The present article deals with the ordering and nematic phase behavior of naphthyl-ester, viz., 4-octylphenyl-6-octyloxy-2-naphthoate based on semiempirical approach at a molecular level. The atomic net charge and dipole moment at each atomic centre has been evaluated using the complete neglect differential overlap method. The modified Rayleigh-Schrodinger perturbation method 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 the short-range interactions. The total interaction energy values obtained through these computations have been used to calculate the probability of each configuration at room temperature, nematic-isotropic transition temperature, and above transition temperature using the Maxwell-Boltzmann formula. Further, the entropy of each configuration has been computed during the different modes of interactions. An effort has been made to develop a computational model at molecular level based on thermodynamic parameter introduced in this article.