Density functional study of zero-field splitting

Density functional theory (DFT) is applied to calculating zero-field splitting (ZFS) parameters caused by spin–orbit coupling (SOC). We examine the behavior and tendency of the method by applying it to some basic molecules such as carbene, binuclear single-molecule magnet (SMM), etc. It shows the method has good accuracy but it fails in particular cases. We suggest applicable region of the method.

Graphical abstractThe zero-field splitting (ZFS) parameters of some basic molecules and a single-molecule magnet [Mn(III)Cu(II)(Br-sap)2Cl(MeOH)] are calculated with the density functional theory (DFT). The DFT is applied to calculating ZFS parameters caused by 1-electron spin-orbit coupling (SOC). The pure DFT methods are in good agreement with the high-precision CI or MCSCF methods.Figure optionsDownload full-size imageDownload as PowerPoint slide