Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations.
Identifieur interne : 000163 ( PubMed/Checkpoint ); précédent : 000162; suivant : 000164Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations.
Auteurs : B. Sirjean [France] ; P A Glaude ; M F Ruiz-Lopez ; R. FournetSource :
- The journal of physical chemistry. A [ 1089-5639 ] ; 2006.
Abstract
This work reports a theoretical study of the gas-phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data(DeltaHf(o), S(o), Cp(o)) for all the involved species have been obtained by means of isodesmic reactions. The contribution of hindered rotors has also been included. Activation barriers of each reaction have been analyzed to assess the energetically most favorable pathways for the decomposition of biradicals. Rate constants have been derived for all elementary reactions using transition-state theory at 1 atm and temperatures ranging from 600 to 2000 K. Global rate constant for the decomposition of the cyclic alkanes in molecular products have been calculated. Comparison between calculated and experimental results allowed us to validate the theoretical approach. An important result is that the rotational barriers between the conformers, which are usually neglected, are of importance in decomposition rate of the largest biradicals. Ring strain energies (RSE) in transition states for ring opening have been estimated and show that the main part of RSE contained in the cyclic reactants is removed upon the activation process.
DOI: 10.1021/jp0651081
PubMed: 17107122
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Sirjean</name><affiliation wicri:level="3"><nlm:affiliation>Département de Chimie Physique des Réactions, UMR 7630 CNRS-INPL, ENSIC, 1, rue Grandville, BP 20451, 54001 Nancy Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Département de Chimie Physique des Réactions, UMR 7630 CNRS-INPL, ENSIC, 1, rue Grandville, BP 20451, 54001 Nancy Cedex</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region><settlement type="city">Nancy</settlement></placeName></affiliation></author><author><name sortKey="Glaude, P A" sort="Glaude, P A" uniqKey="Glaude P" first="P A" last="Glaude">P A Glaude</name></author><author><name sortKey="Ruiz Lopez, M F" sort="Ruiz Lopez, M F" uniqKey="Ruiz Lopez M" first="M F" last="Ruiz-Lopez">M F Ruiz-Lopez</name></author><author><name sortKey="Fournet, R" sort="Fournet, R" uniqKey="Fournet R" first="R" last="Fournet">R. Fournet</name></author></titleStmt><publicationStmt><idno type="wicri:source">PubMed</idno><date when="2006">2006</date><idno type="doi">10.1021/jp0651081</idno><idno type="RBID">pubmed:17107122</idno><idno type="pmid">17107122</idno><idno type="wicri:Area/PubMed/Corpus">000160</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Corpus" wicri:corpus="PubMed">000160</idno><idno type="wicri:Area/PubMed/Curation">000160</idno><idno type="wicri:explorRef" wicri:stream="PubMed" wicri:step="Curation">000160</idno><idno type="wicri:Area/PubMed/Checkpoint">000160</idno><idno type="wicri:explorRef" wicri:stream="Checkpoint" wicri:step="PubMed">000160</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en">Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations.</title><author><name sortKey="Sirjean, B" sort="Sirjean, B" uniqKey="Sirjean B" first="B" last="Sirjean">B. Sirjean</name><affiliation wicri:level="3"><nlm:affiliation>Département de Chimie Physique des Réactions, UMR 7630 CNRS-INPL, ENSIC, 1, rue Grandville, BP 20451, 54001 Nancy Cedex, France.</nlm:affiliation><country xml:lang="fr">France</country><wicri:regionArea>Département de Chimie Physique des Réactions, UMR 7630 CNRS-INPL, ENSIC, 1, rue Grandville, BP 20451, 54001 Nancy Cedex</wicri:regionArea><placeName><region type="region" nuts="2">Grand Est</region><region type="old region" nuts="2">Lorraine (région)</region><settlement type="city">Nancy</settlement></placeName></affiliation></author><author><name sortKey="Glaude, P A" sort="Glaude, P A" uniqKey="Glaude P" first="P A" last="Glaude">P A Glaude</name></author><author><name sortKey="Ruiz Lopez, M F" sort="Ruiz Lopez, M F" uniqKey="Ruiz Lopez M" first="M F" last="Ruiz-Lopez">M F Ruiz-Lopez</name></author><author><name sortKey="Fournet, R" sort="Fournet, R" uniqKey="Fournet R" first="R" last="Fournet">R. Fournet</name></author></analytic><series><title level="j">The journal of physical chemistry. A</title><idno type="ISSN">1089-5639</idno><imprint><date when="2006" type="published">2006</date></imprint></series></biblStruct></sourceDesc></fileDesc><profileDesc><textClass></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">This work reports a theoretical study of the gas-phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data(DeltaHf(o), S(o), Cp(o)) for all the involved species have been obtained by means of isodesmic reactions. The contribution of hindered rotors has also been included. Activation barriers of each reaction have been analyzed to assess the energetically most favorable pathways for the decomposition of biradicals. Rate constants have been derived for all elementary reactions using transition-state theory at 1 atm and temperatures ranging from 600 to 2000 K. Global rate constant for the decomposition of the cyclic alkanes in molecular products have been calculated. Comparison between calculated and experimental results allowed us to validate the theoretical approach. An important result is that the rotational barriers between the conformers, which are usually neglected, are of importance in decomposition rate of the largest biradicals. Ring strain energies (RSE) in transition states for ring opening have been estimated and show that the main part of RSE contained in the cyclic reactants is removed upon the activation process.</div></front></TEI><pubmed><MedlineCitation Owner="NLM" Status="PubMed-not-MEDLINE"><PMID Version="1">17107122</PMID><DateCreated><Year>2006</Year><Month>11</Month><Day>19</Day></DateCreated><DateCompleted><Year>2007</Year><Month>01</Month><Day>26</Day></DateCompleted><DateRevised><Year>2007</Year><Month>03</Month><Day>27</Day></DateRevised><Article PubModel="Print"><Journal><ISSN IssnType="Print">1089-5639</ISSN><JournalIssue CitedMedium="Print"><Volume>110</Volume><Issue>46</Issue><PubDate><Year>2006</Year><Month>Nov</Month><Day>23</Day></PubDate></JournalIssue><Title>The journal of physical chemistry. A</Title><ISOAbbreviation>J Phys Chem A</ISOAbbreviation></Journal><ArticleTitle>Detailed kinetic study of the ring opening of cycloalkanes by CBS-QB3 calculations.</ArticleTitle><Pagination><MedlinePgn>12693-704</MedlinePgn></Pagination><Abstract><AbstractText>This work reports a theoretical study of the gas-phase unimolecular decomposition of cyclobutane, cyclopentane and cyclohexane by means of quantum chemical calculations. A biradical mechanism has been envisaged for each cycloalkane, and the main routes for the decomposition of the biradicals formed have been investigated at the CBS-QB3 level of theory. Thermochemical data(DeltaHf(o), S(o), Cp(o)) for all the involved species have been obtained by means of isodesmic reactions. The contribution of hindered rotors has also been included. Activation barriers of each reaction have been analyzed to assess the energetically most favorable pathways for the decomposition of biradicals. Rate constants have been derived for all elementary reactions using transition-state theory at 1 atm and temperatures ranging from 600 to 2000 K. Global rate constant for the decomposition of the cyclic alkanes in molecular products have been calculated. Comparison between calculated and experimental results allowed us to validate the theoretical approach. An important result is that the rotational barriers between the conformers, which are usually neglected, are of importance in decomposition rate of the largest biradicals. Ring strain energies (RSE) in transition states for ring opening have been estimated and show that the main part of RSE contained in the cyclic reactants is removed upon the activation process.</AbstractText></Abstract><AuthorList CompleteYN="Y"><Author ValidYN="Y"><LastName>Sirjean</LastName><ForeName>B</ForeName><Initials>B</Initials><AffiliationInfo><Affiliation>Département de Chimie Physique des Réactions, UMR 7630 CNRS-INPL, ENSIC, 1, rue Grandville, BP 20451, 54001 Nancy Cedex, France.</Affiliation></AffiliationInfo></Author><Author ValidYN="Y"><LastName>Glaude</LastName><ForeName>P A</ForeName><Initials>PA</Initials></Author><Author ValidYN="Y"><LastName>Ruiz-Lopez</LastName><ForeName>M F</ForeName><Initials>MF</Initials></Author><Author ValidYN="Y"><LastName>Fournet</LastName><ForeName>R</ForeName><Initials>R</Initials></Author></AuthorList><Language>eng</Language><PublicationTypeList><PublicationType UI="D016428">Journal Article</PublicationType></PublicationTypeList></Article><MedlineJournalInfo><Country>United States</Country><MedlineTA>J Phys Chem A</MedlineTA><NlmUniqueID>9890903</NlmUniqueID><ISSNLinking>1089-5639</ISSNLinking></MedlineJournalInfo></MedlineCitation><PubmedData><History><PubMedPubDate PubStatus="pubmed"><Year>2006</Year><Month>11</Month><Day>17</Day><Hour>9</Hour><Minute>0</Minute></PubMedPubDate><PubMedPubDate PubStatus="medline"><Year>2006</Year><Month>11</Month><Day>17</Day><Hour>9</Hour><Minute>1</Minute></PubMedPubDate><PubMedPubDate PubStatus="entrez"><Year>2006</Year><Month>11</Month><Day>17</Day><Hour>9</Hour><Minute>0</Minute></PubMedPubDate></History><PublicationStatus>ppublish</PublicationStatus><ArticleIdList><ArticleId IdType="doi">10.1021/jp0651081</ArticleId><ArticleId IdType="pubmed">17107122</ArticleId></ArticleIdList></PubmedData></pubmed><affiliations><list><country><li>France</li></country><region><li>Grand Est</li><li>Lorraine (région)</li></region><settlement><li>Nancy</li></settlement></list><tree><noCountry><name sortKey="Fournet, R" sort="Fournet, R" uniqKey="Fournet R" first="R" last="Fournet">R. Fournet</name><name sortKey="Glaude, P A" sort="Glaude, P A" uniqKey="Glaude P" first="P A" last="Glaude">P A Glaude</name><name sortKey="Ruiz Lopez, M F" sort="Ruiz Lopez, M F" uniqKey="Ruiz Lopez M" first="M F" last="Ruiz-Lopez">M F Ruiz-Lopez</name></noCountry><country name="France"><region name="Grand Est"><name sortKey="Sirjean, B" sort="Sirjean, B" uniqKey="Sirjean B" first="B" last="Sirjean">B. Sirjean</name></region></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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