Gauge-origin independent magneto-optical activity within coupled cluster response theory

Sonia Coriani,a) Christof Hättig,b) Poul Jørgensen
Department of Chemistry, Århus University, DK-8000 Århus C, Denmark

Trygve Helgaker
Department of Chemistry, University of Oslo, P. O. B. 1033, N-0315 Oslo, Norway

J. Chem. Phys. 113, 3561-3572 (1998).
(Received 2 May 2000; accepted 9 June 2000)

A gauge-origin invariant formulation of the frequency-dependent Verdet constant V(&omega) of magneto-optical rotation and of the Faraday B term of magnetic circular dichroism for coupled-cluster wavefunctions is derived within the framework of variational response theory. Working expressions suitable for implementation in {\em ab initio} program packages are presented. These expressions have a structure similar to that of the expressions for the first hyperpolarizability and the two-photon transition moment, respectively, for the Verdet constant and the B term. The approach is general and can easily be extended to other similar frequency-dependent properties as well as to other wavefunction models. Pilot results at the CCSD level are presented for V(ω) of HF and H2.

a) Permanent address: Dipartimento di Scienze Chimiche, Università degli Studi di Trieste, Via Giorgieri 1, I-34127 Trieste, Italy.

a) Present address: Forschungszentrum Karlsruhe, Institute of Nanotechnology, P. O. Box 3640, D-76021 Karlsruhe, Germany

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