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Two-point weighted density approximations for the kinetic energy density functional

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Abstract

We construct a model for the one-electron reduced density matrix that is symmetric and which satisfies the diagonal of the idempotency constraint and then use this model to evaluate the kinetic energy. This strategy for designing density functionals directly addresses the N-representability problem for kinetic energy density functionals. Results for atoms and molecules are encouraging, especially considering the simplicity of the model. However, like all of the other kinetic energy functionals in the literature, quantitative accuracy is not achieved.

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Notes

  1. Even if we had a more general, six-dimensional, model for the Fermi wave vector, forcing idempotency exactly would shift one back to Kohn–Sham-like computational cost and is therefore unacceptable in the context of orbital-free DFT.

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Acknowledgements

Support from Sharcnet, NSERC, and the Canada Research Chairs is appreciated. RCS acknowledges financial support from CONACYT, ITESM and DGRI-SEP.

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  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, Canada

    Debajit Chakraborty, Rogelio Cuevas-Saavedra & Paul W. Ayers

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  1. Debajit Chakraborty
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Correspondence to Paul W. Ayers.

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Chakraborty, D., Cuevas-Saavedra, R. & Ayers, P.W. Two-point weighted density approximations for the kinetic energy density functional. Theor Chem Acc 136, 113 (2017). https://doi.org/10.1007/s00214-017-2149-0

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