title: Spin density and orbital optimization in open shell systems: A rational and computationally efficient proposal.
abstract: The present work describes a new method to compute accurate spin densities for open shell systems. The proposed approach follows two steps: first, it provides molecular orbitals which correctly take into account the spin delocalization; second, a proper CI treatment allows to account for the spin polarization effect while keeping a restricted formalism and avoiding spin contamination. The main idea of the optimization procedure is based on the orbital relaxation of the various charge transfer determinants responsible for the spin delocalization. The algorithm is tested and compared to other existing methods on a series of organic and inorganic open shell systems. The results reported here show that the new approach (almost black-box) provides accurate spin densities at a reasonable computational cost making it suitable for a systematic study of open shell systems.
authors.affiliation: Dipartimento di Scienze Chimiche e Famaceutiche, Universita di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara, Italy.
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Giner
authors.affiliation: Dipartimento di Scienze Chimiche e Famaceutiche, Universita di Ferrara, Via Fossato di Mortara 17, I-44121 Ferrara, Italy.
authors.forename: Celestino
authors.initials: C
authors.lastname: Angeli