General Internal Motion of Molecules, Classical and Quantum-Mechanical Hamiltonian

Abstract

The dynamics and the Hamiltonian of a general asymmetric‐top molecule undergoing almost arbitrary deformations are discussed. s vector notations are used for translational, rotational, and internal‐velocity coordinates. The kinetic energy is formulated by generalizing the G‐matrix technique known from the theory of molecular vibrations. A geometrical definition of the rotational coordinates referring to the instantaneous principal axis system is compared with a dynamical definition involving the over‐all angular momentum. States of general internal motion are associated by definition with zero linear momentum and zero over‐all angular momentum.