Theoretical analysis on phase behaviour of a liquid crystalline material – effect of molecular motions

Abstract

Molecular structure, and phase behaviour of 2-Cyano- N-[4-(4- n-pentyloxybenzoyloxy)-benzylidene] aniline (CPBBA) has been reported with respect to translational and orientational motions. The atomic net charge and dipole moment components at each atomic centre have been evaluated using the complete neglect differential overlap (CNDO/2) method. The modified Rayleigh–Schrodinger perturbation theory along with multicentered–multipole expansion method has been employed to evaluate the long-range intermolecular interactions, while a ‘ 6-exp’ potential function has been assumed for short-range interactions. The interaction energy values obtained through these computations have been used as input to calculate the configurational probability at room temperature (300 K), and nematic–isotropic transition temperature (396.5 K). On the basis of stacking, in-plane, and terminal interaction energy calculations, all possible geometrical arrangements between the molecular pairs have been considered. Molecular arrangements inside a bulk of materials have been discussed in terms of their relative order. Further, translational rigidity parameter has been estimated as a function of temperature to understand the phase behaviour of the compound. The present model is helpful to understand the effect of molecular motions on ordering, and phase behaviour of the mesogenic compounds.