Atomic decomposition of Kohn–Sham molecular energies: the kinetic energy component

Patrikeev, Leonid; Joubert, Laurent; Tognetti, Vincent

doi:10.1080/00268976.2015.1113314

Cited by 18 publications

(16 citation statements)

References 98 publications

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“…A recent article by Patrikeev et al [75]. investigated the performance of several density functionals in their evaluation of both Kohn-Sham and correlation kinetic energies of topological atoms, and also commented on discriminating atom types through such atomic descriptors.…”

Section: Evidence For Atom Typingmentioning

confidence: 99%

The prediction of topologically partitioned intra-atomic and inter-atomic energies by the machine learning method kriging

et al. 2016

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Section: Evidence For Atom Typingmentioning

confidence: 99%

The prediction of topologically partitioned intra-atomic and inter-atomic energies by the machine learning method kriging

et al. 2016

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“…1ðrÞ; r 2 1ðrÞ and G(r) were obtained in 3D grids with the Dgrid code [59] and then used to calculate K(r) according to equation 4. [62] However, T C for diatomic molecules was found to be less than 1 % of the total kinetic energy. Several grid spacings were tested to calculate the numerical derivatives.…”

Section: Computational Detailsmentioning

confidence: 97%

“…In our case, we focused only in T S , but there exist some approximations to include the T c component into KE analysis. [62] However, T C for diatomic molecules was found to be less than 1 % of the total kinetic energy. [63]…”

Section: Computational Detailsmentioning

confidence: 99%

Laplacian of the Hamiltonian Kinetic Energy Density as an Indicator of Binding and Weak Interactions

et al. 2019

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The kinetic energy is the center of a controversy between two opposite points of view about its role in the formation of a chemical bond. One school states that a lowering of the kinetic energy associated with electron delocalization is the key stabilization mechanism of covalent bonding. In contrast, the opposite school holds that a chemical bond is formed by a decrease in the potential energy due to a concentration of electron density within the binding region. In this work, a topographic analysis of the Hamiltonian Kinetic Energy Density (KED) and its laplacian is presented to gain more insight into the role of the kinetic energy within chemical interactions. This study is focused on atoms, diatomic and organic molecules, along with their dimers. In addition, it is shown that the laplacian of the Hamiltonian KED exhibits a shell structure in atoms and that their outermost shell merge when a molecule is formed. A covalent bond is characterized by a concentration of kinetic energy, potential energy and electron densities along the internuclear axis, whereas a charge-shift bond is characterized by a fusion of external concentration shells and a depletion in the bonding region. In the case of weak intermolecular interactions, the external shell of the molecules merge into each other resulting in an intermolecular surface comparable to that obtained by the Non-covalent interaction (NCI) analysis.

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“…We refer the interested reader to the work of Rodriguez and Ayers et al . and to our recent contribution to this topic …”

Section: Theorymentioning

confidence: 99%

On Atoms‐in‐Molecules Energies from Kohn–Sham Calculations

Tognetti

Joubert

2017

ChemPhysChem

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Herein, we discuss three methods to partition the total molecular energy into additive atomic contributions within the framework of Bader's atoms‐in‐molecules theory and in the particular context of Kohn–Sham density functional theory. The first method is derived from the virial theorem, whereas the two other schemes, termed “standard” and “model”, are based on Pendás’ interacting‐quantum‐atoms decomposition. The methods are then compared for a dataset of molecules of interest for direct application in organic chemistry and biochemistry. Finally, the relevance of the three methods for the prediction of intrinsic reactivity properties (e.g., electrophilicity) or for unravelling the nature of chemical bonding (e.g., in halogen bonds, beyond the pure electrostatic point of view), is examined and paves the way for their more systematic use for the in silico design of new reactants.

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Atomic decomposition of Kohn–Sham molecular energies: the kinetic energy component

Cited by 18 publications

References 98 publications

The prediction of topologically partitioned intra-atomic and inter-atomic energies by the machine learning method kriging

The prediction of topologically partitioned intra-atomic and inter-atomic energies by the machine learning method kriging

Laplacian of the Hamiltonian Kinetic Energy Density as an Indicator of Binding and Weak Interactions

On Atoms‐in‐Molecules Energies from Kohn–Sham Calculations

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