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.
Bolvin
Hélène
H
Laboratoire de Chimie Quantique, Institut de Chimie de Strasbourg, LC3-UMR 7177, 4 rue Blaise Pascal, 67000 Strasbourg, France. helene.bolvin@quantix.u-strasbg.fr