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

Citation
S. Coriani et al., Gauge-origin independent magneto-optical activity within coupled cluster response theory, J CHEM PHYS, 113(9), 2000, pp. 3561-3572
Citations number
49
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF CHEMICAL PHYSICS
ISSN journal
00219606 → ACNP
Volume
113
Issue
9
Year of publication
2000
Pages
3561 - 3572
Database
ISI
SICI code
0021-9606(20000901)113:9<3561:GIMAWC>2.0.ZU;2-I
Abstract
A gauge-origin invariant formulation of the frequency-dependent Verdet cons tant V(omega) of magneto-optical rotation and of the Faraday B term of magn etic circular dichroism for coupled-cluster wave functions is derived withi n the framework of variational response theory. Working expressions suitabl e for implementation in ab initio program packages are presented. These exp ressions 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 fo r V(omega) of HF and H-2. (C) 2000 American Institute of Physics. [S0021-96 06(00)30233-1].