A self‐consistent Hirshfeld method for the atom in the molecule based on minimization of information loss

Ghillemijn, Dieter; Bultinck, Patrick; Neck, Dimitri Van; Ayers, Paul W.

doi:10.1002/jcc.21734

Cited by 26 publications

(28 citation statements)

References 33 publications

(43 reference statements)

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“…The atomic weighing factors for the rst charge cycle are computed using neutral reference atoms (eqn (54) and (55)). The atomic weighing factors for the rst charge cycle are computed using neutral reference atoms (eqn (54) and (55)).…”

Section: Determining the Ddec6 Reference Ion Charge Value (Charge Cycmentioning

confidence: 99%

Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology

2016

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Net atomic charges (NACs) are widely used in all chemical sciences to concisely summarize key information about the partitioning of electrons among atoms in materials. The objective of this article is to develop an atomic population analysis method that is suitable to be used as a default method in quantum chemistry programs irrespective of the kind of basis sets employed. To address this challenge, we introduce a new atoms-in-materials method with the following nine properties: (1) exactly one electron distribution is assigned to each atom, (2) core electrons are assigned to the correct host atom, (3) NACs are formally independent of the basis set type because they are functionals of the total electron distribution, (4) the assigned atomic electron distributions give an efficiently converging polyatomic multipole expansion, (5) the assigned NACs usually follow Pauling scale electronegativity trends, (6) NACs for a particular element have good transferability among different conformations that are equivalently bonded, (7) the assigned NACs are chemically consistent with the assigned atomic spin moments, (8) the method has predictably rapid and robust convergence to a unique solution, and (9) the computational cost of charge partitioning scales linearly with increasing system size. We study numerous materials as examples: (a) a series of endohedral C 60 complexes, (b) high-pressure compressed sodium chloride crystals with unusual stoichiometries, (c) metal-organic frameworks, (d) large and small molecules, (e) organometallic complexes, (f) various solids, and (g) solid surfaces. Due to non-nuclear attractors, Bader's quantum chemical topology could not assign NACs for some of these materials. We show for the first time that the Iterative Hirshfeld and DDEC3 methods do not always converge to a unique solution independent of the initial guess, and this sometimes causes those methods to assign dramatically different NACs on symmetry-equivalent atoms. By using a fixed number of charge partitioning steps with well-defined reference ion charges, the DDEC6 method avoids this problem by always converging to a unique solution. These characteristics make the DDEC6 method ideally suited for use as a default charge assignment method in quantum chemistry programs. † Electronic supplementary information (ESI) available: Summary of alternative charge partitioning algorithms considered; summary of integration routines; iterative algorithm for computing the Convex functional NACs; ow diagrams for the DDEC6 method; and .xyz les (which can be read using any text editor or the free Jmol visualization program downloadable from http://jmol.sourceforge.net) containing geometries, net atomic charges, atomic dipoles and quadrupoles, tted tail decay exponents, and ASMs. See

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Section: Determining the Ddec6 Reference Ion Charge Value (Charge Cycmentioning

confidence: 99%

Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology

2016

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“…Indeed, Hirshfeld charges might considerably depend on the used scheme (quality of the chosen free atomic densities, using or not iterative schemes [77] ). Actually, the charges provided by the two pro- …”

Section: Full Paper Wwwc-chemorgmentioning

confidence: 99%

Quantifying electro/nucleophilicity by partitioning the dual descriptor

2015

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Translating local electro/nucleophilicities into the language of reactive sites is an appealing theoretical challenge that could be conducive to strengthen the collaborative dialogue between experimentalists and quantum chemists. The usual schemes for such condensation, relying on atomic charges, may however lead to important information loss, due to a sometimes inappropriate averaging of the reactivity anisotropy. In this article, we present instead an approach based on the dual descriptor Δf, which aims at partitioning real space into nonoverlapping reactive domains that feature a constant Δf sign. This strategy enables not only to identify the nucleo/electrophilic regions inside a molecule but also to quantify meaningful properties (mean value, volume, electron population…). Its interest is then illustrated on two specific chemical problems: the measure of σ-holes in the context of halogen bonds, and of the electrophilicity of organic carbocations, casting the light on the versatility of this method.

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“…(4) is the same partitioning that Hirshfeld had proposed more than two decades earlier, on purely heuristic grounds. 11 Since then, many researchers have elaborated upon this basic approach, either by generalizing (and even optimizing) the choice of pro-atomic densities [12][13][14][15][16][17][18][19] or by using alternative measures of the deviation between densities. 12,[20][21][22] Remarkably, the Hirshfeld partitioning formula, Eq.…”

Section: Introductionmentioning

confidence: 99%

How pervasive is the Hirshfeld partitioning?

Heidar‐Zadeh

Ayers

2015

The Journal of Chemical Physics

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One can partition the molecular density into its atomic contributions by minimizing the divergence of the atom-in-molecule densities from their corresponding reference pro-atomic densities, subject to the constraint that the sum of the atom-in-molecule densities is the total molecular density. We expose conditions on the divergence measure that are necessary, and sufficient, to recover the popular Hirshfeld partitioning. Specifically, among all local measures of the divergence between two probability distribution functions, the Hirshfeld partitioning is obtained only for f-divergences.

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A self‐consistent Hirshfeld method for the atom in the molecule based on minimization of information loss

Cited by 26 publications

References 33 publications

Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology

Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology

Quantifying electro/nucleophilicity by partitioning the dual descriptor

How pervasive is the Hirshfeld partitioning?

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