78 |
|
liquid crystal phases\cite{Lansac2003}. Other anisotropic models |
79 |
|
using Gay-Berne(GB) potential, which produce interactions that favor |
80 |
|
local alignment, give the evidence of the novel packing arrangements |
81 |
< |
of bent-core molecules\cite{Memmer2002,Orlandi2006}. |
81 |
> |
of bent-core molecules\cite{Memmer2002}. |
82 |
|
|
83 |
|
Experimental studies by Levelut {\it et al.}~\cite{Levelut1981} |
84 |
|
revealed that terminal cyano or nitro groups usually induce |
100 |
|
incorporating electrostatic interaction. |
101 |
|
|
102 |
|
In this chapter, we consider system consisting of banana-shaped |
103 |
< |
molecule represented by three rigid GB particles with one or two |
104 |
< |
point dipoles at different location. Performing a series of |
105 |
< |
molecular dynamics simulations, we explore the structural properties |
106 |
< |
of tilted smectic phases as well as the effect of electrostatic |
107 |
< |
interactions. |
103 |
> |
molecule represented by three rigid GB particles with two point |
104 |
> |
dipoles. Performing a series of molecular dynamics simulations, we |
105 |
> |
explore the structural properties of tilted smectic phases as well |
106 |
> |
as the effect of electrostatic interactions. |
107 |
|
|
108 |
|
\section{\label{liquidCrystalSection:model}Model} |
109 |
|
|
206 |
|
\end{equation} |
207 |
|
where $\epsilon _{fs}$ is the permittivity of free space. |
208 |
|
|
209 |
< |
\section{Computational Methodology} |
209 |
> |
\section{Results and Discussion} |
210 |
|
|
211 |
|
A series of molecular dynamics simulations were perform to study the |
212 |
|
phase behavior of banana shaped liquid crystals. In each simulation, |
218 |
|
a $160\times 160 \times 120$ box. After the dipolar interactions are |
219 |
|
switched on, 2~ns NPTi cooling run with themostat of 2~ps and |
220 |
|
barostat of 50~ps were used to equilibrate the system to desired |
221 |
< |
temperature and pressure. |
221 |
> |
temperature and pressure. NPTi Production runs last for 40~ns with |
222 |
> |
time step of 20~fs. |
223 |
|
|
224 |
|
\subsection{Order Parameters} |
225 |
|
|
236 |
|
u_{iy}u_{ix} & u_{iy}u_{iy}-\frac{1}{3} & u_{iy}u_{iz} \\ |
237 |
|
u_{iz}u_{ix} & u_{iz}u_{iy} & u_{iz}u_{iz}-\frac{1}{3} % |
238 |
|
\end{pmatrix}, |
239 |
< |
\label{lipidEq:po1} |
239 |
> |
\label{lipidEq:p2} |
240 |
|
\end{equation} |
241 |
|
where the $u_{i\alpha}$ is the $\alpha$ element of the unit vector |
242 |
|
$\mathbf{\hat{u}}_i$, and the sum over $i$ averages over the whole |
246 |
|
\langle P_2 \rangle = \frac{3}{2}\lambda_{\text{max}}. |
247 |
|
\label{lipidEq:po3} |
248 |
|
\end{equation} |
249 |
< |
In addition to the $P_2$ order parameter, $ R_{2,2}^2$ order |
250 |
< |
parameter for biaxial phase is introduced to describe the ordering |
251 |
< |
in the plane orthogonal to the director by |
252 |
< |
\begin{equation} |
253 |
< |
R_{2,2}^2 = \frac{1}{4}\left\langle {(x_i \cdot X)^2 - (x_i \cdot |
254 |
< |
Y)^2 - (y_i \cdot X)^2 + (y_i \cdot Y)^2 } \right\rangle |
255 |
< |
\end{equation} |
256 |
< |
where $X$, $Y$ and $Z$ are axis of the director frame. |
249 |
> |
%In addition to the $P_2$ order parameter, $ R_{2,2}^2$ order |
250 |
> |
%parameter for biaxial phase is introduced to describe the ordering |
251 |
> |
%in the plane orthogonal to the director by |
252 |
> |
%\begin{equation} |
253 |
> |
%R_{2,2}^2 = \frac{1}{4}\left\langle {(x_i \cdot X)^2 - (x_i \cdot |
254 |
> |
%Y)^2 - (y_i \cdot X)^2 + (y_i \cdot Y)^2 } \right\rangle |
255 |
> |
%\end{equation} |
256 |
> |
%where $X$, $Y$ and $Z$ are axis of the director frame. |
257 |
> |
The unit vector for the banana shaped molecule was defined by the |
258 |
> |
principle aixs of its middle GB particle. The $P_2$ order parameters |
259 |
> |
for the bent-core liquid crystal at different temperature is |
260 |
> |
summarized in Table~\ref{liquidCrystal:p2} which identifies a phase |
261 |
> |
transition temperature range. |
262 |
|
|
263 |
+ |
\begin{table} |
264 |
+ |
\caption{LIQUID CRYSTAL STRUCTURAL PROPERTIES AS A FUNCTION OF |
265 |
+ |
TEMPERATURE} \label{liquidCrystal:p2} |
266 |
+ |
\begin{center} |
267 |
+ |
\begin{tabular}{cccccc} |
268 |
+ |
\hline |
269 |
+ |
Temperature (K) & 420 & 440 & 460 & 480 & 600\\ |
270 |
+ |
\hline |
271 |
+ |
$\langle P_2\rangle$ & 0.984 & 0.982 & 0.975 & 0.967 & 0.067\\ |
272 |
+ |
\hline |
273 |
+ |
\end{tabular} |
274 |
+ |
\end{center} |
275 |
+ |
\end{table} |
276 |
+ |
|
277 |
|
\subsection{Structure Properties} |
278 |
|
|
279 |
< |
It is more important to show the density correlation along the |
280 |
< |
director |
279 |
> |
The molecular organization obtained at temperature $T = 460K$ (below |
280 |
> |
transition temperature) is shown in Figure~\ref{LCFigure:snapshot}. |
281 |
> |
The diagonal view in Fig~\ref{LCFigure:snapshot}(a) shows the |
282 |
> |
stacking of the banana shaped molecules while the side view in n |
283 |
> |
Figure~\ref{LCFigure:snapshot}(b) demonstrates formation of a |
284 |
> |
chevron structure. The first peak of Radial distribution function |
285 |
> |
$g(r)$ in Fig.~\ref{LCFigure:gofrz}(a) shows the minimum distance |
286 |
> |
for two in plane banana shaped molecules is 4.9 \AA, while the |
287 |
> |
second split peak implies the biaxial packing. It is also important |
288 |
> |
to show the density correlation along the director which is given by |
289 |
> |
: |
290 |
|
\begin{equation} |
291 |
< |
g(z) =< \delta (z-z_{ij})>_{ij} / \pi R^{2} \rho |
291 |
> |
g(z) =\frac{1}{\pi R^{2} \rho}< \delta (z-z_{ij})>_{ij} |
292 |
|
\end{equation}, |
293 |
|
where $z_{ij} = r_{ij} \dot Z$ was measured in the director frame |
294 |
< |
and $R$ is the radius of the cylindrical sampling region. |
294 |
> |
and $R$ is the radius of the cylindrical sampling region. The |
295 |
> |
oscillation in density plot along the director in |
296 |
> |
Fig.~\ref{LCFigure:gofrz}(b) implies the existence of the layered |
297 |
> |
structure, and the peak at 27 \AA is attribute to the defect in the |
298 |
> |
system. |
299 |
|
|
300 |
|
\subsection{Rotational Invariants} |
301 |
|
|
305 |
|
scatting\cite{Blum1972}. Latterly, expansion of the orientation pair |
306 |
|
correlation in terms of rotation invariant for molecules of |
307 |
|
arbitrary shape was introduce by Stone\cite{Stone1978} and adopted |
308 |
< |
by other researchers in liquid crystal studies\cite{Berardi2003}. |
309 |
< |
|
308 |
> |
by other researchers in liquid crystal studies\cite{Berardi2003}. In |
309 |
> |
order to study the correlation between biaxiality and molecular |
310 |
> |
separation distance $r$, we calculate a rotational invariant |
311 |
> |
function $S_{22}^{220} (r)$, which is given by : |
312 |
|
\begin{eqnarray} |
313 |
|
S_{22}^{220} (r) & = & \frac{1}{{4\sqrt 5 }} \left< \delta (r - |
314 |
|
r_{ij} )((\hat x_i \cdot \hat x_j )^2 - (\hat x_i \cdot \hat y_j |
315 |
|
)^2 - (\hat y_i \cdot \hat x_j )^2 + (\hat y_i \cdot \hat y_j |
316 |
< |
)^2 ) \right. \\ |
316 |
> |
)^2 ) \right. \notag \\ |
317 |
|
& & \left. - 2(\hat x_i \cdot \hat y_j )(\hat y_i \cdot \hat x_j ) - |
318 |
< |
2(\hat x_i \cdot \hat x_j )(\hat y_i \cdot \hat y_j )) \right> |
318 |
> |
2(\hat x_i \cdot \hat x_j )(\hat y_i \cdot \hat y_j )) \right>. |
319 |
|
\end{eqnarray} |
320 |
+ |
The long range behavior of second rank orientational correlation |
321 |
+ |
$S_{22}^{220} (r)$ in Fig~\ref{LCFigure:S22220} also confirm the |
322 |
+ |
biaxiality of the system. |
323 |
|
|
324 |
< |
\begin{equation} |
325 |
< |
S_{00}^{221} (r) = - \frac{{\sqrt 3 }}{{\sqrt {10} }}\left\langle |
326 |
< |
{\delta (r - r_{ij} )((\hat z_i \cdot \hat z_j )(\hat z_i \cdot |
327 |
< |
\hat z_j \times \hat r_{ij} ))} \right\rangle |
328 |
< |
\end{equation} |
324 |
> |
\begin{figure} |
325 |
> |
\centering |
326 |
> |
\includegraphics[width=4.5in]{snapshot.eps} |
327 |
> |
\caption[Snapshot of the molecular organization in the layered phase |
328 |
> |
formed at temperature T = 460K and pressure P = 1 atm]{Snapshot of |
329 |
> |
the molecular organization in the layered phase formed at |
330 |
> |
temperature T = 460K and pressure P = 1 atm. (a) diagonal view; (b) |
331 |
> |
side view.} \label{LCFigure:snapshot} |
332 |
> |
\end{figure} |
333 |
|
|
334 |
< |
\section{Results and Conclusion} |
335 |
< |
To investigate the molecular organization behavior due to different |
336 |
< |
dipolar orientation and position with respect to the center of the |
337 |
< |
molecule, |
334 |
> |
\begin{figure} |
335 |
> |
\centering |
336 |
> |
\includegraphics[width=\linewidth]{gofr_gofz.eps} |
337 |
> |
\caption[Correlation Functions of a Bent-core Liquid Crystal System |
338 |
> |
at Temperature T = 460K and Pressure P = 10 atm]{Correlation |
339 |
> |
Functions of a Bent-core Liquid Crystal System at Temperature T = |
340 |
> |
460K and Pressure P = 10 atm. (a) radial correlation function |
341 |
> |
$g(r)$; and (b) density along the director $g(z)$.} |
342 |
> |
\label{LCFigure:gofrz} |
343 |
> |
\end{figure} |
344 |
> |
|
345 |
> |
\begin{figure} |
346 |
> |
\centering |
347 |
> |
\includegraphics[width=\linewidth]{s22_220.eps} |
348 |
> |
\caption[Average orientational correlation Correlation Functions of |
349 |
> |
a Bent-core Liquid Crystal System at Temperature T = 460K and |
350 |
> |
Pressure P = 10 atm]{Correlation Functions of a Bent-core Liquid |
351 |
> |
Crystal System at Temperature T = 460K and Pressure P = 10 atm. (a) |
352 |
> |
radial correlation function $g(r)$; and (b) density along the |
353 |
> |
director $g(z)$.} \label{LCFigure:S22220} |
354 |
> |
\end{figure} |
355 |
> |
|
356 |
> |
\section{Conclusion} |
357 |
> |
|
358 |
> |
We have presented a simple dipolar three-site GB model for banana |
359 |
> |
shaped molecules which are capable of forming smectic phases from |
360 |
> |
isotropic configuration. Various order parameters and correlation |
361 |
> |
functions were used to characterized the structural properties of |
362 |
> |
these smectic phase. However, the forming layered structure still |
363 |
> |
had some defects because of the mismatching between the layer |
364 |
> |
structure spacing and the shape of simulation box. This mismatching |
365 |
> |
can be broken by using NPTf integrator in further simulations. The |
366 |
> |
role of terminal chain in controlling transition temperatures and |
367 |
> |
the type of mesophase formed have been studied |
368 |
> |
extensively\cite{Pelzl1999}. The the lack of flexibility in our |
369 |
> |
model due to the missing terminal chains could explained the fact |
370 |
> |
that we did not find evidence of chirality. |