Theoretical and Computational Chemistry

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



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.


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Supplementary material

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