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Fromager E, Réal F, Wåhlin P, et al. On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species. J Chem Phys. 2009;131(5):054107doi: 10.1063/1.3187032.
Fromager, E., Réal, F., Wåhlin, P., Wahlgren, U., & Jensen, H. J. (2009). On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species. The Journal of chemical physics, 131(5), 054107. https://doi.org/10.1063/1.3187032
Fromager, Emmanuel, et al. "On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species." The Journal of chemical physics vol. 131,5 (2009): 054107. doi: https://doi.org/10.1063/1.3187032
Fromager E, Réal F, Wåhlin P, Wahlgren U, Jensen HJ. On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species. J Chem Phys. 2009 Aug 07;131(5):054107. doi: 10.1063/1.3187032. PMID: 19673551.
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J Chem Phys. 2009 Aug 07;131(5):054107. doi: 10.1063/1.3187032.

On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species.

The Journal of chemical physics

Emmanuel Fromager, Florent Réal, Pernilla Wåhlin, Ulf Wahlgren, Hans Jørgen Aa Jensen

Affiliations

  1. Laboratoire de Chimie Quantique, Institut de Chimie, CNRS/Université de Strasbourg, 4 rue Blaise Pascal, 67000 Strasbourg, France. [email protected].

PMID: 19673551 DOI: 10.1063/1.3187032

Abstract

In a previous paper [Fromager et al., J. Chem. Phys. 126, 074111 (2007)], some of the authors proposed a recipe for choosing the optimal value of the mu parameter that controls the long-range/short-range separation of the two-electron interaction in hybrid multiconfigurational self-consistent field short-range density-functional theory (MC-srDFT) methods. For general modeling with MC-srDFT methods, it is clearly desirable that the same universal value of mu can be used for any molecule. Their calculations on neutral light element compounds all yielded mu(opt)=0.4 a.u. In this work the authors investigate the universality of this value by considering "extreme" study cases, namely, neutral and charged isoelectronic f(0) actinide compounds (ThO(2), PaO(2)(+), UO(2)(2+), UN(2), CUO, and NpO(2)(3+)). We find for these compounds that mu(opt)=0.3 a.u. but show that 0.4 a.u. is still acceptable. This is a promising result in the investigation of a universal range separation. The accuracy of the currently best MC-srDFT (mu=0.3 a.u.) approach has also been tested for equilibrium geometries. Though it performs as well as wave function theory and DFT for static-correlation-free systems, it fails in describing the neptunyl (VII) ion NpO(2)(3+) where static correlation is significant; bending is preferred at the MC-srDFT (mu=0.3 a.u.) level, whereas the molecule is known to be linear. This clearly shows the need for better short-range functionals, especially for the description of the short-range exchange. It also suggests that the bending tendencies observed in DFT for NpO(2)(3+) cannot be fully explained by the bad description of static correlation effects by standard functionals. A better description of the exchange seems to be essential too.

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