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dc.contributor.authorSambrano, JR
dc.contributor.authorGracia, L.
dc.contributor.authorAndres, J.
dc.contributor.authorBerski, S.
dc.contributor.authorBeltran, A.
dc.date.accessioned2014-05-20T13:26:30Z
dc.date.available2014-05-20T13:26:30Z
dc.date.issued2004-12-09
dc.identifierhttp://dx.doi.org/10.1021/jp047229b
dc.identifier.citationJournal of Physical Chemistry A. Washington: Amer Chemical Soc, v. 108, n. 49, p. 10850-10860, 2004.
dc.identifier.issn1089-5639
dc.identifier.urihttp://hdl.handle.net/11449/8552
dc.description.abstractThe potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.en
dc.format.extent10850-10860
dc.language.isoeng
dc.publisherAmer Chemical Soc
dc.relation.ispartofJournal of Physical Chemistry A
dc.sourceWeb of Science
dc.titleA theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2en
dc.typeArtigo
dcterms.licensehttp://pubs.acs.org/paragonplus/copyright/jpa_form_a.pdf
dcterms.rightsHolderAmer Chemical Soc
dc.contributor.institutionUniv Jaume 1
dc.contributor.institutionUniversidade Estadual Paulista (Unesp)
dc.contributor.institutionUniv Wroclaw
dc.description.affiliationUniv Jaume 1, Dept Ciencies Expt, Castello 12080, Spain
dc.description.affiliationUniv Estadual Paulista, Lab Simulacao Mol, Dept Math, BR-17033360 Bauru, Brazil
dc.description.affiliationUniv Wroclaw, Fac Chem, PL-50383 Wroclaw, Poland
dc.description.affiliationUnespUniv Estadual Paulista, Lab Simulacao Mol, Dept Math, BR-17033360 Bauru, Brazil
dc.identifier.doi10.1021/jp047229b
dc.identifier.wosWOS:000225548900012
dc.rights.accessRightsAcesso restrito
unesp.campusUniversidade Estadual Paulista (Unesp), Faculdade de Ciências, Baurupt
dc.identifier.lattes6284168579617066
unesp.author.lattes6284168579617066
unesp.author.orcid0000-0003-0232-3957[3]
unesp.author.orcid0000-0001-9684-2568[2]
unesp.author.orcid0000-0001-9665-5527[5]
dc.relation.ispartofjcr2.836
dc.relation.ispartofsjr1,170
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