Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane
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Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane

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Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane

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dc.contributor.author Arenas, Juan F.
dc.contributor.author Otero, Juan C.
dc.contributor.author Peláez, Daniel
dc.contributor.author Soto, Juan
dc.contributor.author Serrano Andrés, Luis
dc.date.accessioned 2010-06-14T08:13:03Z
dc.date.available 2010-06-14T08:13:03Z
dc.date.issued 2004
dc.identifier.uri http://hdl.handle.net/10550/12948
dc.language.iso en en
dc.relation http://scitation.aip.org/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JCPSA6000121000009004127000001&idtype=cvips&prog=normal&doi=10.1063/1.1772357 en
dc.source ARENAS, Juan F. ; OTERO, Juan C. ; PELÁEZ, Daniel ; SOTO, Juan ; SERRANO ANDRÉS, Luis. Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane. En: Journal of Chemical Physics, 2004, vol.121, no. 9 en
dc.subject Organic Compounds ; Negative Ions ; Potential Energy Surfaces ; Dissociation ; Ion-Molecule Reactions ; Perturbation Theory ; Density Functional Theory ; SCF Calculations en
dc.title Multiconfigurational second-order perturbation study of the decomposition of the radical anion of nitromethane en
dc.type info:eu-repo/semantics/article en
dc.type info:eu-repo/semantics/publishedVersion en
dc.subject.unesco UNESCO::FÍSICA::Química física en
dc.identifier.doi 10.1063/1.1772357 en
dc.description.abstractenglish The doublet potential energy surfaces involved in the decomposition of the nitromethane radical anion (CH3NO2−) have been studied by using the multistate extension of the multiconfigurational second-order perturbation method (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets. A very low energy barrier is found for the decomposition reaction: CH3NO2−→[CH3NO2]−→CH3+NO2−. No evidence has been obtained on the existence of an isomerization channel leading to the initial formation of the methylnitrite anion (CH3ONO−) which, in a subsequent reaction, would yield nitric oxide (NO). In contrast, it is suggested that NO is formed through the bimolecular reaction: CH3+NO2−→[CH3O-N-O]−→CH3O−+NO. In particular, the CASSCF/MS-CASPT2 results indicate that the methylnitrite radical anion CH3ONO− does not represent a minimum energy structure, as concluded by using density functional theory (DFT) methodologies. The inverse symmetry breaking effect present in DFT is demonstrated to be responsible for such erroneous prediction. en
dc.description.private luis.serrano@uv.es en
dc.identifier.idgrec 014448 en

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