Calculation of Verdet constants with time-dependent density functional theory: implementation and results for small molecules.
We report the implementation of a method by which to calculate Verdet constants for molecules. The method is based on gauge-including atomic orbitals (GIAOs) and density functional theory. Calculations based on this method afford magneto-optical rotations of the right magnitude for the molecules H2, N2, CO, HF, CH4, C2H2, H2O, and CS2. The results are in satisfactory agreement with experiment. We investigate the dependency of the results on the gauge origin if GIAOs are not chosen, the convergence of the results with the size of the basis set for AOs and GIAOs, and for H2O and CS2 a comparison of gas-phase and liquid phase values. For the small molecules studied here, large polarized basis sets with diffuse functions are required to obtain well converged results. The use of an asymptotically correct Kohn-Sham potential is advantageous.
Krykunov
Mykhaylo
M
Department of Chemistry, State University of New York at Buffalo, Buffalo, New York 14260-3000, USA.
Banerjee
Arup
A
Ziegler
Tom
T
Autschbach
Jochen
J