A relativistic configuration interaction method with general expansions and initial applications to electronic g-factors

• Published in: The Journal of chemical physics 2023-07, Vol.159 (4)
• Main Authors: Nyvang, Andreas, Olsen, Jeppe
• Format: Article
• Language: English
• Subjects: Algorithms; Configuration interaction; Convergence; Electron spin; Electrons; Excitation; Hamiltonian functions; Mathematical analysis; Optimization; Physics; Relativistic effects; Routines
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0152655

A new implementation of the orbital-based two-component relativistic configuration interaction approach is reported and applied to calculations of the electronic g-shifts of three diatomic radicals: AlO, HgF, and PdH. The new implementation augments efficient routines for the calculation of nonrelativistic Hamiltonians with new vectorized routines for the calculation of the action of the one-electron spin–orbit operator and allows efficient calculations for the expansion of generalized active space type. The program makes full use of double group as well as time-reversal symmetry. Particle–hole reorganization of the operators is used to improve the efficiency for expansions with nearly fully occupied orbital spaces. The flexibility of the algorithm and program is used to investigate the convergence of electronic g-shifts for the three diatomic radicals as functions of the active space, states included in the orbital optimization, and excitation levels. It was possible to converge to the valence limits within a few percent using expansions containing up to quadruple excitations. However, when excitations from the core orbitals were added, it was not possible to demonstrate convergence to within a few percent with expansions containing at most 10 × 109 determinants.