ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
We present a formalism for molecular liquids in which the interatomic force depends upon both the internuclear separation and on internal, quantum degrees of freedom. The internal degrees of freedom are spin and orbital angular momenta, and they are eventually approximated to yield a purely classical function for the interatomic interaction. We show that the interpolative character of the classical energy function is derived from a resolution of a model Hamiltonian. The formal derivation of the potential energy function is illustrated with an explicit calculation for some nonpolar and polar systems, and with discussion for ionic systems. Our derivation emphasizes an alternative to the ever more popular three-body potential energy functions for statistical mechanics studies of liquids. We outline the path to be followed in computer simulations and analytical studies of liquids with our pairwise-additive, spin-dependent potential energy functions.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.457653
