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Spin-Orbit Matrix Elements for a Combined Spin-Flip and IP/EA Approach

submitted on 28.01.2020, 14:27 and posted on 29.01.2020, 06:35 by Oinam Meitei, Shannon Houck, Nicholas Mayhall
We present a practical approach for computing the Breit-Pauli spin-orbit matrix elements of multiconfigurational systems with both spin and spatial degeneracies based on our recently developed RAS-nSF-IP/EA method (JCTC, 15,
2278, 2019). The spin-orbit matrix elements over all the multiplet components are computed using a single one-particle reduced density matrix as a result of the Wigner-Eckart theorem. A mean field spin-orbit approximation was used to account for the two-electron contributions. Basis set dependence as well as the effect of including additional excitations is presented. The effect of correlating the core and semi-core orbitals is also examined. Surprisingly accurate results are obtained for spin-orbit coupling constants, despite the fact that the efficient wavefunction approximations we explore neglect the bulk of dynamical correlation.


Email Address of Submitting Author


Virginia Tech


United States

ORCID For Submitting Author


Declaration of Conflict of Interest



Read the published paper

in Journal of Chemical Theory and Computation