Atom-pair formulation of the rotational and vibrational motions of molecules

Abstract

We have expressed the angular momentum and the internal kinetic energy of a molecule (a system of point masses) in terms of atom-pair contributions, paralleling the use of pairwise additive potential energy functions. The partitioning of the internal kinetic energy into rotational and vibrational contributions is then made following the analysis of Jellinek, J., and Li, D. H., 1989, 98, Phys. Rev. Lett., 62, 241. The resulting expressions contain pair position and velocity variables whose redundancy may be removed by transformation to Jacobi vector coordinates. These expressions should prove especially useful for describing the internal motions of clusters of like atoms.