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A Gradient Corrected Two-Point Weighted Density Approximation for Exchange Energies

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Abstract

A successful symmetric, two-point, nonlocal weighted density approximation for the exchange energy of atoms and molecules can be constructed using a power mean with constant power p when symmetrizing the exchange-correlation hole [Phys. Rev. A 85, 042519 (2012)]. In this work, we consider how this parameter depends on the system’s charge. Exchange energies for all ions with charge from \(-1\) to \(+12\) of the first eighteen atoms of the periodic table are computed and optimized. Appropriate gradient corrections to the current model, based on rational functions, are designed based on the optimal p values we observed for the ionic systems. All of the advantageous features (non-locality, uniform electron gas limit and no self-interaction error) of the original model are preserved.

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Acknowledgements

Support from Compute Canada, NSERC, and the Canada Research Chairs is appreciated.

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Authors and Affiliations

  1. Department of Chemistry and Chemical Biology, McMaster University, Hamilton, ON, L8S 4M1, Canada

    R. Cuevas-Saavedra, D. Chakraborty, M. Chan & P. W. Ayers

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  1. R. Cuevas-Saavedra
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  2. D. Chakraborty
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  3. M. Chan
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  4. P. W. Ayers
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Correspondence to P. W. Ayers .

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Editors and Affiliations

  1. Dipartimento di Fisica e Astronomia, Università di Catania, Catania, Italy

    G.G.N Angilella

  2. Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Pisa, Italy

    C. Amovilli

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Cuevas-Saavedra, R., Chakraborty, D., Chan, M., Ayers, P.W. (2018). A Gradient Corrected Two-Point Weighted Density Approximation for Exchange Energies. In: Angilella, G., Amovilli, C. (eds) Many-body Approaches at Different Scales. Springer, Cham. https://doi.org/10.1007/978-3-319-72374-7_18

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