Calculation of molecular g-tensors by sampling spin orientations of generalised Hartree-Fock states

Abstract

The variational inclusion of spin–orbit coupling in self-consistent field (SCF) calculations affords single-determinant wave functions that completely break spin symmetry. The individual components of the molecular g-tensor are commonly obtained from separate SCF solutions that align the magnetic moment along one of the three principal tensor axes. However, this strategy raises the question if energy differences between solutions are relevant, or how convergence is achieved if the principal axis system is not determined by molecular symmetry. The present work resolves these issues by a simple two-step procedure akin to the generator coordinate method (GCM). First, the orientation of the magnetic moment is constrained in generalised Hartree-Fock (GHF) calculations. Then, non-orthogonal configuration interaction between GHF determinants yields a Kramers doublet for the calculation of the complete g-tensor. Alternatively, diagonalisation in a basis spanned by spin rotations of a single GHF determinant results in qualitatively correct g-tensors by eliminating errors related to spin contamination. For small first-row molecules, these approaches are evaluated against experimental data and full configuration interaction results. It is further demonstrated for two fictitious tetrahedral and species that a GCM strategy can describe the spin–orbit splitting of orbitally-degenerate ground states, which may lead to negative g-values.