The Renner effect in a bent triatomic molecule executing a large amplitude bending vibration

Abstract

The theory is given for a model hamiltonian which combines the effects of large amplitude bending for a bent triatomic molecule with those arising from the coupling of vibrational, electronic and spin angular momenta characteristic of linear molecules. Two numerical examples are given for the application of the theory. (i) The vibronic and spin-orbit coupling between the Ã, ² A ₁ and [Xtilde], ² B ₁ states of PH₂ is discussed in detail in terms of the ²Π _u state of linear PH₂ with which they correlate. The v ₂ and K dependence of the doublet splitting in the à state is well represented in terms of a single spin coupling parameter for the ²Π _u state. (ii) The calculations give a quantitative account of the inversion for high v ₂ of the K = 0 and K = 1 levels of the bent B ₂ component of the ã, ³ A ₂ state of CS₂ arising from its correlation with a ³Δ_2u state of linear CS₂.