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


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layer correlations of the in-plane order extending a molecules be connected by other types of bonds.
few layers in the SmF and only one layer in the SmI Molecules at the same height are joined by higher
[3]. The CrG and SmF tilt direction is between the energy flat-bonds with energy E(O) > E ( 1 ), rep-
bond directions of nearest neighbours (n.n), while resented by a plain line (Fig. la). A 12 % displace-
the tilt in the CrJ and SmI is along nearest neighbour ment would result in the higher energy (E(2))
bonds [7, 12]. configuration which we call a double-tilt-bond and
We consider a 2D hexagonal array which repre- would be represented by a double arrow. The
sents the projection of the molecular centers of mass assumption that there is an energy minimum as-
on a plane normal to the nematic director sociated with a particular molecular displacement is
(molecules long axis). Similar to roughening formu- based on the fact that this configuration is the
lations, associated with each 2D position (ri), is the structure of the low-temperature phase (CrG)
position of the molecule in the direction of its long (Fig. 2) in this sequence. We speculate that a
axis (hi ) - hi is the height of the average plane passing possible source of such a preferred configuration
through ri. Clearly, an average gradient of the might be the steric hindrance of the aromatic rings in
molecular heights corresponds to a net tilt of the adjacent molecules, which sweep out a large area
molecules relative to the layer normal. when the molecules are free to rotate about their
The principal assumption of this model is that long axes. In the diagrams (such as Figs. 2, 3, 4), we
draw the lines of flat-bonds (contours of constant
throughout the temperature range of interest, the
most energetically favorable configuration among height) with one independent arrow between adjac-
ent contours to show the direction of the tilt-bonds.
in-plane nearest neighbours is the one in which they
are displaced from each other along their nematic
It is redundant to draw all the tilt-bonds.
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 Fig. 2.-

CrG/SmF structure without defects. The posi-


adjacent molecules to be connected by tilt-bonds, tions of the molecules in a layer are projected on a plane
normal to the nematic director. The redundant tilt-bond
requires that even in the lowest energy state, some 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
Fig. 1. (a) A schematic showing preferred tilt-bond on
-

favour increased planar order. In other words, we


right and higher energy flat-bond on left. Below each, are assume a greater energy cost associated with planar
the bonds drawn on the lattice points, in the projection disorder of the layers at the surface. One motivation
used throughout the paper. The shape of the molecule
for this assumption comes from the experimental
portrayed qualitatively represents the volume swept out by observation that smectic ordering occurs at the
the rotation of molecule about its long axis. We only
surface of nematic liquid crystals [14]. Since, within
speculate that this might be the cause of a preference for
tilt-bonds. (b, c) Schematic showing side view of tilted the context of this model, the surface area per
structure and its projection. From (b) to (c), the tilt molecule does not change (i.e. in all structures the
decreases, the number of possible states increase and molecules have on average two flat-bonds, two
planar order decreases, as in SmA -> SmC. inward pointing tilt-bonds and two outward pointing
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tilt-bonds) surface tension does not come into play where the double sums are over all pairs of nearest
for the bulk interior layers. For the free surface neighbours in a layer, o- is the surface tension, A is
layer, there is a surface tension, because it is the the surface area, C is the spring constant due to
total exposed area which must be minimized. Interior intralayer forces which acts to keep a single layer flat
layers have their freedom to independently ripple and c (x ) is the effective spring constant due to the
constrained by the presence of adjacent layers and to sandwiching between adjacent layers which also
a simplest approximation, one can consider the keeps the molecules coplanar. x is a parameter
molecules to be bound midway between adjacent which is 0 when the molecules are all stacked end to
layers, by an effective harmonic potential. end and increases to 1 when they are at interstitial
Motivated by the fact that the molecules in the sites. c(x) decreases with increasing x. Since the
lowest temperature phases (CrG and CrB-AAA) are chains of the molecules have some flexibility even
on average stacked end to end, we make the added c(0) is finite. g (x) is the energy associated with the
assumption that the molecules in adjacent layers molecules not being end to end, and increases with
energetically prefer to be stacked so that their ends x.

are adjacent. The above assumptions can be sum- While we have proposed sources of, and forms for
marized in following Hamiltonians, for interior and the energies associated with planar order, the qual-
surface layers : itative development below does not depend on the

exact form but only the qualitative feature that there structures had a higher enthalpy, but also a larger
is an energetic cost for planar disorder, which is number of variants (entropy). Such a structure is
enhanced at the surface. portrayed in figure 3. Like the CrG, it has a maxi-
One mum number of tilt-bonds and no double-tilt-bonds.
important characteristic of this model is that
no explicit temperature-dependence of the interac- However, there is some planar disorder, where the
tions (i.e. specific conformal changes of the CrG had none. Planar disorder occurs because the
molecules) need be postulated to qualitatively pro- equal height contours are locally not always normal
duce the different phases. Internal degrees of free- to the direction of average tilt. The average tilt is
dom need not change with temperature, so tilt- toward the direction of a nearest neighbour, not
bonds always are energetically preferred. Thus, the between them as in the CrG phase. This is the
transitions are driven by the entropy associated with experimentally observed structure of the CrJ phase.
the degrees of freedom inherent in the model. While In order to be a stable phase, this structure must
it is clear that the molecules temperature-dependent have a higher entropy. In addition to defects (such as
internal degrees of freedom play a role in determin- flat-bond triangles ; or short breaks in a contour
ing E (n ), g (x ) etc., and are therefore required to resulting in double-tilt-bonds) common to both this
calculate the exact transitions in a particular ma- and the CrG phase, in the CrJ the wiggle of the
terial, they are not needed to explain the general contour need not be regular ( + - + - + - + ), but
features of the phase diagram. can have a whole class of variants (i.e. + - -

With the above assumptions, we will qualitatively + - + + ) not accessible in the phase with CrG

predict the phase sequence and thickness depen- symmetry. For a contour N bonds long, there are
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
Fig. 3.
-

CrJ/SmI structure. (a) and (b) are 2 of a whole


direction. class of variants which give this state higher entropy than
A higher temperature phase would be one whose CrG. Note that the points are not co-planar.
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N ! / [ (N /2 ) !]2 such CrJ conformations. This model CrJ/SmI should be preferred in thinner films. This
therefore predicts that CrJ/SmI should appear, in phase fits the description of the observed CrB
general, at higher temperature than CrG/SmF. phases, which are squeezed out by the lower tem-
Throughout the literature, this is always the case. perature tilted phases in thinner films [3]. The
Since surfaces give preference to the state with structure described here involves concentric regions
greater planar order, the model predicts that displaced from each other normal to the layers, thus
CrG/SmF would replace CrJ/SmI in thinner films. providing a mechanism for a modulation of the
The increasing temperature of the SmF - SmI tran- layers. These regions could be disordered, or
sition as film thickness is reduced [3, 15] shows that ordered in either one or two dimensions. It has been
the thickness dependence predicted by the model is experimentally determined that all the CrB phases
qualitatively correct. (in this phase sequence) are modulated, with the
We find that the entropy can be further increased modulation becoming ordered as the temperature is
by allowing the direction of the arrows between the reduced [3]. (The present model does not address
contours to alternate randomly. This leads to a the issue of the wavelength and ordering of the
structure with no net molecular tilt and a greater modulation.) Energetically, the molecules prefer to
enthalpy due to the larger layer ripple. To determine stack end to end ; however, even when the average
the shape of the contours we look for conformations stacking is end to end, the large disorder associated
of high entropy. In this case, entropy favors a large with layers sliding over one another in the crystalline
number of independent arrows, avoiding energy phases and the short interlayer correlation lengths in
costly terminating contours. This can be ac- the tilted hexatic phases show that locally all
complished by forming closed contour loops of finite molecules are not end to end (i.e. x > 0) and some
size, packed together in some conformation (Fig. 4). interpenetration is possible. In this phase, unlike the
This phase is non-tilted and is predicted to occur at CrG and CrJ phases, the entropy would be greatly
higher temperature than the CrG and CrJ. Because enhanced by allowing the arrows in adjacent layers
of their greater planar order, the CrG/SmF and 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.
4. CrB structure (a) shows typical closed concen- When all the arrows between contours point in the
Fig. -

same direction, tilt is maximized. As some arrows


tricloops. Note, a small closed loop defect. (b) Shows how
are reversed, the tilt decreases, the planar disorder
loops might fit together. The contours are of finite size,
creating a large number of independent arrows (not enthalpy increases and the number of possible states
shown). The fact that the bold contour spans the entire increase. Thus, the observed decrease in tilt as the
layer, shows that the structure is not tilted. SmC - SmA transition is approached, may be ex-
1447

plained in terms of the trade-off of entropy and per 35 molecules ; the CrG -> CrB latent heat would
planar disorder (Fig. 1b, c). The preference for correspond to 1 per 21 molecules.
planar order at the surface yields the prediction of an We have presented a simple model which we have
increase in the SmA --> SmC transition temperature argued may explain a variety of observed liquid
in thin films, which is experimentally observed [17]. crystal phases. The apparent diverse effects of a
In the nematic phase, the surface favors smectic surface on various structures was shown to be merely
ordering [14]. We have shown that the thickness manifestations of the energetic preference of the
dependence of the various other transitions is merely surface to be flat. We hope that the model proposed
another manifestation of surface induced planar here, will stimulate work to explain the details of the
order, sometimes appearing as surface induced tilt. many transitions of interest, through calculations
The entropies of transition (dS ) between these which may include defects in the tilt-bond structure
phases are of particular interest. In most typical first and the underlying lattice, as well as the incomplete
order transitions, dS - 0.7 R (i.e. in 70.7 : Nema- saturation of the nematic order parameter. One
tic > Isotropic dS 0.77 R and Nematic - SmA
=
might consider these transitions as forms of pre-
dS = 0.80 R) [10] corresponding to an opening of roughening in each layer [18], where the smectic to
one degree of freedom per molecule. However, the nematic transition is the final stage. We suggest that
transitions between the phases discussed in this an analogue to the SmF - SmI transition may be

paper show anomalously low dS, but cannot be found in vicinal FCC (111) crystal surfaces, or any
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 repulsive or straightening forces. We suggest that
transitions are not of the usual first order type, and this may be the case in double chain lyotropic
the small dS must come from large cooperative systems [19] where the possible pairings of the chains
effects, and not a molecular conformational or may lead to contour-like structures.
nearest neighbour structural change. Looking at
these numbers in terms of the model, we see that at Acknowledgments.
the CrG -> CrJ transition, there is 1 degree of free- I wish to acknowledge helpful conversations with
dom opened for every - 1000 molecules implying C. R. Safinya, D. R. Nelson, B. I. Halperin, S. K.
that in our model, 1000 contours (within and be- Sinha, K. S. Liang and G. S. Smith. I especially
tween layers) have conformal wiggles. Since the thank Prof. P. S. Pershan without whose support
period of the CrB modulation is - 20 molecular and guidance, this work would not have been
spacings [3], there are - 350 molecules in 10 contour possible. The part of this work done at Harvard was
rings, giving a rough estimate of 1 degree of freedom under support of N.S.F. grant DMR-80-20247.

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