Generalized Spin in the Variance-Based Wave Function Optimization Method within the Doubly Occupied Configuration Interaction Framework

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 128; no. 34; pp. 7277 - 7283
• Main Authors: Alcoba, Diego R., Lain, Luis, Torre, Alicia, Ayala, Tomás R., Oña, Ofelia B., Massaccesi, Gustavo E., Peralta, Juan E., Melo, Juan I.
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 29-08-2024
• Subjects: A: New Tools and Methods in Experiment and Theory
• ISSN: 1089-5639; 1520-5215; 1520-5215
• DOI: 10.1021/acs.jpca.4c02742

In this work, we implement a generalized spin formulation of the doubly occupied configuration interaction methodology using the energy variance of the N-electron Hamiltonian. We perform the optimization of the N-electron wave functions and calculate their corresponding energies, using a unified variational treatment for ground and excited states based on the energy variance, which allows us to describe the entire energy spectra on an equal footing. We analyze the effects produced by the breakdown of the Ŝ​2 and Ŝ z symmetries in the spectra of model hydrogenic clusters in terms of energies and spin-related quantities, arising from the restricted, unrestricted, and generalized spin methods. The results are compared with other related methods as well as full configuration interaction.