Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5375585 | Chemical Physics | 2009 | 7 Pages |
Abstract
In an effort towards the reliable calculation of EPR parameters of molybdenum and tungsten enzyme active sites, the effect of higher-order spin-orbit effects and of exchange-correlation functional on the electronic g-tensors of small [MVOCl5]2â and medium-sized [MVO(bdt)2]â (bdt = benzene-1,2-dithiolate), [MVOCl3(bpy)] (bpy = bipyridine) complexes (M = Mo or W) has been evaluated. Comparison of one-component calculations with perturbational treatment of spin-orbit coupling and two-component non-collinear spin density functional calculations indicate the substantial importance of higher-order spin-orbit effects, in particular for the tungsten species. Pseudopotential calculations tend to underestimate the spin-orbit effects compared to all-electron calculations based on the Douglas-Kroll-Hess Hamiltonian. Hybrid functionals with somewhat enhanced exact-exchange admixture tend to provide better agreement with experiment than pure gradient-corrected functionals.
Keywords
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Peter Hrobárik, Olga L. Malkina, Vladimir G. Malkin, Martin Kaupp,