Basis Electronic Activity of Molecular Systems. A Theory of Bond Reactivity

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dc.catalogadorgjm
dc.contributor.authorBenítez Olivares, Francisca Javiera
dc.contributor.authorGutiérrez Oliva, Soledad
dc.contributor.authorHerrera Pisani, Bárbara Andrea
dc.contributor.authorToro Labbé, Alejandro
dc.date.accessioned2024-03-13T20:14:23Z
dc.date.available2024-03-13T20:14:23Z
dc.date.issued2024
dc.description.abstractIn this paper, we present a new finding, the basis electronic activity (BEA) of molecular systems; it corresponds to the significant, although nonreactive, vibrationally induced electronic activity that takes place in any molecular system. Although the molecule’s BEA is composed of an equal number of local contributions as the vibrational degrees of freedom, our results indicate that only stretching modes contribute to it. To account for this electronic activity, a new descriptor, the bond electronic flux (BEF), is introduced. The BEF combined with the force constant of the potential well hosting the electronic activity gives rise to the effective bond reactivity index (EBR), which turns out to be the first density functional theory-based descriptor that simultaneously accounts for structural and electronic effects. Besides quantifying the bond reactivity, EBR provides a basis to compare the reactivities of bonds inserted in different chemical environments and paves the way for the exertion of selective control to enhance or inhibit their reactivities. The new concepts formulated in this paper and the associated computational tools are illustrated with characterization of the BEA of a set of representative molecules. In all cases, the BEFs follow the same linear pattern, whose slopes indicate the intensity of the electronic activity and quantify the reactivity of chemical bonds.
dc.fuente.origenORCID
dc.identifier.doi10.1021/acs.jpca.4c00359
dc.identifier.urihttps://doi.org/10.1021/acs.jpca.4c00359
dc.identifier.urihttps://repositorio.uc.cl/handle/11534/84384
dc.information.autorucEscuela de Química; Benítez Olivares, Francisca Javiera; S/I; 1092282
dc.information.autorucEscuela de Química; Gutiérrez Oliva, Soledad; 0000-0002-3436-1985; 1004064
dc.information.autorucEscuela de Química; Herrera Pisani, Bárbara Andrea; 0000-0003-1911-4473; 4439
dc.information.autorucEscuela de Química; Toro Labbe, Alejandro Miguel; 0000-0001-9906-2153; 99827
dc.issue.numero10
dc.language.isoen
dc.nota.accesoContenido parcial
dc.pagina.final1972
dc.pagina.inicio1737
dc.revistaThe Journal of Physical Chemistry A
dc.rightsacceso restringido
dc.subjectChemical bonding
dc.subjectMolecular electronics
dc.subjectMolecules
dc.subjectOscillation
dc.subjectReactivity
dc.subject.ddc600
dc.subject.deweyTecnologíaes_ES
dc.titleBasis Electronic Activity of Molecular Systems. A Theory of Bond Reactivity
dc.typeartículo
dc.volumen128
sipa.codpersvinculados1092282
sipa.codpersvinculados1004064
sipa.codpersvinculados4439
sipa.codpersvinculados99827
sipa.trazabilidadORCID;2024-03-11
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