Calculation of origin-independent optical rotation tensor components in approximate time-dependent density functional theory.
We outline an implementation of the origin-independent optical rotation tensor, which includes electric dipole-magnetic dipole and electric dipole-electric quadrupole polarizability. The method is based on approximate time-dependent density functional theory. We utilize time-periodic magnetic-field-dependent basis functions as well as a modified velocity-gauge formulation of dynamic polarizability tensors in order to obtain a gauge-origin independence. To ensure gauge-origin independence of the results within a given numerical accuracy, density fit coefficient derivatives are employed. A damping constant has been introduced into the linear response equations to treat both resonance and nonresonance regions of optical activity. We present calculations for trans-2,3-dimethyloxirane and derivatives thereof as well as calculations for androst-4,17-dien-3-one. In the Appendix, we derive the equivalence between the common-gauge origin and gauge-including atomic orbitals formulations for the optical rotation tensor in time-dependent DFT.
Krykunov
Mykhaylo
M
Department of Chemistry, State University of New York at Buffalo, 312 Natural Sciences Complex, Buffalo, NY 14260-3000, USA.
Autschbach
Jochen
J