A comparative computer simulation on two liquid crystalline disubstituted biphenylcyclohexanes (BCHs) of general formula R-C6H10-C6H4-X with R: C3H7; X: H (BCH30) and R: C5H11; X: CN (BCH5CN) has been carried out on the basis of quantum mechanics and intermolecular forces. The net atomic charge and atomic dipole moment at each atomic center has been evaluated using the CNDO/2 method. The configurational energy has been computed using the Rayleigh-Schrodinger perturbation method. The obtained energies were used to calculate the probability of each configuration at phase transition temperature, using the Maxwell-Boltzmann's formula. The flexibility of various configurations has been studied in terms of variation of probability due to small departures from the most probable configurations. Further, the various possible geometrical arrangements between a molecular pair during the different modes of interactions have been considered. An attempt has been made to explain the mesogenic behavior of these compounds in terms of their relative order.