Hybrid Treatments Based on Determinant Seniority Numbers and Spatial Excitation Levels in the Configuration Interaction Framework

TORRE, ALICIA; MASSACCESI, GUSTAVO E.; LAIN, LUIS; CAPUZZI, PABLO; ALCOBA, DIEGO R.; OÑA, OFELIA B.

ADVANCES IN QUANTUM CHEMISTRY

ELSEVIER ACADEMIC PRESS INC

Año: 2018 vol. 76 p. 315 - 332

0065-3276

In this work we project the Hamiltonian of an N-electron system onto a set of N-electron determinants cataloged by their seniority numbers and their excitation levels with respect to a reference determinant. We show that, in open-shell systems, the diagonalization of the N-electron Hamiltonian matrix leads to eigenstates of the operator Ŝ2 when the excitation levels are counted in terms of spatial orbitals instead of spin-orbitals. Our proposal is based on the commutation relations between the N-electron operators seniority number and spatial excitation level, as well as between these operators and the spin operators Ŝ2 and Ŝz. Energy and 〈Ŝ2〉 expectation values of molecular systems obtained from our procedure are compared with those arising from the standard hybrid configuration interaction methods based on seniority numbers and spin-orbital-excitation levels. We analyze the behavior of these methods, evaluating their computational costs and establishing their usefulness.