Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO
Autor(a) principal: | |
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Data de Publicação: | 2008 |
Outros Autores: | |
Tipo de documento: | Artigo |
Idioma: | eng |
Título da fonte: | Journal of the Brazilian Chemical Society (Online) |
Texto Completo: | http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532008000100012 |
Resumo: | Theoretical calculations using effective core potential (ECP) based methods were performed for a large number of molecular systems related to SF6. Hartree-Fock (HF), MP2 and QCISD(T) methods were used. The quantities computed include equilibrium molecular geometries, bond dissociation energies, and adiabatic ionization energies. Where possible these quantities are compared with information available in the literature. The equilibrium geometries produced using the ECP-based methods are in very good agreement with structures reported in the literature. For the various energy differences, corresponding to the processes listed above, the ECP-based energies reproduce the trends. In addition to calculations on individual molecules, the reaction of SF6 with CO+ was studied. The first objective was to locate the reactant ion-molecule complex, the transition state, and the product ion-molecule complex for each of these systems. In this reaction neither a transition state nor a reactant ion-molecule complex could be located using HF-based forces and energies, reaction seemed to pass without a barrier to SF5+ + FCO. The use of a CASSCF(7,7)/B0 method was required to find the reactant ion-molecule complex. Finally more detailed studies were made of how the energy and charge distribution change as the reaction proceeds from reactants to products. It was observed that the reaction SF6 + CO+ -> SF5+ + FCO occurs via F- abstraction, with the electronic energy barrier of 103.86 kJ mol-1. |
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Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCOgas phase reactionsanthropogenic chemical compoundQCISD(T)pseudopotentialTheoretical calculations using effective core potential (ECP) based methods were performed for a large number of molecular systems related to SF6. Hartree-Fock (HF), MP2 and QCISD(T) methods were used. The quantities computed include equilibrium molecular geometries, bond dissociation energies, and adiabatic ionization energies. Where possible these quantities are compared with information available in the literature. The equilibrium geometries produced using the ECP-based methods are in very good agreement with structures reported in the literature. For the various energy differences, corresponding to the processes listed above, the ECP-based energies reproduce the trends. In addition to calculations on individual molecules, the reaction of SF6 with CO+ was studied. The first objective was to locate the reactant ion-molecule complex, the transition state, and the product ion-molecule complex for each of these systems. In this reaction neither a transition state nor a reactant ion-molecule complex could be located using HF-based forces and energies, reaction seemed to pass without a barrier to SF5+ + FCO. The use of a CASSCF(7,7)/B0 method was required to find the reactant ion-molecule complex. Finally more detailed studies were made of how the energy and charge distribution change as the reaction proceeds from reactants to products. It was observed that the reaction SF6 + CO+ -> SF5+ + FCO occurs via F- abstraction, with the electronic energy barrier of 103.86 kJ mol-1.Sociedade Brasileira de Química2008-01-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532008000100012Journal of the Brazilian Chemical Society v.19 n.1 2008reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532008000100012info:eu-repo/semantics/openAccessMorgon,Nelson H.Kennedy,Richard A.eng2008-03-10T00:00:00Zoai:scielo:S0103-50532008000100012Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2008-03-10T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false |
dc.title.none.fl_str_mv |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
title |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
spellingShingle |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO Morgon,Nelson H. gas phase reactions anthropogenic chemical compound QCISD(T) pseudopotential |
title_short |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
title_full |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
title_fullStr |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
title_full_unstemmed |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
title_sort |
Theoretical study of the gas-phase reaction: SF6 + CO+ -> SF5+ + FCO |
author |
Morgon,Nelson H. |
author_facet |
Morgon,Nelson H. Kennedy,Richard A. |
author_role |
author |
author2 |
Kennedy,Richard A. |
author2_role |
author |
dc.contributor.author.fl_str_mv |
Morgon,Nelson H. Kennedy,Richard A. |
dc.subject.por.fl_str_mv |
gas phase reactions anthropogenic chemical compound QCISD(T) pseudopotential |
topic |
gas phase reactions anthropogenic chemical compound QCISD(T) pseudopotential |
description |
Theoretical calculations using effective core potential (ECP) based methods were performed for a large number of molecular systems related to SF6. Hartree-Fock (HF), MP2 and QCISD(T) methods were used. The quantities computed include equilibrium molecular geometries, bond dissociation energies, and adiabatic ionization energies. Where possible these quantities are compared with information available in the literature. The equilibrium geometries produced using the ECP-based methods are in very good agreement with structures reported in the literature. For the various energy differences, corresponding to the processes listed above, the ECP-based energies reproduce the trends. In addition to calculations on individual molecules, the reaction of SF6 with CO+ was studied. The first objective was to locate the reactant ion-molecule complex, the transition state, and the product ion-molecule complex for each of these systems. In this reaction neither a transition state nor a reactant ion-molecule complex could be located using HF-based forces and energies, reaction seemed to pass without a barrier to SF5+ + FCO. The use of a CASSCF(7,7)/B0 method was required to find the reactant ion-molecule complex. Finally more detailed studies were made of how the energy and charge distribution change as the reaction proceeds from reactants to products. It was observed that the reaction SF6 + CO+ -> SF5+ + FCO occurs via F- abstraction, with the electronic energy barrier of 103.86 kJ mol-1. |
publishDate |
2008 |
dc.date.none.fl_str_mv |
2008-01-01 |
dc.type.driver.fl_str_mv |
info:eu-repo/semantics/article |
dc.type.status.fl_str_mv |
info:eu-repo/semantics/publishedVersion |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532008000100012 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532008000100012 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1590/S0103-50532008000100012 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
dc.publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
publisher.none.fl_str_mv |
Sociedade Brasileira de Química |
dc.source.none.fl_str_mv |
Journal of the Brazilian Chemical Society v.19 n.1 2008 reponame:Journal of the Brazilian Chemical Society (Online) instname:Sociedade Brasileira de Química (SBQ) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
_version_ |
1750318168575836160 |