Reversing and Mimicking the Characteristics of Vibronic Jahn-Teller Structures via Far Off-Resonance Interstate Interactions

Vibronic structures and splitting patterns whose characteristics are almost completely in reverse or highly similar to those resulting in the linear E ⊗ e Jahn-Teller (J-T) case may ensue when one doubly degenerate electronic state is coupled to another such state, well separated energywise, via linear vibronic interactions involving one of its potentially J-T active doubly degenerate modes. The vibronic splittings resulting via such interaction schemes are quite appreciable for typical cases and may be many times larger than those observed in the X̃(A1) → C̃(E) 1750 Å system of CF3I which has provided the classic manifestation for the action of the linear J-T effect.