J. Phys.

France 49 (1988) 1443-1448 AOT 1988, E 1443

Classification
Physics Abstracts
61.30B - 64.70

A model for a generalized liquid crystal phase sequence

E. B. Sirota(*)
Department of Physics, Harvard University, Cambridge, MA 02138, U.S.A.

(Reu le 23 novembre 1987, rvis et accept le 12 avril 1988)

Rsum. On prsente un modle simple qui explique qualitativement les structures de la squence
2014

gnralise de phases cristal-liquide : cristal G/smectique F ~ cristal J/smectique I cristal B ~ smectique

~

C ~ smectique A. Le modle suppose un potentiel effectif longue distance qui impose des couches plates et
une interaction partiellement frustre entre proches voisins qui induit une inclinaison des molcules. Le
modle explique galement leffet dune surface libre sur le diagramme de phases.

Abstract. A simple model is presented which is shown to qualitatively explain the structures of the
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generalized liquid crystal phase sequence : Crystalline-G/Smectic-F ~ Crystalline-J/Smectic-I ~ Crystalline-

B ~ Smectic-C ~ Smectic-A. The model assumes an effectively long range potential which keeps the layers
flat, and a partially frustrated nearest neighbour interaction which induces molecular tilt. In addition to
determining the order of the phases, the model also explains the observed effects of a free surface, on the
phase diagram.

Liquid crystals are known to exhibit a large variety
of smectic, or layered phases [1]. Transitions be-
tween these phases can be described in terms of
changes in different types of order including the 2-
dimensional (2D) positional and bond orientational
order of the molecules [2-4] and the freezing out and
ordering of the rotational degree of freedom [5]. The
one to be discussed below, involves the relative
displacements of the molecules, along their long
axes. This is directly related to molecular tilt. We
propose a model, similar to roughening models [6]
which can explain the structure of the observed
phases, their relative position in the phase sequence
and the effect of a free surface on the phase diagram.
The experimentally observed transitions between
the phases are first order, and their anomalously low
latent heats make them particularly novel from a
statistical mechanics point of view.
We will primarily be concerned with the
generalized phase sequence: Crystalline-
G(CrG)/Smectic-F(SmF) Crystalline-
- polar liquid smectics and reentrant nematics [11].
J(CrJ)/Smectic-I(SmI) --+ Crystalline-B(CrB)
Smectic-C(SmC) -+ Smectic-A(SmA) which is exhi-
bited by many homologous series [3, 5, 7-9]. 4-n-
heptyloxybenzylidene-4-n-heptylaniline (70.7),
whose thickness dependent phase diagram (in freely
suspended films) has been studied in detail, exhibits
all these phases (except CrJ), including the various
modulated CrB stacking sequences [3, 8, 10]. We
will use 70.7 to quote specific numbers ; however,
the qualitative properties of the phase diagram are
the same in other materials. As the rotational degree
of freedom of the molecules is not included in the
present model, the tendency of some of these
systems to order into a herringbone structure [5] at
lower temperatures, turning the crystalline-G, J and
B phases into H, K and E respectively, will not be
explained by this model. Some liquid crystalline
materials have sequences such as SmA - Hexatic-
B -> CrB, or a series of bilayer SmA phases where
the tilt does not drive the transitions and the model
presented here would not directly apply ; however, a
similar model has been used in conjunction with
To remind the reader ; the CrG, CrJ and CrB
phases are layered 3D crystals with soft modes
corresponding to the layers sliding over one another.
The CrG and CrJ are tilted. When occurring between
tilted phases (the case described in this paper) the
CrB is modulated with wavevector(s) in the plane of
the layers and polarization normal to the layers. The
SmF and SmI are stacked tilted hexatics with inter-

Article published online by EDP Sciences and available at http://dx.doi.org/10.1051/jphys:019880049080144300

1444
layer correlations of the in-plane order extending a
few layers in the SmF and only one layer in the SmI
[3]. The CrG and SmF tilt direction is between the
bond directions of nearest neighbours (n.n), while
the tilt in the CrJ and SmI is along nearest neighbour
bonds [7, 12].
We consider a 2D hexagonal array which repre-
sents the projection of the molecular centers of mass
on a plane normal to the nematic director
(molecules long axis). Similar to roughening formu-
lations, associated with each 2D position (ri), is the
position of the molecule in the direction of its long
axis (hi ) - hi is the height of the average plane passing
through ri. Clearly, an average gradient of the
molecular heights corresponds to a net tilt of the
molecules relative to the layer normal.
The principal assumption of this model is that
throughout the temperature range of interest, the
most energetically favorable configuration among
in-plane nearest neighbours is the one in which they
are displaced from each other along their nematic
director by - 6 % of their length (Fig. la). We will
refer to such pairs of molecules as being connected
by a tilt-bond of energy E(1 ), which we graphically
represent by an arrow connecting the lattice sites,
pointing toward the molecule with greater height.
(In this simple model, we only consider integral
multiples of this displacement.) The inherent frus-
tration caused by the inability of three mutually
adjacent molecules to be connected by tilt-bonds,
requires that even in the lowest energy state, some
Fig. 1. (a) A schematic showing preferred tilt-bond on
-
right and higher energy flat-bond on left. Below each, are
the bonds drawn on the lattice points, in the projection
used throughout the paper. The shape of the molecule
portrayed qualitatively represents the volume swept out by
the rotation of molecule about its long axis. We only
speculate that this might be the cause of a preference for
tilt-bonds. (b, c) Schematic showing side view of tilted
structure and its projection. From (b) to (c), the tilt
decreases, the number of possible states increase and
planar order decreases, as in SmA -> SmC.
molecules be connected by other types of bonds.
Molecules at the same height are joined by higher
energy flat-bonds with energy E(O) > E ( 1 ), rep-
resented by a plain line (Fig. la). A 12 % displace-
ment would result in the higher energy (E(2))
configuration which we call a double-tilt-bond and
would be represented by a double arrow. The
assumption that there is an energy minimum as-
sociated with a particular molecular displacement is
based on the fact that this configuration is the
structure of the low-temperature phase (CrG)
(Fig. 2) in this sequence. We speculate that a
possible source of such a preferred configuration
might be the steric hindrance of the aromatic rings in
adjacent molecules, which sweep out a large area
when the molecules are free to rotate about their
long axes. In the diagrams (such as Figs. 2, 3, 4), we
draw the lines of flat-bonds (contours of constant
height) with one independent arrow between adjac-
ent contours to show the direction of the tilt-bonds.
It is redundant to draw all the tilt-bonds.
Fig. 2.-
CrG/SmF structure without defects. The posi-
tions of the molecules in a layer are projected on a plane
normal to the nematic director. The redundant tilt-bond
arrows are replaced by single arrows between contours.
The contours extend indefinitely.
The second ingredient of this model is the energy
associated with planar disorder. In the layered
smectic-like phases, the molecules tend to lie in
planes nearly normal to the nematic director. We
assume that the layering is maintained by an effec-
tively long range potential, such as induced dipoles
[13], which favors keeping the molecules in the
plane. The layers at a free surface are kept flat by
surface tension. The existence of flat layers is
energetically preferred by the system, and a rippling
or corrugation of the layers costs energy. Qualitat-
ively speaking, our only assumption involving the
effect of the free surfaces of the sample is that they
favour increased planar order. In other words, we
assume a greater energy cost associated with planar
disorder of the layers at the surface. One motivation
for this assumption comes from the experimental
observation that smectic ordering occurs at the
surface of nematic liquid crystals [14]. Since, within
the context of this model, the surface area per
molecule does not change (i.e. in all structures the
molecules have on average two flat-bonds, two
inward pointing tilt-bonds and two outward pointing

tilt-bonds) surface tension does not come into play
for the bulk interior layers. For the free surface
layer, there is a surface tension, because it is the
total exposed area which must be minimized. Interior
layers have their freedom to independently ripple
constrained by the presence of adjacent layers and to
a simplest approximation, one can consider the
molecules to be bound midway between adjacent
layers, by an effective harmonic potential.
Motivated by the fact that the molecules in the
lowest temperature phases (CrG and CrB-AAA) are
on average stacked end to end, we make the added
assumption that the molecules in adjacent layers
energetically prefer to be stacked so that their ends
are adjacent. The above assumptions can be sum-
marized in following Hamiltonians, for interior and
surface layers :
exact form but only the qualitative feature that there
is an energetic cost for planar disorder, which is
enhanced at the surface.
One
important characteristic of this model is that
no explicit temperature-dependence of the interac-
tions (i.e. specific conformal changes of the
molecules) need be postulated to qualitatively pro-
duce the different phases. Internal degrees of free-
dom need not change with temperature, so tilt-
bonds always are energetically preferred. Thus, the
transitions are driven by the entropy associated with
the degrees of freedom inherent in the model. While
it is clear that the molecules temperature-dependent
internal degrees of freedom play a role in determin-
ing E (n ), g (x ) etc., and are therefore required to
calculate the exact transitions in a particular ma-
terial, they are not needed to explain the general
features of the phase diagram.
With the above assumptions, we will qualitatively
predict the phase sequence and thickness depen-
dence, based on the tilt-bond preference and the
trade-off of the enthalpy of planar disorder and
entropy. The low-temperature phase is the one with
lowest enthalpy and has the CrG structure shown in
figure 2. There is a maximum fraction of tilt-bonds
(2/3), perfect planar order (molecules are all co-
planar) and end to end average stacking. The
structure which satisfies this condition is the one
with infinite, straight, parallel flat-bond contours
with the independent arrows all pointing in the same
direction.
A higher temperature phase would be one whose
1445
where the double sums are over all pairs of nearest
neighbours in a layer, o- is the surface tension, A is
the surface area, C is the spring constant due to
intralayer forces which acts to keep a single layer flat
and c (x ) is the effective spring constant due to the
sandwiching between adjacent layers which also
keeps the molecules coplanar. x is a parameter
which is 0 when the molecules are all stacked end to
end and increases to 1 when they are at interstitial
sites. c(x) decreases with increasing x. Since the
chains of the molecules have some flexibility even
c(0) is finite. g (x) is the energy associated with the
molecules not being end to end, and increases with
x.
While we have proposed sources of, and forms for
the energies associated with planar order, the qual-
itative development below does not depend on the
structures had a higher enthalpy, but also a larger
number of variants (entropy). Such a structure is
portrayed in figure 3. Like the CrG, it has a maxi-
mum number of tilt-bonds and no double-tilt-bonds.
However, there is some planar disorder, where the
CrG had none. Planar disorder occurs because the
equal height contours are locally not always normal
to the direction of average tilt. The average tilt is
toward the direction of a nearest neighbour, not
between them as in the CrG phase. This is the
experimentally observed structure of the CrJ phase.
In order to be a stable phase, this structure must
have a higher entropy. In addition to defects (such as
flat-bond triangles ; or short breaks in a contour
resulting in double-tilt-bonds) common to both this
and the CrG phase, in the CrJ the wiggle of the
contour need not be regular ( + - + - + - + ), but
can have a whole class of variants (i.e. + - -
+ - + + ) not accessible in the phase with CrG
symmetry. For a contour N bonds long, there are
Fig. 3.
-
CrJ/SmI structure. (a) and (b) are 2 of a whole
class of variants which give this state higher entropy than
CrG. Note that the points are not co-planar.
1446
N ! / [ (N /2 ) !]2 such CrJ conformations. This model
therefore predicts that CrJ/SmI should appear, in
general, at higher temperature than CrG/SmF.
Throughout the literature, this is always the case.
Since surfaces give preference to the state with
greater planar order, the model predicts that
CrG/SmF would replace CrJ/SmI in thinner films.
The increasing temperature of the SmF - SmI tran-
sition as film thickness is reduced [3, 15] shows that
the thickness dependence predicted by the model is
qualitatively correct.
We find that the entropy can be further increased
by allowing the direction of the arrows between the
contours to alternate randomly. This leads to a
structure with no net molecular tilt and a greater
enthalpy due to the larger layer ripple. To determine
the shape of the contours we look for conformations
of high entropy. In this case, entropy favors a large
number of independent arrows, avoiding energy
costly terminating contours. This can be ac-
complished by forming closed contour loops of finite
size, packed together in some conformation (Fig. 4).
This phase is non-tilted and is predicted to occur at
higher temperature than the CrG and CrJ. Because
of their greater planar order, the CrG/SmF and
4. CrB structure (a) shows typical closed concen-
Fig. -
tricloops. Note, a small closed loop defect. (b) Shows how
loops might fit together. The contours are of finite size,
creating a large number of independent arrows (not
shown). The fact that the bold contour spans the entire
layer, shows that the structure is not tilted.
CrJ/SmI should be preferred in thinner films. This
phase fits the description of the observed CrB
phases, which are squeezed out by the lower tem-
perature tilted phases in thinner films [3]. The
structure described here involves concentric regions
displaced from each other normal to the layers, thus
providing a mechanism for a modulation of the
layers. These regions could be disordered, or
ordered in either one or two dimensions. It has been
experimentally determined that all the CrB phases
(in this phase sequence) are modulated, with the
modulation becoming ordered as the temperature is
reduced [3]. (The present model does not address
the issue of the wavelength and ordering of the
modulation.) Energetically, the molecules prefer to
stack end to end ; however, even when the average
stacking is end to end, the large disorder associated
with layers sliding over one another in the crystalline
phases and the short interlayer correlation lengths in
the tilted hexatic phases show that locally all
molecules are not end to end (i.e. x > 0) and some
interpenetration is possible. In this phase, unlike the
CrG and CrJ phases, the entropy would be greatly
enhanced by allowing the arrows in adjacent layers
to vary independently of each other. By having the
ends of the molecules lying on average at interstitial
sites of the ends in adjacent layers (x --> 1 ), the
energy cost associated with independent rippling of
adjacent layers would be reduced, thus reducing the
energy associated with many independent confor-
mations, effectively making them allowable states.
This trade-off of energy and entropy would tend to
favor ABAB-like stacking at high temperature and
AAA at low temperature. Virtually all CrB phases
show this restacking, with the molecules always
moving from interstitial sites, toward end to end
stacking, with decreasing temperature [3, 8, 16].
Furthermore, from the model, we would never
expect to see such restacking in the CrG, and hardly
ever in the CrJ. Restacking is not observed in those
phases.
In systems where the CrB is absent, the Semi -
SmC transition can be continuous [4]. This suggests
that the local packing of molecules is the same,
namely, that the preference for tilt-bonds remains,
even in the more disordered high temperature
phases. Thus we can consider drawing the contours
even though the underlying lattice sites are not
crystalline. We had expected the untilted CrB struc-
ture to include tilt-bonds since it occurs between the
SmI and SmC. The above description of CrB is
consistent with this idea.
When all the arrows between contours point in the
same direction, tilt is maximized. As some arrows
are reversed, the tilt decreases, the planar disorder
enthalpy increases and the number of possible states
increase. Thus, the observed decrease in tilt as the
SmC - SmA transition is approached, may be ex-

plained in terms of the trade-off of entropy and
planar disorder (Fig. 1b, c). The preference for
planar order at the surface yields the prediction of an
increase in the SmA --> SmC transition temperature
in thin films, which is experimentally observed [17].
In the nematic phase, the surface favors smectic
ordering [14]. We have shown that the thickness
dependence of the various other transitions is merely
another manifestation of surface induced planar
order, sometimes appearing as surface induced tilt.
The entropies of transition (dS ) between these
phases are of particular interest. In most typical first
order transitions, dS - 0.7 R (i.e. in 70.7 : Nema-
tic > Isotropic dS 0.77 R and Nematic - SmA
=
dS = 0.80 R) [10] corresponding to an opening of
one degree of freedom per molecule. However, the
transitions between the phases discussed in this
paper show anomalously low dS, but cannot be
continuous. For CrB -> CrG dS 0.049 R, for the
= other system where one can reduce the problem to
CrB restacking transitions dS 0.0004 R [10] and
= that of contours on a hexagonal lattice with effective
for CrG - CrJ dS 0.0007 R [7]. Clearly, these
transitions are not of the usual first order type, and
the small dS must come from large cooperative
effects, and not a molecular conformational or
nearest neighbour structural change. Looking at
these numbers in terms of the model, we see that at
the CrG -> CrJ transition, there is 1 degree of free-
dom opened for every - 1000 molecules implying
that in our model, 1000 contours (within and be-
tween layers) have conformal wiggles. Since the
period of the CrB modulation is - 20 molecular
spacings [3], there are - 350 molecules in 10 contour
rings, giving a rough estimate of 1 degree of freedom
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1447
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We have presented a simple model which we have
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crystal phases. The apparent diverse effects of a
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Acknowledgments.
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Sinha, K. S. Liang and G. S. Smith. I especially
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