Charge Sensitivity Approach to Electronic Structure and Chemical Reactivity

Nalewajski, Roman F.; Korchowiec, Jacek

doi:10.1142/2735

Cited by 74 publications

(144 citation statements)

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“…of this equation. This quantity has a unique information‐theoretic interpretation involving the subsystem Fukui function 14, 15, 19, measuring the equilibrium AIM density response per unit change in its overall electron population: f α ( r )=[∂ρ α ( r )/∂ N α ] ν ≡ f α [ N α ,ν; r ], where ν( r ) is the external potential due to the nuclei, common to both the molecular system and the associated atomic promolecule.…”

Section: Illustrative Results and Discussionmentioning

confidence: 99%

“…Therefore, the subsystem surprisals { I α ( r )}, representing the fragment entropy deficiency density per electron, are locally equalized for all the Hirshfeld AIM components at the global surprisal value. This and other local information distance equalization rules are complementary to the familiar energetic criterion of the subsystem chemical potential (electronegativity) equalization 3, 13–15. It should be observed, however, that—contrary to these entropic criteria—the electronegativity equalization is satisfied for any exhaustive division of the ground‐state density into open subsystems, thus failing to distinguish one partitioning scheme from the other 3.…”

Section: Hirshfeld Division Of Molecular Electron Density and Alternamentioning

confidence: 99%

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Information distance analysis of molecular electron densities

Nalewajski

Świtka

Michalak

2002

Int J of Quantum Chemistry

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ABSTRACT:The information-theoretic basis of the Hirshfeld partitioning of the molecular electronic density into the densities of the "stockholder" atoms-in-molecules (AIM) is summarized. It is argued that these AIM densities minimize both the directed divergence (Kullback-Leibler) and divergence (Kullback) measures of the entropy deficiency between the AIM and their free atom analogs of the promolecule. The local equalization of the information distance densities of the Hirshfeld components, at the local value of the corresponding global entropy deficiency density, is outlined and several approximate relations are established between the alternative local measures of the missing information and the familiar function of a difference between the molecular and promolecule densities. Various global (of the system as a whole) and atomic measures of the entropy deficiency or the displacements relative to the isoelectronic promolecule, defined for densities or probabilities (shape functions) in both the local resolution and the Hirshfeld AIM discretization, are introduced and tested. This analysis is performed also for the valence electron (frozen-core) approximation. Illustrative results for representative linear molecules, including diatomics, triatomics, and tetraatomics, are reported. They are interpreted as complementary characteristics of changes in the net AIM charge distribution and of the displacements in the information content of the electron distributions of bonded atoms. These numerical results confirm the overall similarity of the stockholder AIM to their free atom analogs and reflect the information displacements due to the AIM polarization and charge transfer in molecules. They also demonstrate the semiquantitative nature of the approximate relations established between the entropy deficiency densities and the related functions involving the density difference function. This development extends the range of interpretations based on the density difference diagrams into probing the associated information displacements in a molecule accompanying the formation of the chemical bonds.

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Section: Illustrative Results and Discussionmentioning

confidence: 99%

Section: Hirshfeld Division Of Molecular Electron Density and Alternamentioning

confidence: 99%

Information distance analysis of molecular electron densities

Nalewajski

Świtka

Michalak

2002

Int J of Quantum Chemistry

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“…Our findings are yet another, dynamical evidence that MH rule really works. One should not mix MH rule with the minimum hardness principle . The former is valid for grand canonical ensemble (constant temperature and constant chemical potential), whereas the latter says that hardness functional,

η [g] = \iint g (\vec{r}) η (\vec{r}, \vec{r}') g (\overset{⇀}{r}') d \vec{r} d \vec{r}'

, reaches minimum value at constant external potential when the trial function g is the same as FF of eq.…”

Section: Resultsmentioning

confidence: 99%

“…The distance criterion becomes insufficient as it does not reflect the electronic origin of the bf/bb process. Information about “electronic” degree of freedom is readily available from CSA . CSA originates from DFT and is based on electronegativity equalization (EE) principle .…”

Section: Bond Descriptorsmentioning

confidence: 99%

“…Nevertheless, apart from information about charge reorganization, CSA offers a variety of properties of great importance in determining the behavior of the system. This article deals with a couple of such properties applied to hydrogen‐bonded systems, namely, electronegativity (χ), hardness (η), Fukui function ( f , FF), and linear response (polarization or internal softness, β) data in global and molecular fragment resolutions …”

Section: Bond Descriptorsmentioning

confidence: 99%

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Bond detectors for molecular dynamics simulations, Part I: Hydrogen bonds

Stachowicz

Korchowiec

2013

J Comput Chem

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Charge sensitivity analysis in AMBER force-field resolution has been used in quest for detectors of hydrogen bonds (HBs). The process of HB formation was investigated on ab initio classical trajectories (B3LYP/6-31G*) of different nucleobase pairs. Several charge sensitivities, namely: electronegativity, hardness, Fukui function (FF), and polarization matrix, were analyzed. The global and constrained equilibria were considered. It was demonstrated that FF indices and polarization matrix elements are good detectors of HB formation.

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Quantum fluid density functional theory of time-dependent processes

Chattaraj

Sengupta

Poddar

1998

Int. J. Quant. Chem.

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ABSTRACT:A quantum fluid density functional theory has been developed through an amalgamation of the quantum fluid dynamics and the time-dependent density functional theory. It is used in studying typical time-dependent processes like ion᎐atom collisions and atom᎐field interaction. Temporal evolution of chemical reactivity parameters as electronegativity, hardness, entropy, and polarizability is monitored for a He atom in its ground and excited states interacting with an external electric field and an incoming proton. It is observed that these reactivity parameters either remain static or oscillate with the external field in the atom᎐field interaction case, whereas during the collision process, hardness and entropy maximize and polarizability minimizes for both the electronic states of the atom. The possibility of a quantum theory of motion within the purview of this quantum fluid density functional framework is also explored.

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Charge Sensitivity Approach to Electronic Structure and Chemical Reactivity

Abstract: Charge Sensitivity Approach to Electronic Structure and Chemical Reactivity Downloaded from www.worldscientific.com by 44.224.250.200 on 12/01/20. Re-use and distribution is strictly not permitted, except for Open Access articles.

Cited by 74 publications

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Information distance analysis of molecular electron densities

Information distance analysis of molecular electron densities

Bond detectors for molecular dynamics simulations, Part I: Hydrogen bonds

Quantum fluid density functional theory of time-dependent processes

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