of S has physical meaning.
Figure 11: Landau theory: dependence of the Gibbs free energy density on the order parameter. The case
of the three special temperatures, T
∗∗
, T
c
, and T
∗
are shown. For illustration we use A = B = C = 1.
The value of S which minimizes Eq. (38) can be found algebraically. It will be a root of the derivative
which is
AS −
1
3
BS
2
+
2
3
CS
3
= 0. (39)
14
The solutions of this equations are
S = 0 isotropic phase (40)
S = (B/4C)[1 + (1 −24β)
1/2
] nematic phase, (41)
where β = AC/B
2
. A third solution, corresponding to a maximum of the free energy, has been suppressed.
The transition temperature T
c
will be such that the free energies of isotropic and nematic phases are equal.
From Eqs. (38) and (41) this point can be determined to be
β =
1
27
; T
c
= T
∗
+
1
27
B
2
A
C
. (42)
Above T
c
the isotropic phase is stable; below T
c
the nematic is stable.
The value of the order parameter at the phase transition is
S
c
= B/3C. (43)
The temperature T
∗
corresponds to the limit of metastability of the isotropic phase. It should be
possible, in principle, to supercool the isotropic liquid to this temperature. At T
∗
, where the coeﬃcient
A in the free energy changes sign, the isotropic phase becomes unstable (because S = 0 is not a local
minimum of the free energy).
Likewise, the nematic phase becomes unstable when β > 1/24. This determines a temperature
T
∗∗
= T
∗
+ B
2
/(24A
C) which is the limit of the nematic phase on heating. The temperatures T
∗
and T
∗∗
also have the signiﬁcance that they are apparent “critical points” for the isotropic and ordered
phases, respectively. Thus susceptibilities and correlation lengths, which increase as the transition point
is approached, will appear to headed for a divergence at a temperature slightly beyond the transition
temperature T
c
.
4.2 MaierSaupe theory
Maier and Saupe in a series of paper (19581960) have given a microscopic model for the phase transition
in a nematic liquid crystal.
The MaierSaupe theory is based on three assumptions:
1. An attractive, orientationdependent van der Waals interaction between the molecules.
2. The conﬁguration of the centers of mass is not aﬀected by the orientationdependent interaction.
3. The mean ﬁeld approximation.
We consider rodlike, nonpolar molecules interacting via van der Waals interactions. We restrict ourselves
to the orientationdependent part and assume that a particular molecule feels the averaged interaction
of the surrounding molecules. We also assume that molecules are arranged in a spherically symmetric
way (positional correlations are isotropic) and that the distribution of orientations of each molecule is
described by the average order parameter S
αβ
.
This assumptions allow to derive the eﬀective potential for each molecule with orientation u
V (u, S) = −
3
2
AS
αβ
(u
α
u
β
−
1
3
δ
αβ
) (44)
The probability distribution for the orientation of a molecule in the presence of this external ﬁeld is
f(u) =
1
Z
exp
¸
−
V (u, S)
kT
(45)
where Z =
duexp(−V (u, S)/kT) is the normalization factor, du indicates an integration over all
orientations of u.
15
The theory is made selfconsistent by requiring that the average value of u
α
u
β
−
1
3
δ
αβ
be equal to
S
αβ
.
S
αβ
=
du
u
α
u
β
−
1
3
δ
αβ
f(u). (46)
In the case of a uniaxial liquid crystal this equation can be simpliﬁed. Taking the preferred direction
(director) to be the z axis. and deﬁning θ to be the angle between u and z, the zz component of Eq. (46)
can be written
S =
2π
Z
π
0
3
2
cos
2
θ −
1
2
exp
¸
−
V (θ, S)
kT
sin θdθ, (47)
where, according to Eq. (44)
V (θ, S) = −AS
3
2
cos
2
θ −
1
2
(48)
and Z can now be written
Z = 2π
π
0
exp
¸
−
V (θ, S)
kT
sin θdθ. (49)
It is readily seen that one solution of Eqs. (47) and (49) is S = 0, which corresponds to the isotropic
phase. Nontrivial solutions also exist. After integration by parts Eq. (47) can be written in a parametric
form
S =
3
4
¸
exp(x
2
)
xD(x)
−
1
x
2
−
1
2
(50)
kT
A
=
3
2
S
x
2
, (51)
where D(x) =
x
0
exp(y
2
)dy is Dawson’s integral.
For each value of x Eq. (51) determines a corresponding value of S and T. The resulting relationship
between S and T is shown in Fig. (12).
Figure 12: MaierSaupe theory: dependence of free energy F and order parameter S on temperature.
The stable mesophase is given by the solution which minimizes the free energy per particle, which
may be calculated as
F(T, S) = −
1
2
A
0
S
2
+kT ln C/4π (52)
The MaierSaupe theory predicts a ﬁrstorder phase transition at a temperature T
c
deﬁned by
k
B
T
c
= 0.22A
0
, (53)
and the value of the order parameter at the transition is
S
c
= 0.43. (54)
16
4.3 Onsager theory
Onsager theory [11] is a form of molecular ﬁeld theory, with the diﬀerence that the conﬁgurational average
energy is replaced by the orientationdependent conﬁgurational entropy. Onsager theory is a forerunner
of modern densityfunctional theory [12].
Consider an ensemble of elongated particles interacting pairwise through some potential V(1, 2) which
depends on both positions and orientations of the molecules: 1 = (r
1
, Ω
1
). Onsager has shown how the
Mayer cluster theory may be used to give an expansion for the equation of state of this system [11].
Onsager’s expression for the Helmholtz free energy per particle is expressed in terms of the singleparticle
density, ρ(1), which gives the number of molecules per unit solid angle and per unit volume
βF[ρ] =
ρ(1)
¸
ln ρ(1)Λ
3
−1 −βµ +βU(1)
¸
d(1) −
1
2
f(1, 2)ρ(1)ρ(2)d(1)d(2). (55)
Here β = 1/k
B
T, Λ is the de Broglie wavelength, µ is the chemical potential, U(1) is the external potential
energy,
f(1, 2) = exp [−V(1, 2)/k
B
T] −1 (56)
is the Mayer ffunction.
The equilibrium singleparticle density that minimizes the free energy (55) is a solution of the following
Euler–Lagrange equation
ln ρ(1)Λ
3
−βµ +βU(1) −
f(1, 2)ρ(2)d(2) = 0, (57)
which can be obtained from the variation of the functional (55).
In principle, the equation (57) can be solved numerically for any form of the second virial coeﬃcient
which can be expanded in Legendre polynomials. However, sometimes it is more convenient to minimize
the functional (55) instead of solving the integral equation (57).
The solutions are qualitatively the same as the solutions of the MaierSaupe equation. The diﬀerence
is that the MaierSaupe theory is commonly applied to liquids, which are only slightly compressible,
whereas the Onsager expansion is applied to dilute suspensions of particles for which the change in free
energy with density is relatively small. The Onsager theory predicts large changes in density at the
transition, as is observed for such systems.
Onsager theory can be explained using simple arguments of a volume taken by a molecule (excluded
volume). In the nematic state, the excluded volume decreases, and this gives rise to the translational
entropy of the system [13]
∆S
tr
= −k
B
ln (1 −V
excl
/V ) ∼ k
B
ρL
2
D, (58)
where ρ = N/V is the density of rods with length L and diameter D. However, there is also a decrease
in orientational entropy in the nematic state, S
N
= k
B
ln Ω
N
, in comparison to the isotropic state,
S
I
= k
B
ln Ω
I
,
∆S
or
= k
B
ln Ω
N
/Ω
I
∼ k
B
, (59)
where Ω
I,N
gives the number of orientational states in the isotropic or nematic mesophase.
At the nematicisotropic transition, these two contributions compensate each other, ∆S
or
+∆S
tr
= 0
and the critical density is ρ
c
∼ 1/(L
2
D), or a critical volume fraction is given by φ
c
= V
rods
/V ∼
(NLD
2
)/(NL
2
D) = D/L. Therefore, increasing lengthtobreadth ratio we favor nematic formation.
In conclusion, we point out that the Onsager theory does not describe the bulk equation of state
perfectly. The reason for this is truncation of the virial expansion of the free energy at the leading,
pairwise term. However, systematic improvements are possible which improve the agreement with the
bulk equation of state [14, 15, 16, 17].
17
5 Response to external ﬁelds
The director ﬁeld is easily distorted and can be aligned by magnetic and electric ﬁelds, and by surfaces
which have been properly prepared.
The magnetic susceptibility of a liquid crystal, owing to the anisotropic form of the molecules com
posing it, is also anisotropic. In the uniaxial case it is a secondrank tensor with two components χ
and
χ
⊥
, which are the susceptibilities per unit volume along and perpendicular to the axis. The susceptibility
tensor thus takes the form
χ
ij
= χ
⊥
δ
ij
+χ
a
n
i
n
j
, (60)
where χ
a
= χ
− χ
⊥
is the anisotropy and is generally positive. It is thus possible to exert torques on
the liquid crystal by applying a ﬁeld. The presence of a magnetic ﬁeld H leads to an extra term in the
free energy of
g
m
= −
1
2
χ
⊥
H
2
−
1
2
χ
a
(n · H)
2
. (61)
The ﬁrst term usually will be omitted as it is independent of the orientation of the director. The last
term gives rise to a torque on the liquid crystal  if χ
a
is positive the molecules will align parallel to the
ﬁeld.
The dielectric susceptibility of a liquid crystal is also anisotropic and has the same form as the magnetic
susceptibility. Thus, in principle, we can achieve the same eﬀect with an electric ﬁeld as with a magnetic
ﬁeld. In an electric ﬁeld E there will be an additional free energy
g
e
= −
1
8π
⊥
E
2
−
1
8π
a
(n · E)
2
. (62)
in practice the alignment of a liquid crystal by an electric ﬁeld is complicated by the presence of conducting
impurities which make it necessary to use alternating electric ﬁelds.
5.1 Frederiks transition in nematics
Consider a nematic liquid crystal between two glass slides. The interaction between the nematic and
the glass is such that the director is constrained to lie perpendicular to the glass at the boundaries.
When a magnetic ﬁeld, applied perpendicular to the director, exceeds a certain critical value, the optical
properties of the system change abruptly. The reason is that both the magnetic ﬁeld and the boundaries
exert torques on the molecules and when the ﬁeld exceeds H
c
it becomes energetically favorable for the
molecules in the bulk of the sample to turn in the direction of the ﬁeld. This eﬀect ﬁrst observed by
Frederiks and Zolina and can be used to measure some of the elastic constants.
Figure 13: Frederiks transition. The liquid crystal is constrained to be perpendicular to the boundary
surfaces and a magnetic ﬁeld is applied in the direction shown. (a) Below a certain critical ﬁeld H
c
, the
alignment is not aﬀected. (b) slightly above H
c
, deviation of the alignment sets in. (c) ﬁeld is increased
further, the deviation increases.
18
Let the z axis be perpendicular to the glass surfaces and the ﬁeld H lie along the x direction (see
Fig. (13)). The director will have the form
n
x
= sin θ(z), n
y
= 0, n
z
= cos θ(z) (63)
so that θ is the angle between the director and the z axis.
First we need to calculate the divergence and curl of our vector
∇· n = −sin θ
∂θ
∂z
,
∇×n = j cos θ
∂θ
∂z
,
n · (∇×n) = 0,
n ×curl n = (kn
x
−in
z
) cos θ
∂θ
∂z
.
The elastic energy per unit area now takes the form
g =
1
2
d/2
−d/2
dz
¸
k
11
sin
2
θ +k
33
cos
2
θ
∂θ
∂z
2
−χ
a
H
2
sin
2
θ
¸
, (64)
where d is the thickness of the sample.
In the undistorted structure (θ = 0) the ﬁeld does not exert a torque on the molecules  they are in
metastable equilibrium. We will suppose one constant approximation, k
11
= k
33
= k.
We deﬁne the length ξ =
k/χ
a
H
2
and Eq. (64) becomes
g =
1
2
k
ξ
2
d/2
−d/2
dz
¸
ξ
2
∂θ
∂z
2
−sin
2
θ
¸
. (65)
Now we have a variational problem  we have to minimize the free energy satisfying the boundary
conditions
θ
z=−d/2,d/2
= 0. (66)
Variation of the free energy leads to the diﬀerential (EulerLagrange) equation
ξ
2
∂
2
θ
∂
2
z
+ sin θ cos θ = 0. (67)
There is a trivial solution θ = 0 which satisﬁes the boundary conditions. If the maximum distortion θ
m
is small
θ = θ
m
cos
z
ξ
(68)
is a good approximate solution. The boundary conditions require that d = ξπ, or, equivalently,
H
c
=
k
33
χ
a
π
d
(69)
which holds even if k
11
= k
33
. Thus a measurement of H
c
is a measurement of k
33
, provided that χ
a
is known. For ﬁelds weaker than H
c
only the trivial solution exists, and there is no distortion on the
nematic structure.
The general solution to Eq. (67) is readily found. The ﬁrst integral is
ξ
2
∂θ
∂z
2
+ sin
2
θ = sin
2
θ
m
. (70)
19
where the constant of integration has been identiﬁed by observing that dθdz = 0, where θ takes on its
maximum value. This maximum presumably lies halfway between the glass surfaces at z = 0. The
equation can be further integrated to give
1
2
d −z = ξ
θ
0
dθ
sin
2
θ
m
−sin
2
θ
1/2
= ξ csc θ
m
F(csc θ
m
, θ), (71)
where F is the incomplete elliptic integral of the ﬁrst kind, csc θ = 1/ sin θ, and we have used the boundary
condition θ = 0 at z =
1
2
d. The maximum distortion is found by putting z = 0, θ = θ
m
,
1
2
d = ξ csc θ
m
F(csc θ
m
, θ
m
) = ξK(sin θ
m
), (72)
where K is the complete elliptic integral of the ﬁrst kind.
For ﬁelds just above H
c
θ
m
∼ 2
¸
H
H
c
−1
1/2
. (73)
The dependence of θ
m
on H is shown in in Fig. (14). In fact, ξ can be directly interpreted as the distance
which a disturbance can propagate into the liquid crystal in the presence of an ordering ﬁeld. The length
ξ is called the magnetic coherence length and arises in many problems involving the distortion produced
by a magnetic ﬁeld.
Figure 14: Dependence of θ
m
on H, as given by Eq. (72).
6 Optical properties
6.1 Nematics
It has already been mentioned in Section 5 that the dielectric susceptibility of a nematic is anisotropic and
in a uniaxial state is a secondrank tensor with two components
and
⊥
, which are the susceptibilities
per unit volume along and perpendicular to the axis.
ij
=
⊥
δ
ij
+
a
n
i
n
j
. (74)
Correspondingly, we can introduce ordinary and extraordinary refractive indexes
n
e
=
√
, n
o
=
√
⊥
, ∆n = n
e
−n
o
. (75)
For typical nematic liquid crystals, n
o
is approximately 1.5 and the maximum diﬀerence, ∆n, may range
between 0.05 and 0.5.
20
Thus, when light enters a birefringent material, such as a nematic liquid crystal sample, the process
is modelled in terms of the light being broken up into the fast (called the ordinary ray) and slow (called
the extraordinary ray) components. Because the two components travel at diﬀerent velocities, the waves
get out of phase. When the rays are recombined as they exit the birefringent material, the polarization
state has changed because of this phase diﬀerence.
Figure 15: Light traveling through a birefringent medium will take one of two paths depending on its
polarization.
The length of the sample is another important parameter because the phase shift accumulates as long
as the light propagates in the birefringent material. Any polarization state can be produced with the
right combination of the birefringence and length parameters.
Consider the case where a liquid crystal sample is placed between crossed polarizers whose transmission
axes are aligned at some angle α between the fast and slow direction of the material.
Because of the birefringent nature of the sample, the incoming linearly polarized light
E
incident
=
E
x
E
y
=
E
0
cos α
E
0
sin α
(76)
becomes elliptically polarized
E
sample
(z) =
E
x
exp(ik
e
z)
E
y
exp(ik
o
z)
(77)
Using Jones calculus for optical polarizer
ˆ
A =
sin
2
α −cos αsin α
−cos αsin α cos
2
α
(78)
We obtain the light behind the second polarizer (analyzer)
E
out
=
ˆ
AE
sample
(z = L) = E
0
sin(2α) sin(∆kL/2) exp[i(k
o
+k
e
)L/2]
sin α
cos α
(79)
and the output intensity becomes
I
out
= E
out

2
= E
2
0
sin
2
(2α) sin
2
∆kL
2
= I
0
sin
2
(2α) sin
2
π∆nL
λ
. (80)
Therefore, when this ray reaches the second polarizer, there is now a component that can pass through,
and the region appears bright. For monochromatic light (single frequency), the magnitude of the phase
diﬀerence is determined by the length and the birefringence of the material. If the sample is very thin,
the ordinary and extraordinary components do not get very far out of phase. Likewise, if the sample
is thick, the phase diﬀerence can be large. If the phase diﬀerence equals 2π, the wave returns to its
original polarization state and is blocked by the second polarizer. The size of the phase shift determines
the intensity of the transmitted light.
21
If the transmission axis of the ﬁrst polarizer is parallel to either the ordinary or extraordinary direc
tions, the light is not broken up into components, and no change in the polarization state occurs. In this
case, there is not a transmitted component and the region appears dark.
In a typical liquid crystal, the birefringence and length are not constant over the entire sample.
This means that some areas appear light and others appear dark, as shown in the microscope picture
of a nematic liquid crystal, Fig. (2a), taken between crossed polarizers. The light and dark areas that
denote regions of diﬀering director orientation, birefringence, and length. The dark regions that represent
alignment parallel or perpendicular to the director are called brushes.
Colors arising from polarized light studies
Birefringence can lead to multicolored images in the examination of liquid crystals under polarized white
light.
Up to this point, we have dealt only with monochromatic light is considering the optical properties of
materials. In understanding the origin of the colors which are observed in the studies of liquid crystals
placed between crossed linear polarizers, it will be helpful to return to the examples of retarding plates.
They are designed for a speciﬁc wavelength and thus will produce the desired results for a relatively
narrow band of wavelengths around that particular value. If, for example, a fullwave plate designed for
wavelength is λ is placed between crossed polarizers at some arbitrary orientation and the combination
illuminated by white light, the wavelength λ will not be aﬀected by the retarder and so will be extinguished
(absorbed) by the analyzer. However, all other wavelengths will experience some retardation and emerge
from the fullwave plate in a variety of polarization states. The components of this light passed by the
analyzer will then form the complementary color to λ.
Color patterns observed in the polarizing microscope are very useful in the study of liquid crystals in
many situations, including the identiﬁcation of textures, of liquid crystal phases and the observations of
phase changes.
Frederiks transition
The distortion of the director by the ﬁled when Frederiks transition (see Section 5.1) occur can be detected
optically because there is a change in the refractive index of the material. The refractive index locally is
(the light is polarized along z axis
n =
n
e
n
o
n
2
e
sin
2
θ +n
o
cos
2
θ
1/2
(81)
The average change in the refractive inde is
δ =
1
d
d/2
−d/2
dz(n
e
−n
o
). (82)
Using Eq. (70), this can be put in the form
δ
n
e
= 1 −
2ξ
d
θm
0
dθ
(1 +ν sin
2
θ)
1/2
(sin
2
θ
m
−sin
2
θ)
1/2
= 1 −
2ξ
d
1
(1 +ν sin
2
θ
m
)
1/2
K
1 +ν
csc
2
θ
m
+ν
.
(83)
where ν = (n
2
e
−n
2
o
)/n
2
o
. For small deformations the change in the refractive index is
δ = n
e
ν
H −H
c
H
c
(84)
and for large ﬁelds approaches n
e
−n
o
.
6.2 Cholesterics
This is your homework.
22
Figure 16: Examples of axial disclinations in a nematic: (a) m = +1, (b) the parabolic disclination,
m = +1/2, (c) the hyperbolic disclination (topologically equivalent to the parabolic one), m = −1/2.
7 Defects
Topological defects appear in physics as a consequence of broken continuous symmetry [3]. They exist
almost in every branch of physics: biological systems [18], superﬂuid helium [19], ferromagnets [20],
crystalline solids [21, 22], liquid crystals [23, 24, 25, 26, 27], quantum Hall ﬂuids [28], and even optical
ﬁelds [29] playing an important role in such phenomena as response to external stresses, the nature and
type of phase transitions. They even arise in certain cosmological models [30].
Liquid crystals are ideal materials for studying topological defects. Distortions yielding defects are
easily produced through control of boundary conditions, surface geometries, and external ﬁelds. The
resulting defects are easily imaged optically. The simplest, nematic liquid crystalline phase owes its name
to the typical threadlike defect which can be seen under a microscope in a nematic or cholesteric phase
[31].
First explanations were given by Friedel [32] who suggested that these threads are lines on which the
director changes its direction discontinuously. In analogy with dislocations in crystals, Frank proposed to
call them disclinations [33]. To classify topological defects the homotopy theory can be employed to study
the order parameter space [34]. For the case of nematics, there are two kinds of stable topological defects
in three dimensions: point defects, called hedgehogs and line defects, called disclinations. Hedgehogs are
characterized by an integer topological charge q specifying the number of times the unit sphere is wrapped
by the director on any surface enclosing the defect core. An analytical expression for q is
q =
1
8π
dS
i
ijk
n · (∂
j
n ×∂
k
n) , (85)
where ∂
α
denotes diﬀerentiation with respect to x
α
,
ijk
is the LeviCivita symbol, and the integral is
over any surface enclosing the defect core. For an order parameter with O
3
, or vector symmetry, the
orderparameter space is S
2
, and hedgehogs can have positive or negative charges. Nematic inversion
symmetry makes positive and negative charges equivalent, and we may, as a result, take all charges to
be positive.
The axial solutions of the EulerLagrange equations representing disclination lines are
φ = mψ +φ
0
, (86)
where n
x
= cos φ, ψ is the azimuthal angle, x = r cos ψ, m is a positive or negative integer or halfinteger
[2]. Examples of disclinations for several m are given in Fig. (16). The elastic energy per unit length
associated with a disclination is πKm
2
ln(R/r
0
), where R is the size of the sample and r
0
is a lower cutoﬀ
radius (the core size) [2]. Since the elastic energy increases as m
2
, the formation of disclinations with
large Frank indices m is energetically unfavorable.
As has already been mentioned, within the continuum Frank theory, disclinations are singular lines
where the gradient in the director becomes inﬁnite; this signals a breakdown in the Frank theory. The
23
region near the singularity where the Frank theory fails is called the disclination core. The phenomeno
logical elastic theory predicts that a uniaxial nematic either melts or exhibits a complex biaxial structure
in the core region [35].
Therefore, the core of the defect cannot be represented by the director ﬁeld only, because of the
possible biaxiality and variation of the order parameter. For this reason, a more general theory based on
the alignment tensor (1) should be applied to provide the correct description of the core region [36, 37, 38].
8 Computer simulation of liquid crystals
Computer simulation is a well established method to study liquid crystalline mesophase. It has already
been applied to study various bulk properties of liquid crystals, such as bulk elastic constants [39, 40, 41,
42, 43, 44, 45], viscosities [46, 47], helical twisting power [48, 49], parameters of the isotropic–nematic
interface [50]. Moreover, recent works have also proved that computer simulation can be eﬀectively
applied to study conﬁned geometries [51, 52]. Another objective accessible for computer simulation is
the study of topological defects in liquid crystals. Indeed, computer simulation provide us with the exact
structure of the disclination core [53, 54] which is not extractable from phenomenological theories.
Molecular dynamics of nonspherical particles
Molecular dynamics is a numerical technique which allows to solve the classical equations of motion for
a system of molecules interacting via a given potential v
ij
.
As has already been mentioned in sec. 1.1, liquid crystal molecules have elongated shape. There
fore, simulation techniques should take into account orientational degrees of freedom, in addition to the
translational degrees. As an example, we consider equations of motion for linear molecules. For a linear
molecule one of the principal moments of inertia vanishes, and the other two inertia components are
equal.
There are diﬀerent ways of discretising of equations of motion in order to advance from one set of the
coordinates to the next: a quaternion algorithm [55], rotation matrix algorithm, involving equations for
Euler angles [8], a Gear predictorcorrector method [56]. They vary in convenience of implementation
and accuracy. The approach we describe here uses the leapfrog method [57].
For a linear molecule, the angular velocity and the torque are both perpendicular to the molecular
axis at all times. If e
i
is a unit vector along the molecular axis, then the torque on a molecule can be
written as
τ
i
= e
i
×g
i
, (87)
where g
i
= −∇
ei
v
ij
is a ‘gorque’ to be determined from the intermolecular forces. The vector g
i
can
always be replaced by its component perpendicular to the molecular axis, without aﬀecting eqn (87)
τ
i
= e
i
×g
⊥
i
, (88)
with g
⊥
i
= g
i
−(g
i
· e
i
)e
i
.
The equations for rotational motion can be written as two ﬁrstorder diﬀerential equations [8]
˙ e
i
= u
i
,
˙ u
i
= g
⊥
i
/I
i
+λe
i
, (89)
where I
i
is the moment of inertia, λ is a Lagrange multiplier, which constrains the bond length (molecule
length) to be a constant of a motion.
The equations of rotational motion (89) and Newton’s equation of motion
m
i
¨r
i
= f
i
, (90)
describe completely the dynamics of motion of a linear molecule.
24
To solve these equations numerically, we have to adopt a proper discretisation of them. There are
certain criteria that this discretisation has to fulﬁll. The original equations of motion are time reversible.
Therefore, discretised system has to be time reversible and conserve energy. The most widely used
algorithms are leapfrog and velocityVerlet algorithms [8].
To solve equation (90) for motion of the center of mass of the molecule using the leapfrog algorithm,
we advance the velocities by half a step, using current accelerations a(t) and the previous velocities
v(t −
1
2
∆t). Then the velocities and a new set of forces can be calculated:
r (t + ∆t) = r(t) + ∆tv(t +
1
2
∆t), (91)
v(t +
1
2
∆t) = v(t −
1
2
∆t) + ∆ta(t). (92)
To evaluate the kinetic energy at time t the current velocities for time t can be calculated using
v(t) =
1
2
v
t +
1
2
∆t
+v
t −
1
2
∆t
. (93)
To solve the equations of rotational motion (89), one ﬁrst obtains a Lagrange multiplier λ by consid
ering the advancement of coordinates over half a time step
u
i
= u
i
(t −
1
2
∆t) +
1
2
∆t
g
⊥
i
(t)/I +λ(t)e
i
(t)
. (94)
Taking the scalar product of both sides with the vector e
i
(t) gives
λ(t)∆t = −2u
i
(t −
1
2
∆t) · e
i
(t). (95)
Using eqn (95) one can calculate ˙ u
i
(t) from eqn (89) and then advance a full step in the integration
algorithm
u
i
(t +
1
2
∆t) = u
i
(t −
1
2
∆t) + ∆t ˙ u
i
(t). (96)
The step is completed using
e
i
(t + ∆t) = e
i
(t) + ∆tu
i
(t +
1
2
∆t). (97)
Forces and torques
To complete the problem, we have to derive forces and torques (or ‘gorques’) from the pairwise inter
particle potential v
ij
(r
ij
, e
i
, e
j
). Let the centers of the molecules be separated by a vector r
ij
, and
molecular axes be along unit vectors e
i
and e
j
. Then the force on molecule i due to j is
f
ij
= −∇
rij
v
ij
. (98)
Using the chain rule, one obtains
f
ij
= −
∂v
ij
∂r
ij
∇
rij
r
ij
−
¸
α=i,j
∂v
ij
∂ (n
ij
· e
α
)
∇
rij
(n
ij
· e
α
) , (99)
where n
ij
= r
ij
/r
ij
.
Taking into account that
∇
rij
(n
ij
· e
α
) = −(n
ij
· e
α
)
r
ij
r
2
ij
+
e
α
r
ij
, (100)
where α = i, j we obtain
f
ij
= −
∂v
ij
∂r
ij
n
ij
−
¸
α=i,j
∂v
ij
∂ (n
ij
· e
α
)
e
α
r
ij
−r
ij
(n
ij
· e
α
)
r
2
ij
. (101)
25
To evaluate the torque on molecule i due to molecule j
τ
ij
= −e
i
×∇
ei
v
ij
we again apply the chain rule, and obtain
τ
ij
= −e
i
×
¸
r
ij
r
ij
∂v
ij
∂ (n
ij
· e
i
)
+e
j
∂v
ij
∂ (e
i
· e
j
)
. (102)
One can see that f
ij
= −f
ji
but τ
ij
= −τ
ji
.
GayBerne intermolecular potential
The most widely used pair potential for liquid crystal simulations is the GayBerne potential. It is
based on the LennardJones potential extended to an anisotropic pair interaction [58, 59]. The complete
GayBerne potential can be expressed as follows
v (e
i
, e
j
, r
ij
) = 4ε (e
i
, e
j
, n
ij
)
ρ
−12
−ρ
−6
, (103)
where ρ = [r
ij
−σ (e
i
, e
j
, n
ij
) +σ
s
]/σ
s
, r
i
deﬁnes the position of the ith molecule, e
i
is a unit vector
along its anisotropy axis, n
ij
= r
ij
/r
ij
, r
ij
= r
ij
.
The molecular shape parameter σ and the energy parameter depend on the molecular unit vectors
e
i
, e
j
as well as on the separation vector n
ij
between the pair of molecules. This dependence is deﬁned
by the following set of equations
σ (e
i
, e
j
, n
ij
) = σ
s
1 −
χ
2
¸
(e
i
· n
ij
+e
j
· n
ij
)
2
1 +χe
i
· e
j
+
(e
i
· n
ij
−e
j
· n
ij
)
2
1 −χe
i
· e
j
¸¸
−1/2
, (104)
ε (e
i
, e
j
, n
ij
) = ε
s
[ε
(e
i
, e
j
, n
ij
)]
µ
×[ε
(e
i
, e
j
)]
ν
, (105)
where
ε
(e
i
, e
j
, n
ij
) = 1 −
χ
2
¸
(e
i
· n
ij
+e
j
· n
ij
)
2
1 +χ
e
i
· e
j
+
(e
i
· n
ij
−e
j
· n
ij
)
2
1 −χ
e
i
· e
j
¸
, (106)
ε
(e
i
, e
j
) =
1 −χ
2
(e
i
· e
j
)
2
−1/2
. (107)
Here χ and χ
denote the anisotropy of the molecular shape and of the potential energy, respectively,
χ =
κ
2
−1
κ
2
+ 1
, χ
=
κ
1/µ
−1
κ
1/µ
+ 1
. (108)
The most important parameters of the potential are the anisotropy parameters κ and κ
. The κ = σ
e
/σ
s
is roughly the molecular elongation and the κ
= ε
s
/ε
e
is the welldepth ratio for the sidebyside and
endtoend conﬁgurations.
As was demonstrated by simulations [60], the Gay–Berne potential describes quite well thermotropic
liquid crystals. The exponents µ and ν deﬁne diﬀerent variants of the potential. The most studied and
widely used parameterizations are given in Table 1.
The Monte Carlo technique
To sample conﬁgurational space using the Monte Carlo technique, one begins with some (usually randomly
selected) conﬁguration of molecular positions and orientations and then randomly moves and rotates
molecules (avoiding molecular overlaps) to generate trial conﬁguration. When the trial conﬁguration is
generated, the diﬀerence in potential energy ∆U = U
trial
−U
old
of the trial and old systems is calculated
26
Table 1: Parameterizations of the Gay–Berne potential
k k
µ ν
3 5 2 1 De Miguel and Rull parameters [61].
Isotropic, nematic, smectic B, vapor, and solid phases [62].
3 5 1 3 Berardi and Zannoni parameters. Wider nematic phase [63].
3 5 1 2 Luckhurst et al [64].
3  0 0 Soft repulsive potential. Allows bigger timestep.
4.4 20 1 1 Bates and Luckhurst parameters [65].
from the sum of the pair potentials. If ∆U < 0, the trial conﬁguration is accepted and the process
is repeated, choosing another molecule to move and rotate. If ∆U > 0 then the Boltzmann weight
κ = exp(−∆U/k
B
T) is compared to a generated random number, α ∈ [0..1]. If α < κ, the move is
accepted; otherwise it is rejected. Therefore, if ∆U is small, the Boltzmann factor is close to 1 and
the acceptance of the trial conﬁguration is highly probable. As ∆U increases, the trial moves become
accepted with lower and lower probability. This means that big ﬂuctuations in the energy are possible,
but suppressed, leading to eﬃcient phase space sampling. It is usual practice that about half of trial
moves should be accepted [8].
Note that forces and torques are never calculated, only potential energies. Neither real time nor real
particle trajectories exist during MC phase sampling.
The MC technique of a canonical (NV T) ensemble can be adapted to the constant pressure (NPT)
ensemble. The volume changes should be implemented, for example by scaling of all the molecular
positions. The probability function also changes, according to the ensemble, κ = exp[−{∆U + P∆V −
Nk
B
T ln(1−∆V/V )}/k
B
T]. Volume changes are attempted far less often than molecular moves, to insure
they are slow compared to molecular motion.
The Metropolis description [66], described above, generates conﬁgurations which are weighted to favor
thermally populated states of the system. However, a number of important properties, for example free
energies, requires substantial sampling over higherenergy conﬁgurations. Then nonBoltzmann sampling
can be used, with the old and trial states additionally weighted by a suitable function. This weight
ing function should have the form which encourages the system to explore regions of phase space not
frequently sampled by the Metropolis method. The weighted averages than should be corrected, giving
desired ensemble averages. A particular example of nonBoltzmann sampling is the umbrellasampling
technique [8].
9 Applications
Liquid crystal technology has had a major eﬀect many areas of science and engineering, as well as device
technology. Applications for this special kind of material are still being discovered and continue to provide
eﬀective solutions to many diﬀerent problems.
Liquid Crystal Displays
The most common application of liquid crystal technology is liquid crystal displays (LCDs.) This ﬁeld
has grown into a multibillion dollar industry, and many signiﬁcant scientiﬁc and engineering discoveries
have been made. The principle of LCD operation is shown in Fig. (17).
Liquid Crystal Thermometers
As demonstrated earlier, chiral nematic (cholesteric) liquid crystals reﬂect light with a wavelength equal
to the pitch. Because the pitch is dependent upon temperature, the color reﬂected also is dependent
27
Figure 17: Activematrix liquid crystal display.
Figure 18: Temperature sensitive cholesteric liquid crystalline ﬁlm. See the following link for more details:
http://www.prospectonellc.com/lcr.htm. “Reversible Temperature Indicating paints, slurries, labels,
Liquid Crystal Thermometers”.
upon temperature. Liquid crystals make it possible to accurately gauge temperature just by looking at
the color of the thermometer, see Fig. (18). By mixing diﬀerent compounds, a device for practically any
temperature range can be built.
Optical Imaging
An application of liquid crystals that is only now being explored is optical imaging and recording. In this
technology, a liquid crystal cell is placed between two layers of photoconductor. Light is applied to the
photoconductor, which increases the material’s conductivity. This causes an electric ﬁeld to develop in
the liquid crystal corresponding to the intensity of the light. The electric pattern can be transmitted by
an electrode, which enables the image to be recorded.
Polymer dispersed liquid crystals
PDLCs consist of liquid crystal droplets that are dispersed in a solid polymer matrix (see Fig. (19)). The
resulting material is a sort of “swiss cheese” polymer with liquid crystal droplets ﬁlling in the holes. These
tiny droplets (a few microns across for practical applications) are responsible for the unique behavior of
the material. By changing the orientation of the liquid crystal molecules with an electric ﬁeld, it is
possible to vary the intensity of transmitted light.
Other Liquid Crystal Applications
Liquid crystals have a multitude of other uses. They are used for nondestructive mechanical testing of
materials under stress. This technique is also used for the visualization of RF (radio frequency) waves
in waveguides. They are used in medical applications where, for example, transient pressure transmitted
28
Figure 19: In a typical PDLC sample, there are many droplets with diﬀerent conﬁgurations and orien
tations. When an electric ﬁeld is applied, however, the molecules within the droplets align along the
ﬁeld and have corresponding optical properties. In the following diagram, the director orientation is
represented by the black lines on the droplet.
by a walking foot on the ground is measured. Low molar mass (LMM) liquid crystals have applications
including erasable optical disks, full color “electronic slides” for computeraided drawing (CAD), and
light modulators for color electronic imaging.
References
[1] P. G. de Gennes and J. Prost. The Physics of Liquid Crystals. Clarendon Press, Oxford, second,
paperback edition, 1995.
[2] M.J. Stephen and J.P Straley. Physics of liquid crystals. Rev. Mod. Phys., 46:617–704, 1974.
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32
Literature
Many excellent books/reviews have been published covering various aspects of liquid crystals. Among them: 1. The bible on liqud crystals: P. G. de Gennes and J. Prost “The Physics of Liquid Crystals”, Ref. [1]. 2. Excellent review of basic properties (many topics below are taken from this review): M. J. Stephen, J. P. Straley “Physics of liquid crystals”, Ref. [2]. 3. Symmetries, hydrodynamics, theory: P. M. Chaikin and T. C. Lubensky “Principles of Condensed Matter Physics”, Ref. [3]. 4. Defects: O. D. Lavrentovich and M. Kleman, “Defects and Topology of Cholesteric Liquid Crystals”, Ref. [4]; Oleg Lavrentovich “Defects in Liquid Crystals: Computer Simulations, Theory and Experiments”, Ref. [5]. 5. Optics: IamChoon Khoo, ShinTson Wu, “Optics and Nonlinear Optics of Liquid Crystals”, Ref. [6]. 6. Textures: Ingo Dierking “Textures of Liquid Crystals”, Ref. [7]. 7. Simulations: Michael P. Allen and Dominic J. Tildesley “Computer simulation of liquids”, Ref. [8]. 8. Phenomenological theories: Epifanio G. Virga “Variational Theories for Liquid Crystals”, Ref. [9]. Finally, the pdf ﬁle of the lecture notes can be downloaded from http://www.mpipmainz.mpg.de:/~andrienk/lectures/IMPRS/liquid_crystals.pdf.
1
What is a liquid crystal
There is always a reason behind everything and this principle does not exclude naming conventions in physics. Hence, to understand what is a “liquid crystal” we need to clarify why would one give such a name to a substance. At ﬁrst, the notion “liquid crystal” seems to be absurd. It, however, suggests that it is an intermediate state of a matter, in between the liquid and the crystal. It must possess some typical properties of a liquid (e. g. ﬂuidity, inability to support shear, formation and coalescence of droplets) as well as some crystalline properties (anisotropy in optical, electrical, and magnetic properties, periodic arrangement of molecules in one spatial direction, etc.). Certain structural features are often found in molecules forming liquid crystal phases, and they may be summarized as follows: 1. The molecules have anisotropic shape (e. g. are elongated). Liquid crystallinity is more likely to occur if the molecules have ﬂat segments, e. g. benzene rings. 2. A fairly good rigid backbone containing double bonds deﬁnes the long axis of the molecule. 3. The existence of strong dipoles and easily polarizable groups in the molecule seems important. 4. The groups attached to the extremities of the molecules are generally of lesser importance.
2
Figure 1: The arrangement of molecules in liquid crystal phases. (a) The nematic phase. The molecules tend to have the same alignment but their positions are not correlated. (b) The cholesteric phase. The molecules tend to have the same alignment which varies regularly through the medium with a periodicity distance p/2. The positions of the molecules are not correlated. (c) smectic A phase. The molecules tend to lie in the planes with no conﬁgurational order within the planes and to be oriented perpendicular to the planes.
1.1
Nematics
The nematic phase is characterized by longrange orientational order, i. e. the long axes of the molecules tend to align along a preferred direction. The locally preferred direction may vary throughout the medium, although in the unstrained nematic it does not. Much of the interesting phenomenology of liquid crystals involves the geometry and dynamics of the preferred axis, which is deﬁned by a vector n(r) giving its local orientation. This vector is called a director. Since its magnitude has no signiﬁcance, it is taken to be unity. There is no longrange order in the positions of the centers of mass of the molecules of a nematic, but a certain amount of shortrange order may exist as in ordinary liquids. The molecules appear to be able to rotate about their long axes and also there seems to be no preferential arrangement of the two ends of the molecules if they diﬀer. Hence the sign of the director is of no physical signiﬁcance, n = −n. Optically a nematic behaves as a uniaxial material with a center of symmetry. A simpliﬁed picture of the relative arrangement of the molecules in the nematic phase is shown in Fig. (1a). The long planar molecules are symbolized by ellipses.
Figure 2: (a) Schlieren texture of a nematic ﬁlm with surface point defects (boojums). (b) Thin nematic ﬁlm on isotropic surface: 1dimensional periodicity. Photos courtesy of Oleg Lavrentovich http://www. lci.kent.edu/ALCOM/oleg.html. (c) Nematic threadlike texture. After these textures the nematic phase was named, as “nematic” comes from the Greek word for “thread”. Photo courtesy of Ingo Dierking. On optical examination of a nematic, one rarely sees the idealized equilibrium conﬁguration. Some very prominent structural perturbation appear as threads from which nematics take their name (Greek 3
The colors are newton colors of thin ﬁlms and depend on the thickness of the sample. Several typical textures of nematics are shown in Fig. The elastic forces work against the resulting “vertical” distortions of the director ﬁeld. In any plane perpendicular to the twist axis the long axes of the molecules tend to align along a single preferred direction in this 4 . Figure 3: Typical compounds forming nematic mesophases: (PAA) pazoxyanisole.“νηµα” means thread). The current picture shows a 1dimensional periodic pattern. From a steric point of view. From every point defect emerge four dark brushes. From a rough steric point of view. the other kind not that colorful. It is a result of the competition between elastic inner forces and surface anchoring forces. The nematic state is found at room temperatures (between 200 C to 470 C). the lowest energy state is surprisingly archived by “horizontal” director deformations in the plane of the ﬁlm.2 Cholesterics The cholesteric phase is like the nematic phase in having longrange orientation order and no longrange order in positions of the centers of mass of molecules. Here the periodic stripe structure is a spectacular consequence of the conﬁned nature of the ﬁlm. For these directions the director is parallel either to the polarizer or to the analyzer. It diﬀers from the nematic phase in that the director varies in direction throughout the medium in a regular way. The ﬁrst one is a schlieren texture of a nematic ﬁlm. (3). This picture was taken under a polarization microscope with polarizer and analyzer crossed. Lacks chemical stability. A few typical examples are sketched in Fig. (5CB) 4pentyl4’cyanobiphenyl. (2). The second texture is a thin ﬁlm on isotropic surface. Many compounds are known to form nematic mesophase. molecules are rigid rods with the breadth to width ratio from 3:1 to 20:1. The surface anchoring forces want to align the liquid crystals parallel to the bottom surface and perpendicular to the top surface of the ﬁlm. 1. These threads are analogous to dislocations in solids and have been termed disclinations by Frank. When the ﬁlm is suﬃciently thin. The nematic state is found at high A A temperatures (between 1160 C and 1350 C at atmospheric pressure). (MMBA) N (pmethoxybenzylidene)pbutylaniline. The conﬁguration is precisely what one would obtain by twisting about the x axis a nematic initially aligned along the y axis. One can see two types of boojums with “opposite sign of topological charge”. The diﬀerence in appearance is due to diﬀerent core structures for these defects of diﬀerent “charge”. The nematic state is found at room temperatures (between 240 C and 350 C). one type with yellow and red brushes. Point defects can only exist in pairs. this is a rigid rod of length ∼ 20˚ and width ∼ 5˚.
The periodicity length of the cholesteric is actually only half this distance since n and −n are indistinguishable. Typical cholesteric textures are shown in Fig. In general a smectic. A number of diﬀerent classes of smectics have been recognized. (4). The spiral arrangement is responsible for the characteristic colors of cholesterics in reﬂection (through Bragg reﬂection by the periodic structure) and their very large rotatory power. The line pattern is due to the helical structure of the cholesteric phase. In smectic A phase the molecules are aligned perpendicular to the layers. become distorted and can slide over one another in order to adjust to the surface conditions. which distinguishes it from the nematic. In particular. Photo courtesy of Per Rudqvist. A nematic liquid crystal is just a cholesteric of inﬁnite pitch. The image presented above illustrates this longrange order in DNA solutions approaching 300 milligrams per milliliter. (1c)). the preferred direction rotates through a ﬁxed angle. they have distinct right. Photo courtesy of Ingo Dierking. In the smectic C phase the preferred axis is not perpendicular to the layers. The bright colors are due to the diﬀerence in rotatory power arising from domains with diﬀerent cholesteric pitch occuring on rapid cooling close to the smectic A* phase where the pitch strongly diverges with decreasing temperature. chemical composition. and thus comparable with the wavelength of visible light. when placed between glass slides. (1b). Parallel lines denoting the periodicity of the cholesteric mesophase appear at approximately 45degrees from the axis of the image boundaries. Figure 4: (a) Cholesteric ﬁngerprint texture. and is not really an independent case. does not assume the simple form of Fig. preserving their thickness. so that the phase has biaxial symmetry. (5). 5 . The secondary structure of the cholesteric is characterized by the distance measured along the twist axis over which the director rotates through a full circle.3 Smectics The important feature of the smectic phase. i. (c) Longrange orientation of cholesteric liquid crystalline DNA mesophases occurs at magnetic ﬁeld strengths exceeding 2 Tesla. The layers. with the helical axis in the plane of the substrate. and applied magnetic or electric ﬁeld.and lefthanded forms. as illustrated in Fig. The molecules are arranged in layers and exhibit some correlations in their positions in addition to the orientational ordering. The optical properties (focal conic texture) of the smectic state arise from these distortions of the layers. In smectic B phase there is hexagonal crystalline order within the layers. The pitch can be quite sensitive to temperature. is its stratiﬁcation. with no longrange crystalline order within a layer (see Fig. 1. e. Typical textures formed by smectics are shown in Fig. and nematic liquid crystals doped with enantiomorphic materials become cholesterics of long (but ﬁnite) pitch. there is no phase transition between nematic and cholesteric phases in a given material. ﬂow. The layers can slide freely over one another. The molecules forming this phase are always optically active.plane. (1c). The pitch of the common cholesterics is of the order of several hundreds nanometers. viewed between crossed polarizers. This distance is called the pitch of the cholesteric. (b) A shortpitch cholesteric liquid crystal in Grandjean or standing helix texture. but in a series of equidistant parallel planes.
warwick.10.6. K(70K) → Colh (100K) → I.Figure 5: (a.3. Examples are: (i) the nematic phase always occurs at at a higher temperature than the smectic phase. hexabenzocoronene and 2. (b) Rectangular phase of a discotic liquid crystal (c) hexagonal columnar liquidcrystalline phase.4 Columnar phases Figure 6: (a) hexagonal columnar phase Colh (with typical spherulitic texture). 1.chem.b) Focalconic fan texture of a chiral smectic A liquid crystal (courtesy of Chandrasekhar S. More images are available here: http://www.7. Figure 7: Typical discotics: derivative of a hexakishexyloxytriphenylene..uk/jpr/lq/liqcry. the phase is called a discotic columnar.11 Diskshaped mesogens can orient themselves in a layerlike fashion known as the discotic nematic phase. If the disks pack into stacks. The columns themselves 6 .ac. The general rule appears to be that the lower temperature phases have a greater degree of crystalline order.html A number of substances exhibit nematic (or cholesteric) and smectic phases. Krishna Prasad and Gita Nair) (c) Focalconic fan texture of a chiral smectic C liquid crystal. (ii) the smectic phases occur in the order A → C → B as the temperature decreases.
It is thus not possible to introduce a vector order parameter for a liquid crystals analogous to 7 . (b) rectangular.1 Long.and shortrange ordering Order tensor We will ﬁrst try to characterize a nematic mesophase. Other columnar phases with longrange order are classiﬁed by their twodimensional lattices: hexagonal. it is more common now to classify this state of matter and compounds with these properties as columnar liquid crystals. Liquid crystalline behavior is also found in certain colloidal solutions. Then we can introduce a unit vector u(i) along the axis of ith molecule which describes its orientation. (8).5 Lyotropic liquid crystals Liquid crystals which are obtained by melting a crystalline solid are called thermotropic. In this phase. Most of the theories outlined below is equally valid for either class. P = 0. 1. Chiral discotic phases. tetragonal. T = 400 K. The discotic nematic phase includes nematic liquid crystals composed of ﬂatshaped discotic molecules without longrange order. Since liquid crystals possess a center of symmetry. Nematic columnar liquid crystals have no longrange order and are less organized than other columnar liquid crystals. are also known. and (c) herringbone. see Fig. For this class concentration (and secondarily temperature) is the important controllable parameter. The columnar phase is a class of liquidcrystalline phases in which molecules assemble into cylindrical structures to act as mesogens. rather then temperature (and secondarily pressure) as in the thermotropic phase. This class of liquid crystals is called lyotropic. these kinds of liquid crystals were called discotic liquid crystals because the columnar structures are composed of ﬂatshaped discotic molecules stacked onedimensionally. rectangular. Since recent ﬁndings provide a number of columnar liquid crystals consisting of nondiscoid mesogens. may be organized into rectangular or hexagonal arrays. and oblique phases. Aromatic cores are highlighted. such as aqueous solutions of tobacco mosaic virus and certain polymers. Columnar liquid crystals are grouped by their structural order and the ways of packing of the columns. Originally. (2. Suppose that the molecules composing a nematic are rigid and rodlike in shape.Figure 8: (1) Columnar phase formed by the discshaped molecules and the most common arrangements of columns in twodimensional lattices: (a) hexagonal. although we will generally have a thermotropic liquid crystal in mind. molecules do not form speciﬁc columnar assemblies but only ﬂoat with their short axes in parallel to the director (a unit vector which deﬁnes the liquidcrystalline alignment and order). Both top and side views are shown. the average of u(i) vanishes.1 MPa.3) MD simulation results: snapshot of the hexabenzocoronene system with the C12 side chains. 2 2. similar to the chiral nematic phase.
x z 3 (3) since u is a unit vector. indexes α. φ) is the probability to ﬁnd a molecule with the orientation given by the angles θ. Properties of the order parameter tensor 1. 3.y. let us transform everything to the spherical coordinate system (in the isotropic phase all directions are equivalent . φ. Sαβ is a symmetric tensor Sαβ = Sβα . e. tensors).spherical coordinates allow simple formulation of this fact) ux uy uz Then Sαβ = 0 2π π = sin θ cos φ = sin θ sin φ = cos θ 1 sin θdθP (θ. β = (x. φ) uα uβ − δαβ . A natural order parameter to describe the ordering in nematics (or cholesteric) is the second rank tensor Sαβ (r) = 1 N 1 (i) u(i) uβ − δαβ α 3 (1) i when the sum is over all the N molecules in a small but macroscopic volume located at the point r. y. It is traceless TrSαβ = α=(x. To prove this.z) (i) (i) (i) (i) (2) Sαα = 1 N i 1 (i) (u(i) )2 + (uy )2 + (u(i) )2 − 3 = 1 − 1 = 0. 8 . 3 (4) dφ 0 (5) where P (θ. z). In the isotropic phase Sαβ = 0. Two previous properties (symmetries) reduce the number of independent components (3 by 3 matrix) from 9 to 5. and it is necessary to consider higher harmonics (i.Figure 9: Orientation of mesogens in a nematic phase. the magnetization in a ferromagnet. iso 4. A unit vector u(i) along the axis of ith molecule describes its orientation. The director n shows the average alignment. since uα uβ = uβ uα and δαβ = δβα . 2.
in some special cases we can ﬁnd a more convenient representation. where the order parameter is a function of spatial coordinates (in the defect core region. Let us consider one of the diagonal components. φ) = 4π . 6. melting of parts of the system. In general. but we double the value of the integral to compensate for the conventional integration from 0 to π in spherical coordinates. (6) Note that the integration over θ is from 0 to π/2. especially in those systems where the degree of ordering is not changing and therefore only the average orientation of the molecules is of interest. This is due the fact the u and −u are indistinguishable (for unpolar molecules). for example Szz 2π π/2 Szz = 2 0 1 dφ 0 sin θdθP (θ. prolate geometry −1/3 0 0 −1/3 0 . for which the opposite directions are of course distinguishable.2 Director In the previous section we showed that the order tensor is a suitable candidate for an order parameter of a nematic mesophase. It equals to zero in the isotropic phase. at the nematicisotropic interface. which include presence of defects. but we nevertheless describe their orientations using vectors. Normalization conditions require that 1 Piso (θ.It is clear that in the isotropic phase Piso is a constant. 5. It is easy to see that in the isotropic phase the cross terms Sxy = Syz = Sxz = 0 because of the integration over φ (periodic function integrated over its full period). In a perfectly aligned nematic (with the molecules along the z axis). 2π π/2 2 0 dφ 0 sin θdθ = 4π. 2. 0 −1/3 (10) These properties tell us that Sαβ is a very good candidate for the order parameter of our system. In a perfectly aligned oblate geometry (uz = 0) 1/6 S oblate = 0 0 (9) (8) 0 0 1/6 0 . etc. it is sensitive to the direction of the average orientation of the molecules as well as to the molecular distribution of the molecules around the their average orientation. rather inconvenient to use since it lacks clear physical interpretation. It is indeed often used to describe “diﬃcult” situations. Keeping in mind that S is symmetric and traceless we obtain (8). i. φ) cos2 θ − 1 3 d(cos θ) = 2 π (x3 − x) 3 1 3 1 0 = = 0. Since this tensor is a symmetric 9 .). Indeed. however. It is. any symmetric secondorder tensor has 3 real eigenvalues and three corresponding orthogonal eigenvectors. (Recall gyration tensor or mass and inertia tensor). (7) 4πPiso 0 cos2 θ − In a similar fashion one can show that the other two diagonal components are also equal to zero. Indeed. e. S prolate = 0 0 0 2/3 To prove this it is suﬃcient to calculate only the Szz component: Szz = uz uz − 1/3 = 1 − 1/3 = 2/3.
2 (12) The scalar quantity S is a measure of the degree of alignment of molecules. If we compare Eq.3. To the extent that Sαβ is a small parameter. 3 3. The order parameter for all such systems can be characterized by a magnitude S and a direction n.1 Phenomenological descriptions Landaude Gennes free energy Once the appropriate order parameter of the system is identiﬁed (here the order tensor Sαβ ) we can assume. the three nonzero components of S are Szz = 2 S. The most important classes of liquid crystals belong to the uniaxial case (the smectic C is a typical counter example). For a uniaxial nematic phase (molecular distribution function has an axial symmetry) two smaller eigenvalues are equal (B = 0) and the order tensor reads 1 Sαβ = S nα nβ − δαβ 3 (11) where nα are the components of n in a laboratory (ﬁxed) coordinate system. Since the free energy must be invariant under rigid rotations. positive values describe prolatelike distributions. if P (θ) sin θdθ is the fraction of molecules whose axes make angles between θ and θ + dθ with the preferred direction π S= 0 1− 3 sin2 θ P (θ)dθ. can never be realized in practice. that the free energy density g(P. of course. and 4. we may expand g in power series. Here the eigenvalues 3 3 are ordered such as S has the biggest aboslute value. and in the nematic (cholesteric) phase 0 < S < 1. In general. Sαβ ) is an analytic function of the order parameter tensor Sαβ . in a spirit of Landau theories. − 1 S + B. all terms of the expansion must be scalar functions of the tensor Sαβ . a Cartesian coordinate system can be found in which it is diagonal with the diagonal 1 elements 2 S. The limit S = 1 corresponds to perfect alignment of all the molecules and. it can be shown that the scalar order parameter S changes in the range from −1/2 to 1 (from perfect oblate to perfect prolate geometry via isotropic phase). Here gi is the free energy density of the isotropic phase. where the latter is the principal axis of the order parameter tensor. and isotropic liquid has S = 0. T. If we choose n along the z axis of the coordinate system. 10 . In particular this expansion is supposed to work well near the transition temperature. we will see that negative values of S correspond to a pancakelike (oblate) molecular distribution. (11) to two previous cases of ideal prolate and oblate molecular distributions. − 3 S − B (principal moments in case of a gyration tensor). n(r). There is just one distinct invariant of the order 2. B is a biaxiality of the molecular distribution. 2 (13) In the isotropic phase S = 0. 3 1 Sxx = Syy = − S. The corresponding eigenvector is called a director. Quantitatively. The most general such expansion has the form 1 1 1 g = gi + ASαβ Sαβ − BSαβ Sβγ Sγα + CSαβ Sαβ Sγδ Sγδ 2 3 4 (14) correct to fourth order in Sαβ . as shown: other forms (such as Sαβ Sβγ Sγδ Sδα ) can be reduced for uniaxial crystals to one of the forms given when consideration is taken of the fact that the trace Sαα vanishes.3 × 3 matrix. The theoretical development depends merely upon the existence of n and is by no means restricted to the case of rigid symmetric molecules.
or. L1 = 6 × 10−12 J/m. y.1). ∂x ∂nx = .45 × 106 J/m3 . The restoring forces which arise to oppose these deformations we will call curvature stresses or torques. It is normally assumed that A has the form A = A (T − T ∗ ) . Evidently it is necessary to retain higher terms in the expansion in S. We consider a uniaxial liquid crystal and let n(r) be a unit vector giving the direction of the preferred orientation at the point r. and C are in general functions of P and T .2) it will be shown that there are three independent constants for nematics in contrast to just two here. Referred to this coordinate system. If these changes in molecular orientation vary slowly in space relative to the molecular distance scale. These terms must be scalars and consistent with the symmetry of a nematic. equivalently. Once n is deﬁned at some point we assume that it varies slowly from point to point. B = 0. If we consider a nematic liquid crystal in which the order parameter is slowly varying in space. In the OseenFrank curvature elasticity theory (see Sec. the six components of curvature at this point are deﬁned as splay twist bend s1 t1 b1 ∂nx . Globally. which we denote as a “director ﬁled”. C = 0. 4. ∂x ∂ny = − . As we discussed before. z with z parallel to n. The question we would like to address here is: how much energy will it take to deform the director ﬁled? We will refer to the deformation of relative orientations away from equilibrium position as curvature strains. (15) The transition temperature itself will prove to be somewhat above T ∗ (see Sec. The coeﬃcients B and C need have no particular properties near T ∗ . The constants L1 and L2 are related to FrankOseen elastic constants by K11 = K33 = 9Q2 (L1 + b L2 /2)/2 and K22 = 9Q2 L1 /2 and Sb is the bulk nematic order parameter. we will be able to describe the response of the liquid crystal with a version of a continuum elastic theory. 3. the sign of this vector has no physical signiﬁcance. L2 = 12 × 10−12 J/m T ∗ = 307 K. that the free energy density is a quadratic function of the curvature strains in which the analog of elastic moduli appear as coeﬃcients. We will assume that the curvature stresses are proportional to the curvature strains when these are suﬃciently small. At r we introduce a local righthanded Cartesian coordinate system x. B. Typical to Landautype theories. we will regard them as constants. ∂z = s2 = ∂ny ∂y ∂nx t2 = ∂y ∂ny b2 = ∂z (17) (18) (19) 11 .2 FrankOseen free energy We have learned that in a given microscopic region of a liquid crystal there is deﬁnitive preferred axis along which the molecules orient themselves (the director).816 × 106 J/m3 .The coeﬃcients A.044 × 106 J/m3 K. The x and y axis can be chosen arbitrarily because the liquid crystal is uniaxial. b Typical values for a nematic compound 5CB [10]: A = 0. The nematicisotropic transition temperature for 5CB is TN I = 308.5 K. the free energy will also contain terms which depend on the gradient of the order parameter. the most general form for the inhomogeneous part of the free energy density is ge = 1 ∂Sij ∂Sij 1 ∂Sij ∂Sik L1 + L2 2 ∂xk ∂xk 2 ∂xj ∂xk (16) We will refer to the constants L1 and L2 as elastic constants. the orientation of the liquid crystal is then characterized by a vector ﬁeld. this model equation of state predicts a phase transition near the temperature where A vanishes. 3. If we conﬁne ourselves to terms O(S 2 ).
We have chosen a righthanded coordinate system in which z is positive in the direction of n. z → −z.j=1 6 (23) where the ki and kij = kji are the curvature elastic constants and for convenience in notation we have put a1 = s1 . 2 ∂nx ∂ny ∂ny ∂nx ∂ − = ∂x ∂y ∂x ∂y ∂x ∂ny ∂y ∂ ∂y ∂ny ∂x (24) The last term can be written s1 s2 + t1 t2 = nx − nx (25) and consequently it will contribute only to to surface energies. a5 = s2 . The general expression for the free energy density. are distributed with equal probability in the two directions. and that of the thirtysix kij . ny (r) = −t1 x + s2 y + b2 z + O(r2 ). x → x. a2 = t2 . relative to its free energy density in the state of uniform orientation can be expanded in terms of six curvature strains 6 g= i=1 ki ai + 1 kij ai aj 2 i. (20) (21) (22) We now postulate that the Gibbs free energy density g of a liquid crystal.Figure 10: The three distinct curvature strains of a liquid crystal: (a) splay. y. nz (r) = 1 + O(r2 ). (26) Invariance of the free energy under this transformation requires k1 = k12 = 0 If k1 = 0. written in terms of a set of eight independent moduli. and (c) bend. becomes g 1 1 = k1 (s1 + s2 ) + k2 (t1 + t2 ) + k11 (s1 + s2 )2 + k22 (t1 + t2 )2 2 2 1 2 2 + k33 (b1 + b2 ) + k12 (s1 + s2 )(t1 + t2 ) − (k22 + k24 )(s1 s2 + t1 t2 ). (b) twist. y → −y. then the choice of the sign of n is arbitrary. Thus we can omit the last term in considerations involving the properties of the bulk liquid crystal. a6 = b2 . In the presence of further symmetries g can have still simpler forms 1. These three curvature strains can also be deﬁned by expanding n(r) in a Taylor series in powers of x. it is readily shown 4 that there are only two independent moduli ki . Because the crystal is uniaxial. the equilibrium state has ﬁnite splay. only ﬁve are independent. A reversal of n which retains the chirality of the coordinate system generates the transformation n → −n. 12 (nonpolar). (27) . z measured from the origin nx (r) = s1 x + t2 y + b1 z + O(r2 ). a rotation about z will make no change in the physical description of the substance. a3 = b1 . a4 = −t1 . and consequently the free energy density g should be invariant under such rotations. 1 By consideration of a few special cases (such as rotations of 2 π and 1 π about z). if polar. If the molecules are nonpolar or.
Brieﬂy about the meaning of diﬀerent symbols: div n = ·n= ∂ ∂ ∂ nx + ny + nz ∂x ∂y ∂z i j k ∂ ∂ ∂ ∂ ∂ × n = ∂x ∂y ∂z = i nz − ny ∂y ∂z nx ny nz curl n = +j ∂ ∂ nx − nz ∂z ∂x +k ∂ ∂ ny − nx ∂x ∂y For the purpose of qualitative calculations it is sometimes useful to consider a nonpolar. We note that s1 + s2 = ∂nx ∂ny + = · n. nonenatiomorphic liquid crystal whose bend. and k12 vanishes unless both polarity and enantiomorphy occur together. ∂x ∂y ∂nx ∂z 2 (32) (33) n)2 (34) −(t1 + t2 ) = b 2 + b2 1 2 = + ∂ny ∂z 2 = (n · which may be substituted back to the expression for the free energy to give g= 1 k11 ( 2 1 1 · n − s0 )2 + k22 (n · curl n + t0 )2 + k33 (n × curl n)2 − k12 ( 2 2 · n)( · curl n) (35) This is the famous FrankOseen elastic free energy density for nematics and cholesterics. k2 in the absence of enantiomorphy. (36) . and twist constants are equal (oneconstant approximation). ∂x ∂y ∂ny ∂nx − = n · ( × n). z → z. Thus the cholesteric phase is characterized by t0 = 0. y → −y. In the absence of enantiomorphism (chiral molecules which have diﬀerent mirror images) g should be invariant under reﬂections under reﬂections in plane containing the z axis. splay. In summary. The free energy density for this theoretician’s substance is g= 1 k ( 2 · n)2 + ( 13 × n)2 . (28) This introduces the constraints k2 = k12 = 0 (mirror symmetry).2. The free energy density can be written in a vector notation. such as the transformation x → x. It is convenient to deﬁne k2 k1 t0 = − (30) s0 = − k11 k22 and to add constants to g g 1 1 = g + k11 s2 + k22 t2 0 0 2 2 1 1 = k11 (s1 + s2 − s0 )2 + k22 (t1 + t2 − t0 )2 2 2 1 k33 (b2 + b2 ) + k12 (s1 + s2 )(t1 + t2 ) − (k22 + k24 )(s1 + s2 )(t1 + t2 ). + 1 2 2 (31) so that now evident that s0 and t0 are the splay and twist of the state which minimizes the free energy the equilibrium state. k1 vanishes in the absence of polarity. (29) If k2 = 0 then the equilibrium state has ﬁnite twist.
T ∗∗ . It will be a root of the derivative which is 2 1 AS − BS 2 + CS 3 = 0.Equations for the director can be obtained by minimization of the free energy constraint n2 = 1 and have the following form − k11 ( · n) + k22 {A[ × n] + [ × (An)]} + k33 {[[ × n] × B] + [ V gdr with an additional × [B × n]]} + µn = 0. (39) 3 3 14 . We consider thermotropic liquid crystals. where A = n · [ × n]. where temperature is the parameter driving the transition. 3 27 9 (38) (37) The equilibrium value of S is that which gives the minimum value for the free energy. µ is an unknown Lagrange multiplier which must be found 4 Nematicisotropic phase transition In this section we will apply existing theories to describe the isotropic to nematic phase transition. The dependence of gi on S for several choices of T is shown in Fig. The source of this ﬁrstorder phase transition lies in the presence of the oddorder powers of S in the expansion. (11). The value of S which minimizes Eq. Tc . × n]]. (38) can be found algebraically.1 Landau theory In Sec. 4. Figure 11: Landau theory: dependence of the Gibbs free energy density on the order parameter. and T ∗ are shown. (14) we obtain 1 2 1 g = gi + AS 2 − BS 3 + CS 4 . The case of the three special temperatures.2 we derived that in a uniaxial liquid crystal the order parameter Sαβ takes the form 1 Sαβ = S nα nβ − δαβ 3 Substituting this into Eq. There is a discontinuous phase transition at a temperature Tc slightly above T ∗ . the existence of these terms is in turn due to the fact that the sign of S has physical meaning. 2. B = [n × [ from the condition n2 = 1. For illustration we use A = B = C = 1.
The transition temperature Tc will be such that the free energies of isotropic and nematic phases are equal. in principle. 4. 15 . This assumptions allow to derive the eﬀective potential for each molecule with orientation u 1 3 V (u. corresponding to a maximum of the free energy.The solutions of this equations are S S = 0 isotropic phase = (B/4C)[1 + (1 − 24β)1/2 ] (40) (41) nematic phase. An attractive. From Eqs. to supercool the isotropic liquid to this temperature. A third solution. where the coeﬃcient A in the free energy changes sign. Thus susceptibilities and correlation lengths. where β = AC/B 2 . will appear to headed for a divergence at a temperature slightly beyond the transition temperature Tc . 3. The mean ﬁeld approximation. 27 Tc = T ∗ + 1 B2 . orientationdependent van der Waals interaction between the molecules. S) = − ASαβ (uα uβ − δαβ ) 2 3 (44) The probability distribution for the orientation of a molecule in the presence of this external ﬁeld is f (u) = 1 V (u. nonpolar molecules interacting via van der Waals interactions. 2. has been suppressed. 27 A C (42) Above Tc the isotropic phase is stable. S)/kT ) is the normalization factor. (38) and (41) this point can be determined to be β= 1 . The conﬁguration of the centers of mass is not aﬀected by the orientationdependent interaction. The temperatures T ∗ and T ∗∗ also have the signiﬁcance that they are apparent “critical points” for the isotropic and ordered phases. (43) The temperature T ∗ corresponds to the limit of metastability of the isotropic phase. below Tc the nematic is stable. We also assume that molecules are arranged in a spherically symmetric way (positional correlations are isotropic) and that the distribution of orientations of each molecule is described by the average order parameter Sαβ . We consider rodlike. The value of the order parameter at the phase transition is Sc = B/3C. S) exp − Z kT (45) where Z = du exp(−V (u. At T ∗ . We restrict ourselves to the orientationdependent part and assume that a particular molecule feels the averaged interaction of the surrounding molecules. the nematic phase becomes unstable when β > 1/24. du indicates an integration over all orientations of u. The MaierSaupe theory is based on three assumptions: 1. which increase as the transition point is approached. respectively. Likewise.2 MaierSaupe theory Maier and Saupe in a series of paper (19581960) have given a microscopic model for the phase transition in a nematic liquid crystal. It should be possible. the isotropic phase becomes unstable (because S = 0 is not a local minimum of the free energy). This determines a temperature T ∗∗ = T ∗ + B 2 /(24A C) which is the limit of the nematic phase on heating.
according to Eq. 1 (46) Sαβ = du uα uβ − δαβ f (u). (51) determines a corresponding value of S and T . 16 (54) (53) .43. (51) A 2 x2 x where D(x) = 0 exp(y 2 )dy is Dawson’s integral. The resulting relationship between S and T is shown in Fig. 3 In the case of a uniaxial liquid crystal this equation can be simpliﬁed. (47) S= Z 0 2 2 kT where. S) sin θdθ. (47) and (49) is S = 0. After integration by parts Eq.The theory is made selfconsistent by requiring that the average value of uα uβ − 1 δαβ be equal to 3 Sαβ . (44) 3 1 V (θ. and deﬁning θ to be the angle between u and z. (12).22A0 . S) = − A0 S 2 + kT ln C/4π (52) 2 The MaierSaupe theory predicts a ﬁrstorder phase transition at a temperature Tc deﬁned by kB Tc = 0. Taking the preferred direction (director) to be the z axis. and the value of the order parameter at the transition is Sc = 0. Nontrivial solutions also exist. (49) Z = 2π exp − kT 0 It is readily seen that one solution of Eqs. which corresponds to the isotropic phase. S) = −AS cos2 θ − (48) 2 2 and Z can now be written π V (θ. (46) can be written 1 V (θ. which may be calculated as 1 F (T. (47) can be written in a parametric form 3 exp(x2 ) 1 1 S = − 2 − (50) 4 xD(x) x 2 kT 3 S = . the zz component of Eq. The stable mesophase is given by the solution which minimizes the free energy per particle. For each value of x Eq. S) 2π π 3 cos2 θ − exp − sin θdθ. Figure 12: MaierSaupe theory: dependence of free energy F and order parameter S on temperature.
Ω1 ). SN = kB ln ΩN . The reason for this is truncation of the virial expansion of the free energy at the leading. In the nematic state. (59) where ΩI. SI = kB ln ΩI .3 Onsager theory Onsager theory [11] is a form of molecular ﬁeld theory. in comparison to the isotropic state. Consider an ensemble of elongated particles interacting pairwise through some potential V(1. f (1. 2)ρ(2)d(2) = 0. 2) which depends on both positions and orientations of the molecules: 1 = (r1 . with the diﬀerence that the conﬁgurational average energy is replaced by the orientationdependent conﬁgurational entropy. U (1) is the external potential energy. the excluded volume decreases. or a critical volume fraction is given by φc = Vrods /V ∼ (N LD2 )/(N L2 D) = D/L.4. the equation (57) can be solved numerically for any form of the second virial coeﬃcient which can be expanded in Legendre polynomials. In principle.N gives the number of orientational states in the isotropic or nematic mesophase. these two contributions compensate each other. The Onsager theory predicts large changes in density at the transition. which gives the number of molecules per unit solid angle and per unit volume βF [ρ] = ρ(1) ln ρ(1)Λ3 − 1 − βµ + βU (1) d(1) − 1 2 f (1. µ is the chemical potential. ∆Sor = kB ln ΩN /ΩI ∼ kB . and this gives rise to the translational entropy of the system [13] ∆Str = −kB ln (1 − Vexcl /V ) ∼ kB ρL2 D. 2) = exp [−V(1. ∆Sor + ∆Str = 0 and the critical density is ρc ∼ 1/(L2 D). In conclusion. The diﬀerence is that the MaierSaupe theory is commonly applied to liquids. Λ is the de Broglie wavelength. ρ(1). 15. Onsager theory is a forerunner of modern densityfunctional theory [12]. as is observed for such systems. The solutions are qualitatively the same as the solutions of the MaierSaupe equation. pairwise term. systematic improvements are possible which improve the agreement with the bulk equation of state [14. The equilibrium singleparticle density that minimizes the free energy (55) is a solution of the following Euler–Lagrange equation ln ρ(1)Λ3 − βµ + βU (1) − f (1. Onsager’s expression for the Helmholtz free energy per particle is expressed in terms of the singleparticle density. However. 17 . increasing lengthtobreadth ratio we favor nematic formation. 16. there is also a decrease in orientational entropy in the nematic state. At the nematicisotropic transition. (57) which can be obtained from the variation of the functional (55). Onsager theory can be explained using simple arguments of a volume taken by a molecule (excluded volume). However. (58) where ρ = N/V is the density of rods with length L and diameter D. Therefore. However. 17]. we point out that the Onsager theory does not describe the bulk equation of state perfectly. 2)ρ(1)ρ(2)d(1)d(2). which are only slightly compressible. 2)/kB T ] − 1 (56) is the Mayer f function. sometimes it is more convenient to minimize the functional (55) instead of solving the integral equation (57). whereas the Onsager expansion is applied to dilute suspensions of particles for which the change in free energy with density is relatively small. (55) Here β = 1/kB T . Onsager has shown how the Mayer cluster theory may be used to give an expansion for the equation of state of this system [11].
In an electric ﬁeld E there will be an additional free energy ge = − 1 8π ⊥E 2 − 1 8π a (n · E)2 . which are the susceptibilities per unit volume along and perpendicular to the axis. In the uniaxial case it is a secondrank tensor with two components χ and χ⊥ . (60) where χa = χ − χ⊥ is the anisotropy and is generally positive. owing to the anisotropic form of the molecules composing it. The magnetic susceptibility of a liquid crystal. in principle. (b) slightly above Hc . It is thus possible to exert torques on the liquid crystal by applying a ﬁeld. The presence of a magnetic ﬁeld H leads to an extra term in the free energy of 1 1 gm = − χ⊥ H 2 − χa (n · H)2 . 5. deviation of the alignment sets in. applied perpendicular to the director. exceeds a certain critical value. This eﬀect ﬁrst observed by Frederiks and Zolina and can be used to measure some of the elastic constants. 18 .1 Frederiks transition in nematics Consider a nematic liquid crystal between two glass slides. (62) in practice the alignment of a liquid crystal by an electric ﬁeld is complicated by the presence of conducting impurities which make it necessary to use alternating electric ﬁelds. the deviation increases.5 Response to external ﬁelds The director ﬁeld is easily distorted and can be aligned by magnetic and electric ﬁelds. The interaction between the nematic and the glass is such that the director is constrained to lie perpendicular to the glass at the boundaries. Figure 13: Frederiks transition. The susceptibility tensor thus takes the form χij = χ⊥ δij + χa ni nj . the optical properties of the system change abruptly. Thus. and by surfaces which have been properly prepared. (61) 2 2 The ﬁrst term usually will be omitted as it is independent of the orientation of the director. (a) Below a certain critical ﬁeld Hc . The reason is that both the magnetic ﬁeld and the boundaries exert torques on the molecules and when the ﬁeld exceeds Hc it becomes energetically favorable for the molecules in the bulk of the sample to turn in the direction of the ﬁeld. The dielectric susceptibility of a liquid crystal is also anisotropic and has the same form as the magnetic susceptibility. The last term gives rise to a torque on the liquid crystal .if χa is positive the molecules will align parallel to the ﬁeld. When a magnetic ﬁeld. The liquid crystal is constrained to be perpendicular to the boundary surfaces and a magnetic ﬁeld is applied in the direction shown. (c) ﬁeld is increased further. the alignment is not aﬀected. is also anisotropic. we can achieve the same eﬀect with an electric ﬁeld as with a magnetic ﬁeld.
If the maximum distortion θm is small z θ = θm cos (68) ξ is a good approximate solution. The boundary conditions require that d = ξπ. 19 (70) . (65) Now we have a variational problem . ∂2z (67) There is a trivial solution θ = 0 which satisﬁes the boundary conditions. (64) becomes g= 1 k 2 ξ2 d/2 dz ξ 2 −d/2 ∂θ ∂z 2 − sin2 θ . Hc = k33 π χa d (69) which holds even if k11 = k33 . The general solution to Eq. For ﬁelds weaker than Hc only the trivial solution exists. (13)). equivalently. We will suppose one constant approximation. and there is no distortion on the nematic structure.Let the z axis be perpendicular to the glass surfaces and the ﬁeld H lie along the x direction (see Fig. First we need to calculate the divergence and curl of our vector ∂θ .d/2 = 0. ∂z ∂θ × n = j cos θ . k11 = k33 = k. or. The director will have the form nx = sin θ(z).we have to minimize the free energy satisfying the boundary conditions θz=−d/2. ∂z n·( n × curl n = The elastic energy per unit area now takes the form g= 1 2 d/2 dz −d/2 k11 sin2 θ + k33 cos2 θ ∂θ ∂z 2 − χa H 2 sin2 θ . ny = 0. ∂z × n) = 0.they are in metastable equilibrium. Thus a measurement of Hc is a measurement of k33 . We deﬁne the length ξ = k/χa H 2 and Eq. nz = cos θ(z) (63) so that θ is the angle between the director and the z axis. · n = − sin θ (knx − inz ) cos θ ∂θ . In the undistorted structure (θ = 0) the ﬁeld does not exert a torque on the molecules . The ﬁrst integral is ξ2 ∂θ ∂z 2 + sin2 θ = sin2 θm . (67) is readily found. (66) Variation of the free energy leads to the diﬀerential (EulerLagrange) equation ξ2 ∂2θ + sin θ cos θ = 0. (64) where d is the thickness of the sample. provided that χa is known.
θ). (72). as given by Eq. The maximum distortion is found by putting z = 0. no = ∆n = ne − no . Figure 14: Dependence of θm on H. we can introduce ordinary and extraordinary refractive indexes √ √ ne = . no is approximately 1. The length ξ is called the magnetic coherence length and arises in many problems involving the distortion produced by a magnetic ﬁeld. (75) For typical nematic liquid crystals. 1 d = ξ csc θm F (csc θm .1 Optical properties Nematics It has already been mentioned in Section 5 that the dielectric susceptibility of a nematic is anisotropic and in a uniaxial state is a secondrank tensor with two components and ⊥ . The equation can be further integrated to give 1 d−z =ξ 2 θ 0 2 dθ sin θm − sin2 θ 1/2 = ξ csc θm F (csc θm . ∆n. csc θ = 1/ sin θ. (74) Correspondingly. 6 6.5. (73) The dependence of θm on H is shown in in Fig. ξ can be directly interpreted as the distance which a disturbance can propagate into the liquid crystal in the presence of an ordering ﬁeld. 2 where K is the complete elliptic integral of the ﬁrst kind. (71) where F is the incomplete elliptic integral of the ﬁrst kind.5 and the maximum diﬀerence. may range between 0. (14). 20 . θm ) = ξK(sin θm ). In fact. where θ takes on its maximum value. ij = ⊥ δij + a ni nj . which are the susceptibilities per unit volume along and perpendicular to the axis. θ = θm . This maximum presumably lies halfway between the glass surfaces at z = 0.where the constant of integration has been identiﬁed by observing that dθdz = 0. For ﬁelds just above Hc H θm ∼ 2 −1 Hc (72) 1/2 . and we have used the boundary 1 condition θ = 0 at z = 2 d. ⊥.05 and 0.
When the rays are recombined as they exit the birefringent material. when light enters a birefringent material. Because the two components travel at diﬀerent velocities.Thus. If the sample is very thin. If the phase diﬀerence equals 2π. For monochromatic light (single frequency). the ordinary and extraordinary components do not get very far out of phase. the waves get out of phase. the wave returns to its original polarization state and is blocked by the second polarizer. The length of the sample is another important parameter because the phase shift accumulates as long as the light propagates in the birefringent material. when this ray reaches the second polarizer. Likewise. if the sample is thick. the magnitude of the phase diﬀerence is determined by the length and the birefringence of the material. Figure 15: Light traveling through a birefringent medium will take one of two paths depending on its polarization. the polarization state has changed because of this phase diﬀerence. The size of the phase shift determines the intensity of the transmitted light. λ (80) Therefore. Any polarization state can be produced with the right combination of the birefringence and length parameters. Consider the case where a liquid crystal sample is placed between crossed polarizers whose transmission axes are aligned at some angle α between the fast and slow direction of the material. the incoming linearly polarized light Eincident = becomes elliptically polarized Esample (z) = Using Jones calculus for optical polarizer ˆ A= sin2 α − cos α sin α − cos α sin α cos2 α (78) Ex exp(ike z) Ey exp(iko z) (77) Ex Ey = E0 cos α E0 sin α (76) We obtain the light behind the second polarizer (analyzer) ˆ Eout = AEsample (z = L) = E0 sin(2α) sin(∆kL/2) exp[i(ko + ke )L/2] and the output intensity becomes 2 Iout = Eout  = E0 sin2 (2α) sin2 2 sin α cos α (79) ∆kL 2 = I0 sin2 (2α) sin2 π∆nL . Because of the birefringent nature of the sample. 21 . there is now a component that can pass through. the phase diﬀerence can be large. and the region appears bright. such as a nematic liquid crystal sample. the process is modelled in terms of the light being broken up into the fast (called the ordinary ray) and slow (called the extraordinary ray) components.
This means that some areas appear light and others appear dark. and no change in the polarization state occurs. In this case. birefringence. They are designed for a speciﬁc wavelength and thus will produce the desired results for a relatively narrow band of wavelengths around that particular value. the wavelength λ will not be aﬀected by the retarder and so will be extinguished (absorbed) by the analyzer. However. Color patterns observed in the polarizing microscope are very useful in the study of liquid crystals in many situations. all other wavelengths will experience some retardation and emerge from the fullwave plate in a variety of polarization states. −d/2 (82) dθ (1 + ν sin 2 θ)1/2 (sin2 θm − sin 2 θ)1/2 =1− 2ξ 1 K d (1 + ν sin2 θm )1/2 csc2 1+ν θm + ν . The light and dark areas that denote regions of diﬀering director orientation. Up to this point. the birefringence and length are not constant over the entire sample. (70). If. H − Hc Hc (84) 6. The components of this light passed by the analyzer will then form the complementary color to λ. Fig.If the transmission axis of the ﬁrst polarizer is parallel to either the ordinary or extraordinary directions. (2a). a fullwave plate designed for wavelength is λ is placed between crossed polarizers at some arbitrary orientation and the combination illuminated by white light.1) occur can be detected optically because there is a change in the refractive index of the material. The refractive index locally is (the light is polarized along z axis ne no (81) n= 1/2 n2 sin2 θ + no cos2 θ e The average change in the refractive inde is δ= Using Eq. Frederiks transition The distortion of the director by the ﬁled when Frederiks transition (see Section 5. In a typical liquid crystal. as shown in the microscope picture of a nematic liquid crystal. The dark regions that represent alignment parallel or perpendicular to the director are called brushes. Colors arising from polarized light studies Birefringence can lead to multicolored images in the examination of liquid crystals under polarized white light. for example. it will be helpful to return to the examples of retarding plates.2 Cholesterics This is your homework. and length. taken between crossed polarizers. of liquid crystal phases and the observations of phase changes. this can be put in the form δ 2ξ =1− ne d θm 0 d/2 1 d dz(ne − no ). including the identiﬁcation of textures. (83) where ν = (n2 − n2 )/n2 . For small deformations the change in the refractive index is e o o δ = ne ν and for large ﬁelds approaches ne − no . we have dealt only with monochromatic light is considering the optical properties of materials. In understanding the origin of the colors which are observed in the studies of liquid crystals placed between crossed linear polarizers. the light is not broken up into components. there is not a transmitted component and the region appears dark. 22 .
m = +1/2. superﬂuid helium [19].Figure 16: Examples of axial disclinations in a nematic: (a) m = +1. Liquid crystals are ideal materials for studying topological defects. liquid crystals [23. the formation of disclinations with large Frank indices m is energetically unfavorable. nematic liquid crystalline phase owes its name to the typical threadlike defect which can be seen under a microscope in a nematic or cholesteric phase [31]. As has already been mentioned. The axial solutions of the EulerLagrange equations representing disclination lines are φ = mψ + φ0 . The simplest. 26. ferromagnets [20]. 24. (b) the parabolic disclination. Examples of disclinations for several m are given in Fig. 22]. quantum Hall ﬂuids [28]. For the case of nematics. Hedgehogs are characterized by an integer topological charge q specifying the number of times the unit sphere is wrapped by the director on any surface enclosing the defect core. Since the elastic energy increases as m2 . 27]. The resulting defects are easily imaged optically. (86) where nx = cos φ. crystalline solids [21. Distortions yielding defects are easily produced through control of boundary conditions. In analogy with dislocations in crystals. and the integral is over any surface enclosing the defect core. within the continuum Frank theory. ψ is the azimuthal angle. and even optical ﬁelds [29] playing an important role in such phenomena as response to external stresses. where R is the size of the sample and r0 is a lower cutoﬀ radius (the core size) [2]. The 23 . and hedgehogs can have positive or negative charges. there are two kinds of stable topological defects in three dimensions: point defects. (c) the hyperbolic disclination (topologically equivalent to the parabolic one). To classify topological defects the homotopy theory can be employed to study the order parameter space [34]. For an order parameter with O3 . take all charges to be positive. m = −1/2. x = r cos ψ. (85) where ∂α denotes diﬀerentiation with respect to xα . and external ﬁelds. this signals a breakdown in the Frank theory. the nature and type of phase transitions. the orderparameter space is S 2 . or vector symmetry. Nematic inversion symmetry makes positive and negative charges equivalent. They exist almost in every branch of physics: biological systems [18]. disclinations are singular lines where the gradient in the director becomes inﬁnite. 25. as a result. (16). called disclinations. ijk is the LeviCivita symbol. They even arise in certain cosmological models [30]. and we may. First explanations were given by Friedel [32] who suggested that these threads are lines on which the director changes its direction discontinuously. called hedgehogs and line defects. Frank proposed to call them disclinations [33]. m is a positive or negative integer or halfinteger [2]. 7 Defects Topological defects appear in physics as a consequence of broken continuous symmetry [3]. surface geometries. An analytical expression for q is q= 1 8π dSi ijk n · (∂j n × ∂k n) . The elastic energy per unit length associated with a disclination is πKm2 ln(R/r0 ).
54] which is not extractable from phenomenological theories. As has already been mentioned in sec. 38]. r describe completely the dynamics of motion of a linear molecule. without aﬀecting eqn (87) ⊥ τ i = ei × gi . a Gear predictorcorrector method [56]. (89) where Ii is the moment of inertia. 49]. ⊥ with gi = gi − (gi · ei )ei . computer simulation provide us with the exact structure of the disclination core [53. 47]. 40. Therefore. Moreover. 45]. simulation techniques should take into account orientational degrees of freedom. and the other two inertia components are equal. Another objective accessible for computer simulation is the study of topological defects in liquid crystals. Molecular dynamics of nonspherical particles Molecular dynamics is a numerical technique which allows to solve the classical equations of motion for a system of molecules interacting via a given potential vij . the core of the defect cannot be represented by the director ﬁeld only. because of the possible biaxiality and variation of the order parameter. then the torque on a molecule can be written as τ i = e i × gi . The equations of rotational motion (89) and Newton’s equation of motion mi ¨i = fi . The vector gi can always be replaced by its component perpendicular to the molecular axis.region near the singularity where the Frank theory fails is called the disclination core. The approach we describe here uses the leapfrog method [57]. 42. For a linear molecule one of the principal moments of inertia vanishes. a more general theory based on the alignment tensor (1) should be applied to provide the correct description of the core region [36. helical twisting power [48. 8 Computer simulation of liquid crystals Computer simulation is a well established method to study liquid crystalline mesophase. 41. 43. in addition to the translational degrees. 52]. There are diﬀerent ways of discretising of equations of motion in order to advance from one set of the coordinates to the next: a quaternion algorithm [55]. liquid crystal molecules have elongated shape. rotation matrix algorithm. It has already been applied to study various bulk properties of liquid crystals. parameters of the isotropic–nematic interface [50]. such as bulk elastic constants [39.1. involving equations for Euler angles [8]. The phenomenological elastic theory predicts that a uniaxial nematic either melts or exhibits a complex biaxial structure in the core region [35]. For this reason. 44. For a linear molecule. As an example. The equations for rotational motion can be written as two ﬁrstorder diﬀerential equations [8] (88) ˙ ei ˙ ui = ui . Indeed. 37. Therefore. we consider equations of motion for linear molecules. 1. viscosities [46. They vary in convenience of implementation and accuracy. 24 (90) . recent works have also proved that computer simulation can be eﬀectively applied to study conﬁned geometries [51. ⊥ = gi /Ii + λei . the angular velocity and the torque are both perpendicular to the molecular axis at all times. which constrains the bond length (molecule length) to be a constant of a motion. λ is a Lagrange multiplier. If ei is a unit vector along the molecular axis. (87) where gi = − ei vij is a ‘gorque’ to be determined from the intermolecular forces.
j ∂vij ∂ (nij · eα ) rij (nij · eα ) . one obtains fij = − where nij = rij /rij .j ∂vij ∂ (nij · eα ) eα (nij · eα ) − rij 2 rij rij . (93) To solve the equations of rotational motion (89). we have to derive forces and torques (or ‘gorques’) from the pairwise interparticle potential vij (rij . rij ij (100) where α = i. (91) (92) To evaluate the kinetic energy at time t the current velocities for time t can be calculated using v(t) = 1 2 1 v t + 2 ∆t + v t − 1 ∆t 2 . (101) 25 . (97) Forces and torques To complete the problem. we have to adopt a proper discretisation of them. Then the force on molecule i due to j is fij = − Using the chain rule. one ﬁrst obtains a Lagrange multiplier λ by considering the advancement of coordinates over half a time step ⊥ 1 1 ui = ui (t − 2 ∆t) + 2 ∆t gi (t)/I + λ(t)ei (t) . Taking into account that rij rij vij . (99) (nij · eα ) = − (nij · eα ) rij eα 2 + r . we advance the velocities by half a step. Then the velocities and a new set of forces can be calculated: 2 r (t + ∆t) v(t + 1 ∆t) 2 1 = r(t) + ∆tv(t + 2 ∆t). To solve equation (90) for motion of the center of mass of the molecule using the leapfrog algorithm. discretised system has to be time reversible and conserve energy. ej ). Let the centers of the molecules be separated by a vector rij . Therefore. using current accelerations a(t) and the previous velocities v(t − 1 ∆t). There are certain criteria that this discretisation has to fulﬁll. The original equations of motion are time reversible. ei . (95) ˙ Using eqn (95) one can calculate ui (t) from eqn (89) and then advance a full step in the integration algorithm 1 ˙ ui (t + 2 ∆t) = ui (t − 1 ∆t) + ∆tui (t). (98) ∂vij ∂rij rij rij − α=i. 1 = v(t − 2 ∆t) + ∆ta(t). (96) 2 The step is completed using 1 ei (t + ∆t) = ei (t) + ∆tui (t + 2 ∆t). and molecular axes be along unit vectors ei and ej . (94) Taking the scalar product of both sides with the vector ei (t) gives 1 λ(t)∆t = −2ui (t − 2 ∆t) · ei (t). The most widely used algorithms are leapfrog and velocityVerlet algorithms [8]. j we obtain fij = − ∂vij ∂rij nij − α=i.To solve these equations numerically.
ej )] . When the trial conﬁguration is generated. As was demonstrated by simulations [60]. nij ) ρ−12 − ρ−6 .To evaluate the torque on molecule i due to molecule j τ ij = −ei × we again apply the chain rule. (102) ei vij One can see that fij = −fji but τ ij = −τ ji . ei is a unit vector along its anisotropy axis. rij = rij . nij ) = 1 − ε (ei . ej . ej as well as on the separation vector nij between the pair of molecules. nij )] × [ε (ei . The molecular shape parameter σ and the energy parameter depend on the molecular unit vectors ei . ej . The exponents µ and ν deﬁne diﬀerent variants of the potential. the Gay–Berne potential describes quite well thermotropic liquid crystals. ej . The Monte Carlo technique To sample conﬁgurational space using the Monte Carlo technique. The complete GayBerne potential can be expressed as follows v (ei . κ 1/µ + 1 (108) The most important parameters of the potential are the anisotropy parameters κ and κ . and obtain τ ij = −ei × rij rij ∂vij ∂ (nij · ei ) + ej ∂vij ∂ (ei · ej ) . κ2 + 1 χ = κ 1/µ − 1 . GayBerne intermolecular potential The most widely used pair potential for liquid crystal simulations is the GayBerne potential. χ= κ2 − 1 . (106) (107) 1 − χ2 (ei · ej ) . the diﬀerence in potential energy ∆U = Utrial − Uold of the trial and old systems is calculated 26 . (104) (105) ε (ei . It is based on the LennardJones potential extended to an anisotropic pair interaction [58. one begins with some (usually randomly selected) conﬁguration of molecular positions and orientations and then randomly moves and rotates molecules (avoiding molecular overlaps) to generate trial conﬁguration. rij ) = 4ε (ei . The most studied and widely used parameterizations are given in Table 1. ej . respectively. ej . nij ) = εs [ε (ei . ej . Here χ and χ denote the anisotropy of the molecular shape and of the potential energy. ri deﬁnes the position of the ith molecule. (103) where ρ = [rij − σ (ei . nij ) = σs 1− χ (ei · nij + ej · nij ) (ei · nij − ej · nij ) + 2 1 + χei · ej 1 − χei · ej µ ν 2 2 −1/2 . ej ) = χ 2 (ei · nij + ej · nij ) (ei · nij − ej · nij ) + 1 + χ ei · ej 1 − χ ei · ej 2 −1/2 2 2 . nij = rij /rij . 59]. The κ = σe /σs is roughly the molecular elongation and the κ = εs /εe is the welldepth ratio for the sidebyside and endtoend conﬁgurations. This dependence is deﬁned by the following set of equations σ (ei . where ε (ei . ej . nij ) + σs ]/σs .
and many signiﬁcant scientiﬁc and engineering discoveries have been made. with the old and trial states additionally weighted by a suitable function. vapor. a number of important properties. Isotropic. The MC technique of a canonical (N V T ) ensemble can be adapted to the constant pressure (N P T ) ensemble. The Metropolis description [66]. Wider nematic phase [63]. Therefore. The volume changes should be implemented. This weighting function should have the form which encourages the system to explore regions of phase space not frequently sampled by the Metropolis method. to insure they are slow compared to molecular motion. according to the ensemble. Liquid Crystal Thermometers As demonstrated earlier. If ∆U > 0 then the Boltzmann weight κ = exp(−∆U/kB T ) is compared to a generated random number. if ∆U is small. Applications for this special kind of material are still being discovered and continue to provide eﬀective solutions to many diﬀerent problems. described above. Liquid Crystal Displays The most common application of liquid crystal technology is liquid crystal displays (LCDs. the trial moves become accepted with lower and lower probability. and solid phases [62]. 1 3 Berardi and Zannoni parameters. Volume changes are attempted far less often than molecular moves. As ∆U increases. The weighted averages than should be corrected. only potential energies. generates conﬁgurations which are weighted to favor thermally populated states of the system. A particular example of nonBoltzmann sampling is the umbrellasampling technique [8].. 1 1 Bates and Luckhurst parameters [65]. the trial conﬁguration is accepted and the process is repeated.1]. κ = exp[−{∆U + P ∆V − N kB T ln(1−∆V /V )}/kB T ]. (17). Allows bigger timestep. It is usual practice that about half of trial moves should be accepted [8]. Because the pitch is dependent upon temperature. If ∆U < 0. 0 0 Soft repulsive potential.) This ﬁeld has grown into a multibillion dollar industry. from the sum of the pair potentials. but suppressed. requires substantial sampling over higherenergy conﬁgurations. chiral nematic (cholesteric) liquid crystals reﬂect light with a wavelength equal to the pitch. for example by scaling of all the molecular positions. This means that big ﬂuctuations in the energy are possible. for example free energies. nematic. as well as device technology. 1 2 Luckhurst et al [64]. leading to eﬃcient phase space sampling. smectic B.4 k 5 5 5 20 Table 1: Parameterizations of the Gay–Berne potential µ ν 2 1 De Miguel and Rull parameters [61]. the Boltzmann factor is close to 1 and the acceptance of the trial conﬁguration is highly probable. Note that forces and torques are never calculated. If α < κ. Then nonBoltzmann sampling can be used. 9 Applications Liquid crystal technology has had a major eﬀect many areas of science and engineering. the move is accepted.k 3 3 3 3 4. The principle of LCD operation is shown in Fig. However. The probability function also changes. the color reﬂected also is dependent 27 . giving desired ensemble averages. Neither real time nor real particle trajectories exist during MC phase sampling. otherwise it is rejected. choosing another molecule to move and rotate. α ∈ [0.
Figure 17: Activematrix liquid crystal display. Liquid Crystal Thermometers”. The electric pattern can be transmitted by an electrode. a liquid crystal cell is placed between two layers of photoconductor.prospectonellc. slurries. In this technology. it is possible to vary the intensity of transmitted light. See the following link for more details: http://www. Liquid crystals make it possible to accurately gauge temperature just by looking at the color of the thermometer. The resulting material is a sort of “swiss cheese” polymer with liquid crystal droplets ﬁlling in the holes. Figure 18: Temperature sensitive cholesteric liquid crystalline ﬁlm.com/lcr. By mixing diﬀerent compounds. (18). This technique is also used for the visualization of RF (radio frequency) waves in waveguides. They are used in medical applications where. These tiny droplets (a few microns across for practical applications) are responsible for the unique behavior of the material. upon temperature. Polymer dispersed liquid crystals PDLCs consist of liquid crystal droplets that are dispersed in a solid polymer matrix (see Fig. labels. which increases the material’s conductivity. Optical Imaging An application of liquid crystals that is only now being explored is optical imaging and recording. This causes an electric ﬁeld to develop in the liquid crystal corresponding to the intensity of the light. a device for practically any temperature range can be built. Other Liquid Crystal Applications Liquid crystals have a multitude of other uses. (19)). transient pressure transmitted 28 . “Reversible Temperature Indicating paints. which enables the image to be recorded. for example. By changing the orientation of the liquid crystal molecules with an electric ﬁeld. see Fig. Light is applied to the photoconductor.htm. They are used for nondestructive mechanical testing of materials under stress.
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