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The influence of correlation on (de)localization indices from a valence bond perspective

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Abstract

When going beyond the Hartree–Fock level to correlated methods, one observes a significant reduction in the delocalization index. This is commonly interpreted as a weakening of electron sharing due to electron correlation, although this is rather counter-intuitive to the concomitant energy lowering. In this study, we use an analytical valence bond model and full CI calculations to show that this reduction in the delocalization index actually goes hand in hand with increased covalent contributions at the expense of ionic contributions. This suggests that we should be careful in formulating interpretations of these results in (de)localization indices.

Variation of the localization Δ(ΩA, ΩA) and delocalization index Δ(ΩA, ΩB) as a function of the parameter ω. By adjusting this parameter ω from \( \frac {\pi }{4}\) to 0, we can gradually change the underlying wave function from a Hartree-Fock to a Heitler-London description.

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Authors and Affiliations

  1. Department of Chemistry, Ghent University, Krijgslaan 281 (S3), Ghent, 900, Belgium

    Guillaume Acke & Patrick Bultinck

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  1. Guillaume Acke
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  2. Patrick Bultinck
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Correspondence to Patrick Bultinck.

Additional information

This paper belongs to Topical Collection International Conference on Systems and Processes in Physics, Chemistry and Biology (ICSPPCB-2018) in honor of Professor Pratim K. Chattaraj on his sixtieth birthday

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Acke, G., Bultinck, P. The influence of correlation on (de)localization indices from a valence bond perspective. J Mol Model 24, 275 (2018). https://doi.org/10.1007/s00894-018-3808-3

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  • DOI: https://doi.org/10.1007/s00894-018-3808-3

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