Journal of Chemical Physics, Vol.103, No.6, 2272-2285, 1995
Towards Phase Transferable Potential Functions - Methodology and Application to Nitrogen
We describe a generalizable approach to the development of phase transferable effective intermolecular potentials and apply the method to the study of N-2 The method is based on a polarizable shell model description of the isolated molecule and uses experimental data to establish the parameters. Consideration of the Ne dimer shows this to be a conceptual advance over point polarizability descriptions of atomic interaction. Our parametrization of N-2 accurately describes not only the molecule’s electrostatic field (i.e., a practical representation of the molecular charge distribution) but also its response to electrical and mechanical stress (polarization and deformation). The purely intermolecular terms in our potential reflect shell-shell interactions. These are parametrized by fitting properties of the low temperature solid phase of nitrogen. We derive a phase transferable potential able to account for the second virial coefficient of the gas phase, the pressure induced phase transition between nitrogen’s cubic and tetragonal phrases, and a wide range of liquid properties (pair distribution function, heat of vaporization, self-diffusion coefficient and dielectric constant).
Keywords:MOLECULAR-DYNAMICS;HIGH-PRESSURE;LIQUID WATER;SOLID NITROGEN;MULTIPOLE MOMENTS;GASEOUS N-2;POLARIZABILITIES;MODEL;DIPOLE;COEFFICIENTS