VARIATIONAL DETERMINATION OF THE TWO-ELECTRON REDUCED DENSITY MATRIX WITHIN THE DOUBLY-OCCUPIED CONFIGURATION INTERACTION SCHEME: AN EXTENSION TO THE STUDY OF OPEN-SHELL SYSTEMS

A. TORRE; E. RIOS; L. LAIN; G.E. MASSACCESI; O.B. OÑA; D.R. ALCOBA

JOURNAL OF CHEMICAL PHYSICS

AMER INST PHYSICS

Lugar: New York; Año: 2020 vol. 153 p. 84101 - 84101

0021-9606

This work proposes to describe open-shell molecules or radicals using the framework of the doubly occupied configuration interaction (DOCI) treatments, so far limited to closed-shell system studies. The proposal is based on considering molecular systems in singlet states generated by adding extra hydrogen atoms located at infinite distance from the target radical system. The energy of this radical is obtained by subtracting the energies of the dissociated hydrogen atoms from that provided by the two-electron reduced density matrix corresponding to the singlet state system in the DOCI space, which is variationally calculated by imposing a set of N-representability conditions. This method is numerically assessed by describing potential energy curves and reduced density matrices in selected ionic and neutral open-shell systems in the doublet spin symmetry ground state.