Influence of effective Hamiltonian transformations on effective dipole moment parameters of C3 v molecules

Abstract

It is found that ambiguity of the effective Hamiltonian for singly excited nondegenerate and degenerate interacting vibrational states of C 3 v molecules (E. I. Lobodenko et al., J. Mol. Spectrosc. 126, 159–170 (1987)) leads to ambiguity of the effective dipole moment operators for the respective interacting fundamental nondegenerate ν n and degenerate ν t bands, for the rotational ν n - ν n , ν t - ν t bands, and for the ν t - ν t hot bands. The effective dipole moment operators for isolated degenerate ν t and rotational ν t - ν t bands also possess some ambiguity if the nondiagonal terms are retained in the respective effective Hamiltonian. The contributions to both the effective dipole moment parameters and the intensity parameters under effective Hamiltonian transformations are derived. Effective dipole moment operator terms are considered up to the third order.