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Benchmarking Approximate Density Functional Theory for s d Excitation Energies in 3d Transition Metal Cations NATHAN E SCHULTZ YAN ZHAO DONALD G TRUHLAR Department of Chemistry and Supercomputing Institute University of Minnesota 207 Pleasant Street Southeast Minneapolis Minnesota 55455 0431 Received 15 October 2006 Revised 31 January 2007 Accepted 4 February 2007 DOI 10 1002 jcc 20717 Published online 13 June 2007 in Wiley InterScience www interscience wiley com Abstract Holthausen has recently provided a comprehensive study of density functional theory for calculating the s d excitation energies of the 3d transition metal cations This study did not include the effects of scalar relativistic effects and we show here that the inclusion of scalar relativistic effects significantly alters the conclusions of the study We find contrary to the previous study that local functionals are more accurate for the excitation energies of 3d transition method cations than hybrid functionals The most accurate functionals of the 38 tested are SLYP PBE BP86 PBELYP and PW91 q 2007 Wiley Periodicals Inc J Comput Chem 29 185 189 2008 Key words density functional theory transition metals relativistic effects Introduction A recent paper by Holthausen1 benchmarked the accuracy of density functional theory2 3 DFT for the excitation energies Te of 3d transition metal cations The study is valuable because the ability of DFT to predict accurate excitation energies of transition metal compounds is an important issue in reactivity functional nanotechnology catalysis and metalloenzyme mechanisms as well as a subject of basic fundamental importance 4 25 The excitations are also of interest from a chemical standpoint because the chemically bonded systems often have depopulated 4s states and enhanced 3d populations The Holthausen1 study had four main thrusts 1 the technical and theoretical difficulties of calculating atomic Te 2 a survey of several DFT methods using the TZVP26 basis set which

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