Bonds, lone pairs, and shells probed by means of on-top dynamical correlations

Abstract

The electron localization function (ELF) by Becke and Edgecombe [A.D. Becke, K.E. Edgecombe, J. Chem. Phys. 92, 5397 (1990)] is routinely adopted as a descriptor of atomic shells and covalent bonds. Since the ELF and its related quantities find useful exploitation also in the construction of modern density functionals, the interest in complementing the ELF is linked to both the quests of improving electronic structure descriptors and density functional approximations. The ELF uses information which is available by considering parallel-spin electron pairs in single-reference many-body states. In this work, we complement this construction with information obtained by considering antiparallel-spin pairs whose short-range correlations are modeled by a density functional approximation. As a result, the approach requires only a contained computational effort. Applications to a variety of systems show that, in this way, we gain a spatial description of the bond in H2 (which is not available with the ELF) together with some trends not optimally captured by the ELF in other prototypical situations.

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Correspondence to Stefano Pittalis.

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Contribution to the Topical Issue “Special issue in honor of Hardy Gross”, edited by C.A. Ullrich, F.M.S. Nogueira, A. Rubio, and M.A.L. Marques.

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Pittalis, S., Varsano, D., Delgado, A. et al. Bonds, lone pairs, and shells probed by means of on-top dynamical correlations. Eur. Phys. J. B 91, 187 (2018). https://doi.org/10.1140/epjb/e2018-90143-4

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