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Computational and Theoretical Chemistry
Article
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Computational and Theoretical Chemistry
Article . 2015 . Peer-reviewed
License: Elsevier TDM
Data sources: Crossref
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A problematic issue for atoms in molecules: Impact of (quasi-)degenerate states on Quantum Theory Atoms in Molecules and Hirshfeld-I properties

Authors: Bultinck, Patrick; Jayatilaka, Dylan; Cárdenas, Carlos;

A problematic issue for atoms in molecules: Impact of (quasi-)degenerate states on Quantum Theory Atoms in Molecules and Hirshfeld-I properties

Abstract

Abstract We examine the dependence of atomic properties derived from the Quantum Theory of Atoms in Molecules and the Hirshfeld-I method on the existence of (quasi-)degenerate states. As atomic charges are mostly used to quickly assess chemical reactivity using the molecular electrostatic potential, we computed the correct zeroth order density matrices using degenerate perturbation theory for a perturbing point charge of given magnitude, sign and position. This density matrix is then used as input for Atoms in Molecules (AIM) analysis and the dependence of atomic charges on the nature of the perturbation examined for two molecules. It is shown that in simple cases, the atomic charges are deceptively robust due to symmetry reasons whereas in a less symmetrical case the atomic charges vary significantly. This establishes that for the prediction of reactivity, for every kind of perturbation, a specific perturbation matrix needs to be diagonalised and the resulting density matrix used for AIM analysis.

Countries
Chile, Belgium
Keywords

Electrostatic potential, Reactivity, TOPOLOGICAL ATOMS, Atoms in Molecules, ELECTROSTATIC POTENTIALS, Hirshfeld-I, Chemistry, ELECTRONIC-STRUCTURE, FUKUI MATRIX, CONVERGENCE, INFORMATION-THEORY, AIM, DENSITIES, Degenerate states, CHARGES, POPULATION ANALYSIS, FRAGMENTS

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    15
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    Top 10%
    influence
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    impulse
    This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
    Top 10%
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selected citations
These citations are derived from selected sources.
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
15
Top 10%
Average
Top 10%
Green
hybrid