Revisiting the (E + A) ⊗ (e + a) problems of polyatomic systems with trigonal symmetry: general expansions of their vibronic Hamiltonians

Abstract

In this work, we derive general expansions in vibrational coordinates for the (E + A) ⊗ (e + a) vibronic Hamiltonians of molecules with one and only one C₃ axis. We first derive the expansion for the lowest C₃ symmetry. Additional symmetry elements systematically eliminate terms in the expansion. We compare our expansions with the previous results for two cases, the and the C₃ (E + A) ⊗ e. The first comparison demonstrates the robustness, completeness, conciseness, and convenience of our formalism. There is a systematic discrepancy in the second comparison. We discuss the origin of the discrepancy and use a numerical example to corroborate our expansion. Our formalism covers 153 vibronic problems in 6 point groups. It also gives general expansions for the spin–orbit vibronic Hamiltonians of the p-type (E + A) ⊗ (e + a) problems.