Calculation of the A term of magnetic circular dichroism based on time dependent-density functional theory I. Formulation and implementation.

A procedure for calculating the A term and the A/D ratio of magnetic circular dichroism (MCD) within time-dependent density functional theory (TD-DFT) is described. Utilizing an implementation of the MCD theory within the Amsterdam Density Functional program, the A term contributions to the MCD spectra of MnO(4) (-), CrO(4) (2-), VO(4) (3-), MoO(4) (2-), VO(4) (3-), MoS(4) (2-), Se(4) (2+), Te(4) (2+), Fe(CN)(6) (4-), Ni(CN)(4) (2-), trichlorobenzene, hexachlorobenzene, tribromobenzene, and hexabromobenzene are calculated. For the most part, agreement between theory and experiment for A/D ratios and the relative magnitude of A terms is found to be good, leading to simulated spectra that are similar in appearance to those derived from measurements.