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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.

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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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Authors and Affiliations

  1. Department Chemie and Catalysis Research Center, Technische Universität München, 85747, Garching, Germany

    Thomas M. Soini & Notker Rösch

  2. Institute of High Performance Computing, Agency for Science, Technology and Research, 1 Fusionopolis Way, Connexis #16-16, Singapore, 138632, Singapore

    Notker Rösch

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  1. Thomas M. Soini
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  2. Notker Rösch
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Correspondence to Notker Rösch.

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Soini, T.M., Rösch, N. A DFT + Umol model study of the self-interaction error in standard density functional calculations of Ni(CO) m (m = 1–4). Theor Chem Acc 133, 1561 (2014). https://doi.org/10.1007/s00214-014-1561-y

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