An Alternative Approach to the g‐Matrix: Theory and Applications

Starting from the formula proposed by Gerloch and McMeeking in 1975, the electronic g-matrix is expressed as a sum of two matrices called Lambda and Sigma describing the orbital and spin contributions respectively. This approach is applied on benchmark diatomic and triatomic molecules, and on TiF3 and Cu(NH3)4(2+) using either CASPT2 or CCSD(T) methods to calculate the spin-free states and SO-RASSI to calculate spin-orbit coupling. Results compare very well to experimental data and to previous theoretical work; and, for each molecule, the anisotropy of the g-matrix is modeled by the mean of a few parameters.