Nuclear Schrödinger Formulation for Bent Triatomic Systems
Development of rovibrational Hamiltonians for even the simple triatomic systems is not routine. As Sutcliffe  has pointed out, Eckart’s notion of an embedded equilibrium geometry for a stable triatomic molecule necessarily leads to differing rovibrational Hamiltonians for bent  and linear  nuclear configurations (as derived by Watson). That is, for a bent triatomic molecule with 3N-6 degrees of freedom, singularities in the mass-dependent potential energy operator (coined the “Watson” operator) necessarily cannot yield a smooth transition to a molecule with only 3N-5 degrees of freedom.
KeywordsTotal Angular Momentum Transformation Coefficient Equilibrium Bond Length Effective Moment Triatomic Molecule
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References to Chapter VI
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