Show simple item record

dc.contributor.authorRedondo Cristóbal, María del Pilar 
dc.contributor.authorLargo Cabrerizo, Antonio 
dc.contributor.authorRayón Rico, Víctor Manuel 
dc.contributor.authorMolpeceres de Diego, Germán
dc.contributor.authorSordo, José Ángel
dc.contributor.authorBarrientos Benito, María Carmen 
dc.date.accessioned2017-03-14T20:20:59Z
dc.date.available2017-03-14T20:20:59Z
dc.date.issued2014
dc.identifier.citationPhysical Chemistry Chemical Physics 2014 Aug 14;16(30), p. 16121-36es
dc.identifier.issn1463-9076es
dc.identifier.urihttp://uvadoc.uva.es/handle/10324/22610
dc.descriptionProducción Científicaes
dc.description.abstractThe reactions, in the gas phase, between alkali-earth monocations (Mg(+), Ca(+), Sr(+), Ba(+)) and CH3X (X = Cl, Br) have been theoretically studied. The stationary points on the potential energy surfaces were characterized at the Density Functional Theory level on the framework of the mPW1K functional with the QZVPP Ahlrichs's basis sets. A complementary kinetics study has also been performed using conventional/variational microcanonical transition state theory. In the reactions of Mg(+) with either chloro- or bromomethane the transition structure lies in energy clearly above the reactants rendering thermal activation of CH3Cl or CH3Br extremely improbable. The remaining reactions are exothermic and barrierless processes; thus carbon-halogen bonds in chloro- or bromomethane can be activated by calcium, strontium or barium monocations to obtain the metal halogen cation and the methyl radical. The Mulliken population analysis for the stationary points of the potential energy surfaces supports a "harpoon"-like mechanism for the halogen-atom abstraction processes. An analysis of the bonding situation for the stationary points on the potential energy surface has also been performed in the framework of the quantum theory of atoms in moleculeses
dc.format.mimetypeapplication/pdfes
dc.language.isoenges
dc.publisherRoyal Society of Chemistryes
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.classificationMoléculases
dc.titleHalogen-abstraction reactions from chloromethane and bromomethane molecules by alkaline-earth monocationses
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.holder© The Royal Society of Chemistryes
dc.identifier.doi10.1039/c4cp02094des
dc.relation.publisherversionhttp://pubs.rsc.orges
dc.identifier.publicationtitlePhysical Chemistry Chemical Physicses
dc.peerreviewedSIes
dc.description.projectJunta de Castilla y León (programa de apoyo a proyectos de investigación – Ref. VA330U13)es
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 International


Files in this item

Thumbnail

This item appears in the following Collection(s)

Show simple item record