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Spin–orbit interaction with nonlinear wave functions

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Abstract

The computation of the spin–orbit interaction is discussed for electronic wave functions expressed in the new nonlinear expansion form. This form is based on spin eigenfunctions using the graphical unitary group approach (GUGA). The nodes of a Shavitt graph in GUGA are connected by arcs, and a Configuration State Function (CSF) is represented as a walk along arcs from the vacuum node to a head node. The wave function is a linear combination of product functions each of which is a linear combination of all CSFs, wherein each CSF coefficient is a product of nonlinear arc factors. When the spin–orbit interaction is included the Shavitt graph is a union of single-headed Shavitt graphs each with the same total number of electrons and orbitals. Thus spin–orbit Shavitt graphs are multiheaded. For full-CI multiheaded Shavitt graphs, analytic expressions are presented for the number of walks, the number of nodes, the number of arcs, and the number of node pairs in the associated auxiliary pair graph. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007

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