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Theoretical investigation of photoelectron spectra and magnetically induced current densities in ring-shaped transition-metal oxides

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Abstract

The molecular structures of cyclic group 6 transition-metal (M = Cr, Mo, W, Sg) oxides (M 3O 0/1−/2−9 ) species have been optimized at density functional theory (DFT) levels. The photoelectron spectra (PES) of M 3O −9 (M = Cr, Mo, W) were calculated at the time-dependent DFT and approximate coupled-cluster singles doubles (CC2) levels and compared with experimental results. The CC2 calculations did not yield any reliable PES, whereas the molecular structures can be identified by comparing PES obtained at the DFT level with experiment. Magnetically induced current densities were calculated at the DFT level using the gauge-including magnetically induced current (gimic) approach. The current strengths and current pathways of the neutral M3O9 and the dianionic M3O 2−9 (M = Cr, Mo) oxides were investigated and analyzed with respect to a previous prediction of d-orbital aromaticity for Mo3O9 anions. Current-density calculations provide ring-current strengths that are used to assess the degree of aromaticity. Comparison of current-density calculations and calculations of nucleus-independent chemical shifts (NICS) shows that NICS calculations are not a reliable tool for determining the degree of aromaticity of the metal oxides.

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Acknowledgments

This research has been supported by the Academy of Finland through its Centers of Excellence Programme 2006–2011 and by Postdoctoral Researcher’s project (126905). H. F. was funded from the Research Grant Motions in Macromolecular Function: New Approaches to Visualize and Simulate Protein Flexibility, awarded 2008 by the Human Frontier of Science Program (HFSP). We thank CSC – the Finnish IT Center for Science for computer time. This article is dedicated to Prof. Pekka Pyykkö on his 70th birthday. The research interests of Prof. Pyykkö comprise relativistic effects and computational inorganic chemistry. He has published nine articles on studies of Cr, Mo, and W compounds showing his interest in the chromium, molybdenum, and tungsten chemistry [75–83].

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Authors and Affiliations

  1. Department of Chemistry, University of Helsinki, POB 55 (A.I. Virtanens plats 1), 00014, Helsinki, Finland

    Heike Fliegl, Olli Lehtonen, Michael Patzschke & Dage Sundholm

  2. Department of Chemistry, Center for Theoretical and Computational Chemistry, University of Tromsø, 9037, Tromsø, Norway

    Ying-Chan Lin

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  1. Heike Fliegl
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  2. Olli Lehtonen
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  3. Ying-Chan Lin
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  4. Michael Patzschke
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  5. Dage Sundholm
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Correspondence to Heike Fliegl.

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Dedicated to Professor Pekka Pyykkö on the occasion of his 70th birthday and published as part of the Pyykkö Festschrift Issue.

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Fliegl, H., Lehtonen, O., Lin, YC. et al. Theoretical investigation of photoelectron spectra and magnetically induced current densities in ring-shaped transition-metal oxides. Theor Chem Acc 129, 701–713 (2011). https://doi.org/10.1007/s00214-011-0946-4

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