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arxiv: quant-ph/0605062 · v2 · submitted 2006-05-06 · 🪐 quant-ph · cond-mat.mtrl-sci

Relevance of the slowly-varying electron gas to atoms, molecules, and solids

classification 🪐 quant-ph cond-mat.mtrl-sci
keywords gradientslowly-varyingatomsbecomeelectronenergiesexchangelarge
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Under a certain scaling, the electron densities of finite systems become both large and slowly-varying, so that the gradient expansions of the density functionals for the Kohn-Sham kinetic and exchange energies become asymptotically exact to order $\nabla^2$. Neutral atoms of large $Z$ scale similarly, but a cusp correction at the nucleus requires generalizing the gradient expansion for exchange, producing the wrong gradient coefficient in the slowly-varying limit. Meta-generalized gradient approximations (meta-GGA's) recover both the slowly-varying and large-$Z$ limits. GGA correlation energies of large-Z atoms are found to be accurate.

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