| Abstract: | A statistical analysis has been carried out to determine the configurationally preference of a pair of 5OCB (4′‐n‐pentyloxy‐4‐biphenylcarbonitrile) molecules with respect to translatory and orientational motions. The CNDO/2 method has been employed to evaluate the net atomic charge and atomic dipole components at each atomic centre of the molecule. Modified Rayleigh‐Schrodinger perturbation theory along with multicentered‐multipole expansion method has been employed to evaluate long‐range intermolecular interactions, while a ‘6‐exp’ potential function has been assumed for short‐range interactions. The total interaction energy values obtained through these computations were used to calculate the probability of each configuration in vacuum and in a dielectric medium at phase transition temperature using Maxwell‐Boltzmann formula. It has been observed that the probabilities are redistributed in dielectric medium and there is considerable rise in the probabilities of interactions, although the order of preference remains the same. On the basis of stacking, in‐plane and terminal interaction energy calculations, all possible geometrical arrangements of the molecular pairs have been considered. The results are discussed in the light of experimental as well as other theoretical observations. |
