Rovibrational Hamiltonians for general polyatomic molecules in spherical polar parametrization. II. Nonorthogonal descriptions of internal molecular geometry

摘要

A rovibrational kinetic energy operator for a two-vector embedded reference frame is derived for general polyatomic molecules of arbitrary structure. New compact expressions for T in terms of angular momentum and linear momentum vector operators are explicitly given for tri-, tetra-, and pentatomic molecules. The necessary actions for the evaluation of kinetic energy matrix elements in a standard rotation-angular basis are summarized. The structure of kinetic energy operators in the body-fixed formulation is explained with the help of Cartesian components of angular momentum and linear momentum vector operators. Kinetic energy operators for tetratomic molecules in a bisector embedded body-fixed formulation and for sequentially bonded pentatomic molecules are derived to show how to use our general result for diverse coordinate systems.