Quantum theory of atoms in molecules in condensed charge density space

Wilson, Timothy R.; Eberhart, Mark E.

doi:10.1139/cjc-2019-0086

Cited by 11 publications

(15 citation statements)

References 27 publications

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“…ED gradient paths emanated from a saddle point, terminating at two maxima and traced along maximum ED, originally named bond paths , are interpreted as interaction lines between atoms and the areas of space delimited by zero‐flux surfaces of ED gradient define atomic basins . However, recent ambiguous results raised a discussion on the limitations of this method, an important point in this debate being precisely the failure of QTAIM to study NCIs.…”

Section: Introductionmentioning

confidence: 99%

A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

Olejniczak

Gomes

Tierny

2019

Int J of Quantum Chemistry

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Topological Data Analysis (TDA) is a powerful mathematical theory, largely unexplored in theoretical chemistry. In this work we demonstrate how TDA provides new insights into topological features of electron densities and reduced density gradients, by investigating the effects of relativity on the bonding of the Au4‐S‐C6H4‐S′‐Au′4 molecule. Whereas recent analyses of this species carried out with the Quantum Theory of Atoms‐In‐Molecules (a previous study) concluded, from the emergence of new topological features in the electron density, that relativistic effects yielded noncovalent interactions between gold and hydrogen atoms, we show from their low persistence values (which decrease with increased basis set size) these features are not significant. Further analysis of the reduced density gradient confirms no relativity‐induced noncovalent interactions in Au4‐S‐C6H4‐S′‐Au′4. We argue TDA should be integrated into electronic structure analysis methods, and be considered as a basis for the development of new topology‐based approaches.

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Section: Introductionmentioning

confidence: 99%

A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

Olejniczak

Gomes

Tierny

2019

Int J of Quantum Chemistry

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“…As we summarized in an earlier article, [53] the space P is constructed through a mapping of gradient paths of electron charge density (1) to points in P. Every gradient path (G) in 1 originates from a local minimum called a cage CP and terminates at a maximum, almost always coincident with a nucleus and hence denoted a nuclear CP. We assume these Gs to be parameterized by arc length, s.…”

Section: Condensed Charge Density Spacementioning

confidence: 99%

Observing the 3D Chemical Bond and its Energy Distribution in a Projected Space

et al. 2019

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Our curiosity‐driven desire to “see” chemical bonds dates back at least one‐hundred years, perhaps to antiquity. Sweeping improvements in the accuracy of measured and predicted electron charge densities, alongside our largely bondcentric understanding of molecules and materials, heighten this desire with means and significance. Here we present a method for analyzing chemical bonds and their energy distributions in a two‐dimensional projected space called the condensed charge density. Bond “silhouettes” in the condensed charge density can be reverse‐projected to reveal precise three‐dimensional bonding regions we call bond bundles. We show that delocalized metallic bonds and organic covalent bonds alike can be objectively analyzed, the formation of bonds observed, and that the crystallographic structure of simple metals can be rationalized in terms of bond bundle structure. Our method also reproduces the expected results of organic chemistry, enabling the recontextualization of existing bond models from a charge density perspective.

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“…Accordingly, we exploit this fact using our new and unique software [ 32 , 48 ] that allows us to compute and partition the energy of, among other things, chemical bonds and electronic basins. For these calculations, we omitted contributions to kinetic energy due to correlation,

[ 49 ].…”

Section: Discussionmentioning

confidence: 99%

Principles Determining the Structure of Transition Metals

et al. 2021

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For the better part of a century researchers across disciplines have sought to explain the crystallography of the elemental transition metals: hexagonal close packed, body centered cubic, and face centered cubic in a form similar to that used to rationalize the structure of organic molecules and inorganic complexes. Pauling himself tried with limited success to address the origins of transition metal stability. These early investigators were handicapped, however, by incomplete knowledge regarding the structure of metallic electron density. Here, we exploit modern approaches to electron density analysis to first comprehensively describe transition metal electron density. Then, we use topological partitioning and quantum mechanically rigorous treatments of kinetic energy to account for the structure of the density as arising from the interactions between metallic polyhedra. We argue that the crystallography of the early transition metals results from charge transfer from the so called “octahedral” to “tetrahedral cages” while the face centered cubic structure of the late transition metals is a consequence of anti-bonding interactions that increase octahedral hole kinetic energy.

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Quantum theory of atoms in molecules in condensed charge density space

Cited by 11 publications

References 27 publications

A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

A Topological Data Analysis perspective on noncovalent interactions in relativistic calculations

Observing the 3D Chemical Bond and its Energy Distribution in a Projected Space

Principles Determining the Structure of Transition Metals

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