A new perturbation expansion for fluids of nonspherical molecules

摘要: The free energy of a fluid composed nonspherical molecules is expanded about that for reference rigid, molecules. expansion procedure involved separating the intermolecular pair potential into repulsive and attractive regions each set relative orientations, similar to used by Weeks, Chandler, Andersen monatomic fluids. properties system are evaluated using Bellemans. Calculated thermodynamic compared with Monte Carlo results fluids uLJ + ua, where Lennard‐Jones model ua either point dipole, quadrupole, or an anisotropic overlap potential. For dipoles, agreement satisfactory values reduced dipole moment μ/(eσ3)1/2 up 1, while quadrupoles good found Q/(eσ5)1/2 0.8. larger multipole moments Bellemans fails. potentials method seemed al...