Analytic Derivative Calculation of Electronic g-Tensors based on Multireference Configuration Interaction Wavefunctions

Frank Neese (1)

1 Institute for Physical and Theoretical Chemistry

A computer program has been written to perform analytic derivative calculations of magnetic response properties based on uncontracted multireference configuration interaction (MRCI) wavefunctions. At this point orbital relaxation is neglected in this treatment and the basis functions are assumed to be independent of the perturbation. It is therefore equivalent to an untruncated sum-over-states (SOS) approach to the g-tensor. Hence, the treatment is more rigorous than all previous MRCI g-tensor calculations that have used truncated SOS formulations. In the present calculations, MR-CI calculations were performed on top of full valence complete-active space self-consistent field (CASSCF) reference wavefunctions without truncation of the reference or correlation spaces. Results are reported for two types of spin-orbit coupling operators, a simple effective nuclear charge approximation and the spin-orbit mean field (SOMF) approximation. The effects of orbital relaxation are discussed. The values obtained can be used in future calibration studies.

Mots clés: Physical Sciences

Frank Neese. Analytic Derivative Calculation of Electronic g-Tensors based on Multireference Configuration Interaction Wavefunctions. Molecular Physics, 2008, 105 (19-22), pp.2507-2514. ⟨10.1080/00268970701549389⟩. ⟨hal-00513126⟩