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image/svg+xml Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Closed Access logo, derived from PLoS Open Access logo. This version with transparent background. http://commons.wikimedia.org/wiki/File:Closed_Access_logo_transparent.svg Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Vrije Universiteit B...arrow_drop_down
image/svg+xml Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao Closed Access logo, derived from PLoS Open Access logo. This version with transparent background. http://commons.wikimedia.org/wiki/File:Closed_Access_logo_transparent.svg Jakob Voss, based on art designer at PLoS, modified by Wikipedia users Nina and Beao
Physical Chemistry Chemical Physics
Article . 2007 . Peer-reviewed
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On the position of the potential wall in DFT temporary anion calculations

Authors: Sablon, Nick; De Proft, Frank; Geerlings, Paul; Tozer, D.j.;

On the position of the potential wall in DFT temporary anion calculations

Abstract

A simple method was recently proposed [D. J. Tozer and F. De Proft, J. Chem. Phys., 2007, 127, 034108] for performing explicit density functional theory (DFT) calculations on temporary anions. The excess electron in the anion is bound by a potential wall, the position of which is determined by a single parameter lambda, chosen to reproduce an approximate, theoretical negative electron affinity in the corresponding neutral. In the present study, the system-dependence of lambda and the sensitivity of the negative affinities to this parameter are investigated for 34 organic molecules. The results demonstrate that the system-dependent lambda values can be replaced by a global, average value, with minimal effect on the affinities. It follows that the orbitals, electron density, and other properties of a temporary anion can be determined from a single DFT calculation on that anion, using a large, diffuse basis set. As an illustration, singly occupied molecular orbitals and spin densities are determined for the anions of guanine and adenine nucleobases. Despite the use of a diffuse basis set, the method yields quantities that are localised in the molecular framework, associated with vertical electron affinities of -1.2 eV and -0.8 eV, respectively.

Country
Belgium
Related Organizations
Keywords

calculation, Anions, Models, Molecular, Guanine, Models, Chemical, Molecular Structure, Adenine, Quantum Theory, Sensitivity and Specificity

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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!
37
Top 10%
Top 10%
Top 10%
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