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Symmetric Nonlocal Weighted Density Approximations from the Exchange-Correlation Hole of the Uniform Electron Gas

by: Rogelio Cuevas-Saavedra, Debajit Chakraborty, Sandra Rabi, Carlos Cardenas, Paul W. Ayers
J. Chem. Theory Comput. In Journal of Chemical Theory and Computation (4 October 2012), doi:10.1021/ct300325t  Key: citeulike:11567811

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Abstract

Nonlocal exchange-correlation energy functionals are constructed using the accurate model exchange-correlation hole for the uniform electron gas developed by Gori-Giorgi and Perdew. The exchange-correlation hole is constrained to be symmetric and normalized, so the resulting functionals can be viewed as symmetrized versions of the weighted density approximation; we call them two-point weighted density approximations. Even without optimization of parameters or functional forms, the exchange-correlation energies for small molecules are competitive with those of the best generalized gradient approximation functionals. Two-point weighted density approximations seem to be an interesting new direction for functional development. A more general version of the ?flat planes? conditions is derived. The generalized flat-planes conditions are closely linked to the normalization of the spin-resolved exchange-correlation hole at noninteger electron number. This and many other properties of the exact exchange-correlation functional can be imposed straightforwardly and directly in symmetrized weighted density approximation.


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