Broken symmetry in valence molecular region within Hartree-Fock calculations

Abstract

Symmetry restricted and unrestricted Hartree-Fock calculations at theab initio LCAO-MO-SCF level have been carried out on the ground, core and valence hole states of N2 at various N-N distances. A one-particle criterion for symmetry breaking is discussed. Strong broken-symmetry effects in the inner valence molecular region of N2 have been found at larger N-N distances. This breaking of symmetry accompanying the symmetry unrestricted Hartree-Fock calculations of the inner valence hole states at large internuclear separations can be considered to be a common phenomenon with all highly symmetric molecules. The outer valence broken-symmetry effects with N2 have showed some deviations as compared with these effects in the inner valence and core molecular regions.