Theoretical Chemistry Accounts

, 133:1561 | Cite as

A DFT + Umol model study of the self-interaction error in standard density functional calculations of Ni(CO) m (m = 1–4)

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Abstract

The trend in the first ligand dissociation energies of the subcarbonyl and carbonyl complexes Ni(CO) m , m = 1–4, is a typical example for consequences of the self-interaction error in calculations using semi-local density functional approximations. The self-interaction effects on bond lengths and ligand dissociation energies are examined with the DFT + Umol approach, an extension of the DFT + U method to molecular orbitals. A detailed analysis shows that (1) the Ni 3d subshell is most affected by self-interaction and (2) the +Umol correction on the CO 2π* orbitals has no major positive effect on the nickel carbonyl complexes, at variance with similar models for the CO adsorption on surfaces of transition metals.

Keywords

Nickel carbonyl complexes Metal–ligand dissociation energy Self-interaction error Molecular DFT + U 
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Notes

Acknowledgments

We thank Dr. Sven Krüger and Dr. Alexander Genest for numerous discussions. TMS is grateful for support by the International Graduate School of Science and Engineering (IGSSE) of Technische Universität München.

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Copyright information

© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Department Chemie and Catalysis Research CenterTechnische Universität MünchenGarchingGermany
  2. 2.Institute of High Performance ComputingAgency for Science, Technology and ResearchSingaporeSingapore

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