AI Article Synopsis
- This work focuses on calculating spin-orbit couplings (SOCs) using the Breit-Pauli Hamiltonian and the RASCI method, incorporating various excitation types for non-relativistic wave functions.
- The implementation utilizes the Wigner-Eckart theorem to efficiently compute the SOC matrix by only calculating one key transition between spin multiplets.
- Results demonstrate that careful consideration of electronic correlation and basis sets is crucial, showcasing RASCI's effectiveness in analyzing spin-forbidden processes and molecular magnetism.
Article Abstract
This work presents the formalism and implementation for calculations of spin-orbit couplings (SOCs) using the Breit-Pauli Hamiltonian and non-relativistic wave functions described by the restricted active space configuration interaction (RASCI) method with general excitation operators of spin-conserving spin-flipping, ionizing, and electron-attaching types. The implementation is based on the application of the Wigner-Eckart theorem within the spin space, which enables the calculation of the entire SOC matrix based on the explicit calculation of just one transition between the two spin multiplets. Numeric results for a diverse set of atoms and molecules highlight the importance of a balanced treatment of correlation and adequate basis sets and illustrate the overall robust performance of RASCI SOCs. The new implementation is a useful addition to the methodological toolkit for studying spin-forbidden processes and molecular magnetism.
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| http://dx.doi.org/10.1063/5.0029146 | DOI Listing |
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