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Generalization of Brillouin theorem for the non-relativistic electronic Schrödinger equation in relation to coupling strength parameter, and its consequences in single determinant basis sets for configuration interactions

2017/08/31 by Sandor Kristyan, Kristyan, Sandor
Physics and Astronomy · #Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Quantum Physics (quant-ph) #physics.chem-ph #quant-ph

paper · pdf · doi:10.48550/arxiv.1709.01137

27 pages, 2 figures

arxiv created 2017/08/31 · arxiv updated 2017/09/06

Abstract

The Brillouin theorem has been generalized for the extended non-relativistic electronic Hamiltonian (Hkin+ Hne+ aHee) in relation to coupling strength parameter (a), as well as for the configuration interactions (CI) formalism in this respect. For a computation support, we have made a particular modification of the SCF part in the Gaussian package: essentially a single line was changed in an SCF algorithm, wherein the operator rij-1 was overwritten as 1/rij to a/rij, and a was used as input. The case a=0 generates an orto-normalized set of Slater determinants which can be used as a basis set for CI calculations for the interesting physical case a=1, removing the known restriction by Brillouin theorem with this trick. The latter opens a door from the theoretically interesting subject of this work toward practice.

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