Matrix Elements of Spin‐Dependent Operators over Total Molecular Wavefunctions

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Abstract
There is given a complete formulation of the evaluation of matrix elements of spin‐dependent operators over total wavefunctions for diatomic molecules. General account is taken of the nonseparability of position and spin spaces for polyelectronic problems, but consideration is restricted to orbital product electronic wavefunctions. The analysis has two phases. The first phase makes a complete reduction (including transformation of the operators to the molecular axis fixed coordinate system) of the N‐electron two‐nuclei coupled angular‐momentum problem using Racah tensor operator techniques. A full derivation is given for Hund's case b coupling scheme. Transformations to other coupling schemes are given in an appendix. The second phase extends the Slater‐Löwdin matrix element analysis for antisymmetric functions to include spin‐dependent operators.