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Authordc.contributor.authorBultinck, Patrick 
Authordc.contributor.authorJayatilaka, Dylan 
Authordc.contributor.authorCárdenas, Carlos 
Admission datedc.date.accessioned2015-08-08T21:33:02Z
Available datedc.date.available2015-08-08T21:33:02Z
Publication datedc.date.issued2015
Cita de ítemdc.identifier.citationComputational and Theoretical Chemistry 1053 (2015) 106–111en_US
Identifierdc.identifier.otherDOI 10.1016/j.comptc.2014.06.017
Identifierdc.identifier.urihttps://repositorio.uchile.cl/handle/2250/132523
General notedc.descriptionArtículo de publicación ISIen_US
Abstractdc.description.abstractWe 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.en_US
Patrocinadordc.description.sponsorshipFondecyt No. 1140313en_US
Lenguagedc.language.isoen_USen_US
Publisherdc.publisherElsevieren_US
Type of licensedc.rightsAtribución-NoComercial-SinDerivadas 3.0 Chile*
Link to Licensedc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/3.0/cl/*
Keywordsdc.subjectElectrostatic potentialen_US
Keywordsdc.subjectDegenerate statesen_US
Keywordsdc.subjectAtoms in Moleculesen_US
Keywordsdc.subjectReactivityen_US
Títulodc.titleA problematic issue for atoms in molecules: Impact of (quasi-)degenerate states on Quantum Theory Atoms in Molecules and Hirshfeld-I propertiesen_US
Document typedc.typeArtículo de revista


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Atribución-NoComercial-SinDerivadas 3.0 Chile
Except where otherwise noted, this item's license is described as Atribución-NoComercial-SinDerivadas 3.0 Chile