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A partition function for atoms and bonds in molecules

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Abstract

A new weight function is proposed to work with the atoms and bonds in molecules theory. The molecular radial electron density (\(\rho _{\mathrm{rad}}{({\mathbf {r}} )}\)) and bond electron density (\(\rho ^{A-B}{({\mathbf {r}} )}\)) are visually illustrated using the proposed weight. The molecular properties including the total number of electrons, the electron–nuclear potential energy, and Coulomb potential energy are calculated numerically using the proposed weight. The computed molecular properties using the proposed weight are compared to those obtained using the Becke weight and as well with molecular properties calculated analytically. Our findings show that the proposed weight gives better bonding-region representations for both \(\rho _{\mathrm{rad}}{({\mathbf {r}} )}\) and \(\rho ^{A-B}{({\mathbf {r}} )}\) than those obtained using the Becke weight. In addition, the proposed weight performs equally well or better than the Becke weight at numerical integration of molecular properties.

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Notes

  1. RHF for closed shell and ROHF for open shell.

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Acknowledgements

We gratefully acknowledge the support of the Natural Sciences and Engineering Council of Canada (NSERC) and the Atlantic Excellence Network (ACENET) and Compute Canada for the computer time.

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  1. Department of Chemistry, Memorial University, St. John’s, NL, A1B 3X7, Canada

    Ibrahim E. Awad & Raymond A. Poirier

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  1. Ibrahim E. Awad
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  2. Raymond A. Poirier
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Correspondence to Ibrahim E. Awad or Raymond A. Poirier.

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Awad, I.E., Poirier, R.A. A partition function for atoms and bonds in molecules. Theor Chem Acc 138, 82 (2019). https://doi.org/10.1007/s00214-019-2468-4

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