A symmetry-based approach to the effective Hamiltonian for symmetric top molecules in degenerate vibronic states

Abstract

The effective Hamiltonian for a symmetric top molecule in a degenerate vibronic state is obtained. Included in this Hamiltonian are the rotational, spin-rotational, spin-orbit coupling and electronic spin-spin interactions. The terms of the Hamiltonian are expressed as the product of molecular ‘constants,’ rotational angular momentum operators, and symmetry operators. A formalism is derived, and tables included, to determine whether or not a symmetry operator vanishes for a given vibronic state of a particular molecular symmetry. In this way, one can easily obtain all the non-vanishing Hamiltonian terms for a particular application.