A test of the Hirshfeld definition of atomic charges and moments

Davidson, Ernest R.; Chakravorty, Subhas J.

doi:10.1007/bf01113058

Cited by 296 publications

(249 citation statements)

References 13 publications

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“…It was found that Hirshfeld charges are always relatively small in absolute value [26], which is not surprising given that the Hirshfeld AIMs are maximally similar to neutral atoms.…”

Section: Stockholder Partitioningmentioning

confidence: 82%

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The conformational sensitivity of iterative stockholder partitioning schemes

Verstraelen¹,

Ayers²,

Speybroeck³

et al. 2012

Chemical Physics Letters

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Chemical interpretation and empirical modeling of partial charges requires a robust partitioning scheme to derive these charges from the molecular electronic density. The degree of undesirable conformational sensitivity is assessed for three iterative stockholder partitioning schemes: Hirshfeld-I (HI), Iterative Stockholder Analysis (ISA) and a new Gaussian ISA variant (GISA). GISA has fewer degrees of freedom than ISA and enforces monotonically decaying pro-atoms. These improvements accelerate the converge of GISA as compared to ISA. However, the conformational sensitivity of the charges does not decrease and is still large compared to HI.

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“…It was found that Hirshfeld charges are always relatively small in absolute value [26], which is not surprising given that the Hirshfeld AIMs are maximally similar to neutral atoms.…”

Section: Stockholder Partitioningmentioning

confidence: 82%

“…The choice for neutral atoms in the Hirshfeld scheme is in principle arbitrary [26]. One could as well use spherically averaged densities of isolated ions.…”

Section: Stockholder Partitioningmentioning

confidence: 99%

The conformational sensitivity of iterative stockholder partitioning schemes

Verstraelen¹,

Ayers²,

Speybroeck³

et al. 2012

Chemical Physics Letters

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“…For this kind of population analysis using the Mulliken formalism, 30 it is widely accepted that the absolute magnitudes of the atomic populations yielded by the formalism above have little physical meaning, since they still have a high degree of sensitivity depending on the atomic basis set with which one performs the analysis. 31 However, consideration of their relative values can yield useful information, 32 as far as a consistent basis set is provided for the population analysis. Figure 2 shows PDOS with respect to the atomic basis functions of the Cu, O, R (=B, C, and N), and the aromatic ring (referred to as Ring) for each of the Cu-terminated BDB, BDC, and DNB molecules.…”

Section: Resultsmentioning

confidence: 99%

Tuning the electron transport of molecular junctions by chemically functionalizing anchoring groups: First-principles study

et al. 2012

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In this first-principles study, we present density-functional calculations of the electronic structures and electron transport properties of organic molecular junctions with several anchoring groups containing atoms with different electronegativities, i.e., benzenediboronate (BDB), benzenedicarboxylate (BDC), and dinitrobenzene (DNB) molecular junctions sandwiched between two Cu(110) electrodes. The electronic-structure calculations exhibit a significant difference in the density of states not only at the anchoring groups but also at the aromatic rings of the molecular junctions, suggesting that the electron transport is specific for each system. Our transport calculations show that the BDB and DNB molecular junctions have finite electron transmissions at the zero-bias limit while the BDC molecular junction has a negligible electron transmission. Moreover, for the BDB and DNB systems, the electron transmission channels around the Fermi energy reveal fingerprint features, which provide specific functionalities for the molecular junctions. Therefore, our theoretical results demonstrate the possibility to precisely tune the electron transport properties of molecular junctions by engineering the anchoring groups at the single-atom level.

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“…[5][6][7][8][9][10][11] This division of the physical space has usually been accomplished by means of Bader's atoms in molecules 13 ͑AIM͒ theory or by the fuzzy atom procedure. [14][15][16] In Ref. 10, we have described a general algorithm to decompose the energy of a molecule into one-and twocenter contributions, according to a partitioning of the real space.…”

Section: Introductionmentioning

confidence: 99%

Energy decompositions according to physical space partitioning schemes: Treatments of the density cumulant

Alcoba

Torre

Laín

et al. 2007

The Journal of Chemical Physics

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Articles you may be interested inA new ab initio potential energy surface for the collisional excitation of HCN by para-and ortho-H2 J. Chem. Phys. 139, 224301 (2013) This article is a continuation of our previous paper on schemes of energy decompositions of molecular systems in the real space ͓D. R. Alcoba et al., J. Chem. Phys. 122, 074102 ͑2005͔͒ now using correlated state functions. We study, according to physical arguments, the appropriate management of the density cumulant arising from the second-order reduced density matrix at correlated level, whose contributions can be assigned to one-center or to two-center terms in the energy partitioning. Our treatments are applied within two physical space partitioning schemes: the Bader partitioning into atomic basins and the fuzzy atom procedure. The results obtained in selected molecules are analyzed and discussed in detail.

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A test of the Hirshfeld definition of atomic charges and moments

Cited by 296 publications

References 13 publications

The conformational sensitivity of iterative stockholder partitioning schemes

The conformational sensitivity of iterative stockholder partitioning schemes

Tuning the electron transport of molecular junctions by chemically functionalizing anchoring groups: First-principles study

Energy decompositions according to physical space partitioning schemes: Treatments of the density cumulant

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