Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential
| العنوان: | Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential |
|---|---|
| المؤلفون: | Petri Heinonen, Markku Räsänen, Ilkka Kilpeläinen, Jaroslaw Kalinowski, R. Benny Gerber |
| المصدر: | Angewandte Chemie (International ed. in English). 53(1) |
| سنة النشر: | 2013 |
| مصطلحات موضوعية: | Ozonolysis, Diradical, Chemistry, General Chemistry, General Medicine, Catalysis, Transition state, chemistry.chemical_compound, Molecular dynamics, Dioxirane, Computational chemistry, Ab initio quantum chemistry methods, Criegee intermediate, Isomerization |
| الوصف: | The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2 , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2 O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2 OO. The implications for reactions of Criegee intermediates are discussed. |
| تدمد: | 1521-3773 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bdb9a94766ce180a4c0dd50f5820a14f https://pubmed.ncbi.nlm.nih.gov/24227050 |
| Rights: | CLOSED |
| رقم الانضمام: | edsair.doi.dedup.....bdb9a94766ce180a4c0dd50f5820a14f |
| قاعدة البيانات: | OpenAIRE |
| ResultId |
1 |
|---|---|
| Header |
edsair OpenAIRE edsair.doi.dedup.....bdb9a94766ce180a4c0dd50f5820a14f 774 3 unknown 773.984558105469 |
| PLink |
https://search.ebscohost.com/login.aspx?direct=true&site=eds-live&scope=site&db=edsair&AN=edsair.doi.dedup.....bdb9a94766ce180a4c0dd50f5820a14f&custid=s6537998&authtype=sso |
| FullText |
Array
(
[Availability] => 0
)
Array ( [0] => Array ( [Url] => https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bdb9a94766ce180a4c0dd50f5820a14f# [Name] => EDS - OpenAIRE [Category] => fullText [Text] => View record in OpenAIRE [MouseOverText] => View record in OpenAIRE ) ) |
| Items |
Array
(
[Name] => Title
[Label] => Title
[Group] => Ti
[Data] => Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential
)
Array ( [Name] => Author [Label] => Authors [Group] => Au [Data] => <searchLink fieldCode="AR" term="%22Petri+Heinonen%22">Petri Heinonen</searchLink><br /><searchLink fieldCode="AR" term="%22Markku+Räsänen%22">Markku Räsänen</searchLink><br /><searchLink fieldCode="AR" term="%22Ilkka+Kilpeläinen%22">Ilkka Kilpeläinen</searchLink><br /><searchLink fieldCode="AR" term="%22Jaroslaw+Kalinowski%22">Jaroslaw Kalinowski</searchLink><br /><searchLink fieldCode="AR" term="%22R%2E+Benny+Gerber%22">R. Benny Gerber</searchLink> ) Array ( [Name] => TitleSource [Label] => Source [Group] => Src [Data] => <i>Angewandte Chemie (International ed. in English)</i>. 53(1) ) Array ( [Name] => DatePubCY [Label] => Publication Year [Group] => Date [Data] => 2013 ) Array ( [Name] => Subject [Label] => Subject Terms [Group] => Su [Data] => <searchLink fieldCode="DE" term="%22Ozonolysis%22">Ozonolysis</searchLink><br /><searchLink fieldCode="DE" term="%22Diradical%22">Diradical</searchLink><br /><searchLink fieldCode="DE" term="%22Chemistry%22">Chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22General+Chemistry%22">General Chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22General+Medicine%22">General Medicine</searchLink><br /><searchLink fieldCode="DE" term="%22Catalysis%22">Catalysis</searchLink><br /><searchLink fieldCode="DE" term="%22Transition+state%22">Transition state</searchLink><br /><searchLink fieldCode="DE" term="%22chemistry%2Echemical%5Fcompound%22">chemistry.chemical_compound</searchLink><br /><searchLink fieldCode="DE" term="%22Molecular+dynamics%22">Molecular dynamics</searchLink><br /><searchLink fieldCode="DE" term="%22Dioxirane%22">Dioxirane</searchLink><br /><searchLink fieldCode="DE" term="%22Computational+chemistry%22">Computational chemistry</searchLink><br /><searchLink fieldCode="DE" term="%22Ab+initio+quantum+chemistry+methods%22">Ab initio quantum chemistry methods</searchLink><br /><searchLink fieldCode="DE" term="%22Criegee+intermediate%22">Criegee intermediate</searchLink><br /><searchLink fieldCode="DE" term="%22Isomerization%22">Isomerization</searchLink> ) Array ( [Name] => Abstract [Label] => Description [Group] => Ab [Data] => The isomerization and decomposition dynamics of the simplest Criegee intermediate CH2 OO have been studied by classical trajectory simulations using the multireference ab initio MR-PT2 potential on the fly. A new, accelerated algorithm for dynamics with MR-PT2 was used. For an initial temperature of 300 K, starting from the transition state from CH2 OO→CH2 O2 , the system reaches the dioxirane structure in around 50 fs, then isomerizes to formic acid (in ca. 2800 fs), and decomposes into CO+H2 O at around 2900 fs. The contributions of different configurations to the multiconfigurational total electronic wave function vary dramatically along the trajectory, with diradical contributions being important for transition states corresponding to H-atom transfers, while being only moderately significant for CH2 OO. The implications for reactions of Criegee intermediates are discussed. ) Array ( [Name] => ISSN [Label] => ISSN [Group] => ISSN [Data] => 1521-3773 ) Array ( [Name] => URL [Label] => Access URL [Group] => URL [Data] => <link linkTarget="URL" linkTerm="https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bdb9a94766ce180a4c0dd50f5820a14f" linkWindow="_blank">https://explore.openaire.eu/search/publication?articleId=doi_dedup___::bdb9a94766ce180a4c0dd50f5820a14f</link><br /><link linkTarget="URL" linkTerm="https://pubmed.ncbi.nlm.nih.gov/24227050" linkWindow="_blank">https://pubmed.ncbi.nlm.nih.gov/24227050</link> ) Array ( [Name] => Copyright [Label] => Rights [Group] => Cpyrght [Data] => CLOSED ) Array ( [Name] => AN [Label] => Accession Number [Group] => ID [Data] => edsair.doi.dedup.....bdb9a94766ce180a4c0dd50f5820a14f ) |
| RecordInfo |
Array
(
[BibEntity] => Array
(
[Languages] => Array
(
[0] => Array
(
[Text] => Undetermined
)
)
[Subjects] => Array
(
[0] => Array
(
[SubjectFull] => Ozonolysis
[Type] => general
)
[1] => Array
(
[SubjectFull] => Diradical
[Type] => general
)
[2] => Array
(
[SubjectFull] => Chemistry
[Type] => general
)
[3] => Array
(
[SubjectFull] => General Chemistry
[Type] => general
)
[4] => Array
(
[SubjectFull] => General Medicine
[Type] => general
)
[5] => Array
(
[SubjectFull] => Catalysis
[Type] => general
)
[6] => Array
(
[SubjectFull] => Transition state
[Type] => general
)
[7] => Array
(
[SubjectFull] => chemistry.chemical_compound
[Type] => general
)
[8] => Array
(
[SubjectFull] => Molecular dynamics
[Type] => general
)
[9] => Array
(
[SubjectFull] => Dioxirane
[Type] => general
)
[10] => Array
(
[SubjectFull] => Computational chemistry
[Type] => general
)
[11] => Array
(
[SubjectFull] => Ab initio quantum chemistry methods
[Type] => general
)
[12] => Array
(
[SubjectFull] => Criegee intermediate
[Type] => general
)
[13] => Array
(
[SubjectFull] => Isomerization
[Type] => general
)
)
[Titles] => Array
(
[0] => Array
(
[TitleFull] => Isomerization and decomposition of a Criegee intermediate in the ozonolysis of alkenes: dynamics using a multireference potential
[Type] => main
)
)
)
[BibRelationships] => Array
(
[HasContributorRelationships] => Array
(
[0] => Array
(
[PersonEntity] => Array
(
[Name] => Array
(
[NameFull] => Petri Heinonen
)
)
)
[1] => Array
(
[PersonEntity] => Array
(
[Name] => Array
(
[NameFull] => Markku Räsänen
)
)
)
[2] => Array
(
[PersonEntity] => Array
(
[Name] => Array
(
[NameFull] => Ilkka Kilpeläinen
)
)
)
[3] => Array
(
[PersonEntity] => Array
(
[Name] => Array
(
[NameFull] => Jaroslaw Kalinowski
)
)
)
[4] => Array
(
[PersonEntity] => Array
(
[Name] => Array
(
[NameFull] => R. Benny Gerber
)
)
)
)
[IsPartOfRelationships] => Array
(
[0] => Array
(
[BibEntity] => Array
(
[Dates] => Array
(
[0] => Array
(
[D] => 19
[M] => 08
[Type] => published
[Y] => 2013
)
)
[Identifiers] => Array
(
[0] => Array
(
[Type] => issn-print
[Value] => 15213773
)
[1] => Array
(
[Type] => issn-locals
[Value] => edsair
)
)
[Numbering] => Array
(
[0] => Array
(
[Type] => volume
[Value] => 53
)
[1] => Array
(
[Type] => issue
[Value] => 1
)
)
[Titles] => Array
(
[0] => Array
(
[TitleFull] => Angewandte Chemie (International ed. in English)
[Type] => main
)
)
)
)
)
)
)
|
| IllustrationInfo |