Application of magnetically-perturbed time-dependent density functional theory to magnetic circular dichroism. IV. The influence of zero-field splitting on the spectra of S > 1/2 molecules

An implementation into the ADF program of a method for calculating zero-field splitting (ZFS) of molecules with spin degenerate ground states and S > 1/2 is reported. ZFS can influence temperature-dependent magnetic circular dichroism (MCD) intensity. Previously published equations for the calculation of MCD with time-dependent density functional theory are modified to take zero-field splitting into account. The MCD spectra of the group 15 hydrides and the complex formed from iron (III), ethylenedi-aminetetraacetate and peroxide, [Fe(III)(EDTA)O-2](3) are simulated. These spectra are analyzed with particular reference to the influence of ZFS on the MCD intensity. (C) 2011 Elsevier B.V. All rights reserved.