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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.citation	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.identifier.uri	http://hdl.handle.net/10550/12948
dc.description.abstract	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_US
dc.language.iso	en	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	journal article	es_ES
dc.subject.unesco	UNESCO::FÍSICA::Química física	en
dc.identifier.doi	10.1063/1.1772357	en
dc.identifier.idgrec	014448	en
dc.type.hasVersion	VoR	es_ES
dc.identifier.url	http://scitation.aip.org/getpdf/servlet/GetPDFServlet?filetype=pdf&id=JCPSA6000121000009004127000001&idtype=cvips&prog=normal&doi=10.1063/1.1772357	en