Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile
Identifieur interne : 000704 ( Main/Corpus ); précédent : 000703; suivant : 000705Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile
Auteurs : Wibke Sudholt ; Andrzej L. Sobolewski ; Wolfgang DomckeSource :
- Chemical Physics [ 0301-0104 ] ; 1998.
Abstract
The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.
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DOI: 10.1016/S0301-0104(98)00368-1
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<record><TEI wicri:istexFullTextTei="biblStruct"><teiHeader><fileDesc><titleStmt><title>Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title><author><name sortKey="Sudholt, Wibke" sort="Sudholt, Wibke" uniqKey="Sudholt W" first="Wibke" last="Sudholt">Wibke Sudholt</name><affiliation><mods:affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</mods:affiliation></affiliation></author><author><name sortKey="Sobolewski, Andrzej L" sort="Sobolewski, Andrzej L" uniqKey="Sobolewski A" first="Andrzej L" last="Sobolewski">Andrzej L. Sobolewski</name><affiliation><mods:affiliation>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</mods:affiliation></affiliation></author><author><name sortKey="Domcke, Wolfgang" sort="Domcke, Wolfgang" uniqKey="Domcke W" first="Wolfgang" last="Domcke">Wolfgang Domcke</name><affiliation><mods:affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:DC1FA6F5EDCAA94238E255344BDF6B768E44C01B</idno><date when="1999" year="1999">1999</date><idno type="doi">10.1016/S0301-0104(98)00368-1</idno><idno type="url">https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/fulltext/pdf</idno><idno type="wicri:Area/Main/Corpus">000704</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title><author><name sortKey="Sudholt, Wibke" sort="Sudholt, Wibke" uniqKey="Sudholt W" first="Wibke" last="Sudholt">Wibke Sudholt</name><affiliation><mods:affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</mods:affiliation></affiliation></author><author><name sortKey="Sobolewski, Andrzej L" sort="Sobolewski, Andrzej L" uniqKey="Sobolewski A" first="Andrzej L" last="Sobolewski">Andrzej L. Sobolewski</name><affiliation><mods:affiliation>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</mods:affiliation></affiliation></author><author><name sortKey="Domcke, Wolfgang" sort="Domcke, Wolfgang" uniqKey="Domcke W" first="Wolfgang" last="Domcke">Wolfgang Domcke</name><affiliation><mods:affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Chemical Physics</title><title level="j" type="abbrev">CHEMPH</title><idno type="ISSN">0301-0104</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998">1998</date><biblScope unit="volume">240</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="9">9</biblScope><biblScope unit="page" to="18">18</biblScope></imprint><idno type="ISSN">0301-0104</idno></series><idno type="istex">DC1FA6F5EDCAA94238E255344BDF6B768E44C01B</idno><idno type="DOI">10.1016/S0301-0104(98)00368-1</idno><idno type="PII">S0301-0104(98)00368-1</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0301-0104</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.</div></front></TEI><istex><corpusName>elsevier</corpusName><author><json:item><name>Wibke Sudholt</name><affiliations><json:string>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</json:string></affiliations></json:item><json:item><name>Andrzej L Sobolewski</name><affiliations><json:string>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</json:string></affiliations></json:item><json:item><name>Wolfgang Domcke</name><affiliations><json:string>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><abstract>The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.</abstract><qualityIndicators><score>6.932</score><pdfVersion>1.2</pdfVersion><pdfPageSize>540 x 712 pts</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>1151</abstractCharCount><pdfWordCount>5377</pdfWordCount><pdfCharCount>30986</pdfCharCount><pdfPageCount>10</pdfPageCount><abstractWordCount>161</abstractWordCount></qualityIndicators><title>Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title><pii><json:string>S0301-0104(98)00368-1</json:string></pii><genre><json:string>research-article</json:string></genre><host><volume>240</volume><pii><json:string>S0301-0104(00)X0702-1</json:string></pii><pages><last>18</last><first>9</first></pages><issn><json:string>0301-0104</json:string></issn><issue>1–2</issue><genre></genre><language><json:string>unknown</json:string></language><title>Chemical Physics</title><publicationDate>1999</publicationDate></host><categories><wos><json:string>PHYSICS, ATOMIC, MOLECULAR & CHEMICAL</json:string><json:string>CHEMISTRY, PHYSICAL</json:string></wos></categories><publicationDate>1998</publicationDate><copyrightDate>1999</copyrightDate><doi><json:string>10.1016/S0301-0104(98)00368-1</json:string></doi><id>DC1FA6F5EDCAA94238E255344BDF6B768E44C01B</id><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>ELSEVIER</publisher><availability><p>ELSEVIER</p></availability><date>1999</date></publicationStmt><notesStmt><note type="content">Fig. 1: Projection of the CIS optimized geometries of DMABN along different reaction paths onto the plane spanned by the twisting and wagging coordinates. Crosses denote reaction paths where the Lb-like LE and La-like CT states can be distinguished by symmetry. Pluses denote the reaction path of C1 symmetry, where only the lowest excited singlet state can be optimized.</note><note type="content">Fig. 2: Potential-energy functions for the lowest excited singlet states calculated along the wagging reaction path for planar (a,c,e) and fully twisted (b,d,f) DMABN. Triangles denote the Lb-like LE state, squares the La-like CT state. (a,b): CIS energy for the optimized structures; (c,d): CASSCF energy calculated at CIS geometries; (e,f): CASPT2 energy calculated at CIS geometries. Energies are given relatively to the HF (a,b), CASSCF (c,d) and CASPT2 (e,f) ground-state energies calculated at the MP2 C2v minimum of the ground state.</note><note type="content">Fig. 3: CASSCF dipole moments for the lowest excited singlet states calculated along the wagging reaction path for planar (a) and fully twisted (b) DMABN. Triangles refer to the Lb-like LE state, squares to the La-like CT state, and circles to the ground state. Solid lines refer to a geometry optimized for the same state, dashed lines to a geometry optimized for the corresponding CT state.</note><note type="content">Fig. 4: Potential-energy functions for the lowest excited singlet states of DMABN calculated along the reaction paths for pure twisting (a,c,e) and combined twisting and wagging (b,d,f). The optimal values of δ are given in Fig. 1. Triangles denote the Lb-like LE state, squares the La-like CT state. Solid lines refer to a single-state optimized wavefunction at a geometry optimized for the same state, dashed lines refer to a single-state optimized wavefunction at a geometry optimized for the corresponding CT state, and dotted lines refer to a state-averaged wavefunction. (a,b): CIS energy for the optimized structures; (c,d): CASSCF energy calculated at CIS geometries; (e,f): CASPT2 energy calculated at CIS geometries. Energies are given relatively to the HF (a,b), CASSCF (c,d) and CASPT2 (e,f) ground-state energies calculated at the MP2 C2v minimum of the ground state. The point at θ=75° on the “S2” potential-energy curve in (f) is skipped due to its significant lower reference weight.</note><note type="content">Fig. 5: CASSCF dipole moments for the lowest excited singlet states of DMABN calculated along the reaction paths for pure twisting (a) and combined twisting and wagging (b). The optimal values of δ are given in Fig. 1. Triangles refer to the Lb-like LE state, squares to the La-like CT state, and circles to the ground state. Solid lines refer to a single-state optimized wavefunction at a geometry optimized for the same state, dashed lines refer to a single-state optimized wavefunction at a geometry optimized for the corresponding CT state, and dotted lines refer to a state-averaged wavefunction.</note><note type="content">Fig. 6: CASPT2 potential-energy functions for the lowest excited singlet states of DMABN calculated along the twisting coordinate (a) and the wagging coordinate (b) with all other coordinates frozen. Triangles denote the Lb-like LE state, squares the La-like CT state. Energies are given relatively to the CASPT2 ground-state energy calculated at the MP2 C2v minimum of the ground state.</note><note type="content">Table 1: Definition of active electrons and frozen, inactive and active orbitals in the CASSCF single-point calculations of DMABN following the different reaction paths along the twisting and wagging coordinates</note><note type="content">Table 2: Assignment of the lowest excited singlet states of DMABN in each point group to the Lb-like LE and La-like CT states following the different reaction paths along the twisting and wagging coordinates</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title><author><persName><forename type="first">Wibke</forename><surname>Sudholt</surname></persName><affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</affiliation></author><author><persName><forename type="first">Andrzej L</forename><surname>Sobolewski</surname></persName><affiliation>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</affiliation></author><author><persName><forename type="first">Wolfgang</forename><surname>Domcke</surname></persName><affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</affiliation></author></analytic><monogr><title level="j">Chemical Physics</title><title level="j" type="abbrev">CHEMPH</title><idno type="pISSN">0301-0104</idno><idno type="PII">S0301-0104(00)X0702-1</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998"></date><biblScope unit="volume">240</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="9">9</biblScope><biblScope unit="page" to="18">18</biblScope></imprint></monogr><idno type="istex">DC1FA6F5EDCAA94238E255344BDF6B768E44C01B</idno><idno type="DOI">10.1016/S0301-0104(98)00368-1</idno><idno type="PII">S0301-0104(98)00368-1</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>1999</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.</p></abstract></profileDesc><revisionDesc><change when="1998-08-28">Received</change><change when="1998">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Elsevier, elements deleted: ce:floats; body; tail"><istex:xmlDeclaration>version="1.0" encoding="utf-8"</istex:xmlDeclaration><istex:docType PUBLIC="-//ES//DTD journal article DTD version 4.5.2//EN//XML" URI="art452.dtd" name="istex:docType"><istex:entity SYSTEM="fx1" NDATA="IMAGE" name="fx1"></istex:entity><istex:entity SYSTEM="gr1" NDATA="IMAGE" name="gr1"></istex:entity><istex:entity SYSTEM="gr2" NDATA="IMAGE" name="gr2"></istex:entity><istex:entity SYSTEM="gr3" NDATA="IMAGE" name="gr3"></istex:entity><istex:entity SYSTEM="gr4" NDATA="IMAGE" name="gr4"></istex:entity><istex:entity SYSTEM="gr5" NDATA="IMAGE" name="gr5"></istex:entity><istex:entity SYSTEM="gr6" NDATA="IMAGE" name="gr6"></istex:entity></istex:docType><istex:document><converted-article version="4.5.2" docsubtype="fla"><item-info><jid>CHEMPH</jid><aid>3422</aid><ce:pii>S0301-0104(98)00368-1</ce:pii><ce:doi>10.1016/S0301-0104(98)00368-1</ce:doi><ce:copyright year="1999" type="full-transfer">Elsevier Science B.V.</ce:copyright></item-info><head><ce:title>Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</ce:title><ce:author-group><ce:author><ce:given-name>Wibke</ce:given-name><ce:surname>Sudholt</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:author><ce:given-name>Andrzej L</ce:given-name><ce:surname>Sobolewski</ce:surname><ce:cross-ref refid="AFF2">b</ce:cross-ref></ce:author><ce:author><ce:given-name>Wolfgang</ce:given-name><ce:surname>Domcke</ce:surname><ce:cross-ref refid="AFF1">a</ce:cross-ref></ce:author><ce:affiliation id="AFF1"><ce:label>a</ce:label><ce:textfn>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</ce:textfn></ce:affiliation><ce:affiliation id="AFF2"><ce:label>b</ce:label><ce:textfn>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</ce:textfn></ce:affiliation></ce:author-group><ce:date-received day="28" month="8" year="1998"></ce:date-received><ce:abstract><ce:section-title>Abstract</ce:section-title><ce:abstract-sec><ce:simple-para>The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.</ce:simple-para></ce:abstract-sec></ce:abstract></head></converted-article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Ab initio study of the amino group twisting and wagging reaction paths in the intramolecular charge transfer of 4-(N,N-dimethylamino)benzonitrile</title></titleInfo><name type="personal"><namePart type="given">Wibke</namePart><namePart type="family">Sudholt</namePart><affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Andrzej L</namePart><namePart type="family">Sobolewski</namePart><affiliation>Institute of Physics, Polish Academy of Sciences, PL-02-668 Warsaw, Poland</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Wolfgang</namePart><namePart type="family">Domcke</namePart><affiliation>Institute of Theoretical Chemistry, Heinrich-Heine-University, D-40225 Düsseldorf, Germany</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="research-article" displayLabel="Full-length article"></genre><originInfo><publisher>ELSEVIER</publisher><dateIssued encoding="w3cdtf">1998</dateIssued><dateCaptured encoding="w3cdtf">1998-08-28</dateCaptured><copyrightDate encoding="w3cdtf">1999</copyrightDate></originInfo><language><languageTerm type="code" authority="iso639-2b">eng</languageTerm><languageTerm type="code" authority="rfc3066">en</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType></physicalDescription><abstract lang="en">The behaviour of 4-(N,N-dimethylamino)benzonitrile in its locally-excited and charge-transfer singlet states following the twisting and wagging displacements of the amino group has been investigated theoretically. These reaction paths are expected to play a decisive role in the intramolecular charge transfer observed for this compound in polar solvents. Minimum-energy paths for the lowest excited singlet states have been determined at the CIS level. The corresponding potential-energy profiles have been calculated with the CASSCF and CASPT2 methods. The potential-energy functions depend strongly on the amount of electron correlation included. It can be concluded that, except for large twist angles, wagging leads only to minor changes in the potential-energy curves and dipole moments. The results suggest that the wagging angle can be excluded as a reaction coordinate for the intramolecular charge-transfer process as well as a coupling coordinate of the two lowest excited singlet states. Twisting of the amino group appears to be the relevant reaction coordinate for the intramolecular charge transfer in 4-(N,N-dimethylamino)benzonitrile.</abstract><note type="content">Fig. 1: Projection of the CIS optimized geometries of DMABN along different reaction paths onto the plane spanned by the twisting and wagging coordinates. Crosses denote reaction paths where the Lb-like LE and La-like CT states can be distinguished by symmetry. Pluses denote the reaction path of C1 symmetry, where only the lowest excited singlet state can be optimized.</note><note type="content">Fig. 2: Potential-energy functions for the lowest excited singlet states calculated along the wagging reaction path for planar (a,c,e) and fully twisted (b,d,f) DMABN. Triangles denote the Lb-like LE state, squares the La-like CT state. (a,b): CIS energy for the optimized structures; (c,d): CASSCF energy calculated at CIS geometries; (e,f): CASPT2 energy calculated at CIS geometries. Energies are given relatively to the HF (a,b), CASSCF (c,d) and CASPT2 (e,f) ground-state energies calculated at the MP2 C2v minimum of the ground state.</note><note type="content">Fig. 3: CASSCF dipole moments for the lowest excited singlet states calculated along the wagging reaction path for planar (a) and fully twisted (b) DMABN. Triangles refer to the Lb-like LE state, squares to the La-like CT state, and circles to the ground state. Solid lines refer to a geometry optimized for the same state, dashed lines to a geometry optimized for the corresponding CT state.</note><note type="content">Fig. 4: Potential-energy functions for the lowest excited singlet states of DMABN calculated along the reaction paths for pure twisting (a,c,e) and combined twisting and wagging (b,d,f). The optimal values of δ are given in Fig. 1. Triangles denote the Lb-like LE state, squares the La-like CT state. Solid lines refer to a single-state optimized wavefunction at a geometry optimized for the same state, dashed lines refer to a single-state optimized wavefunction at a geometry optimized for the corresponding CT state, and dotted lines refer to a state-averaged wavefunction. (a,b): CIS energy for the optimized structures; (c,d): CASSCF energy calculated at CIS geometries; (e,f): CASPT2 energy calculated at CIS geometries. Energies are given relatively to the HF (a,b), CASSCF (c,d) and CASPT2 (e,f) ground-state energies calculated at the MP2 C2v minimum of the ground state. The point at θ=75° on the “S2” potential-energy curve in (f) is skipped due to its significant lower reference weight.</note><note type="content">Fig. 5: CASSCF dipole moments for the lowest excited singlet states of DMABN calculated along the reaction paths for pure twisting (a) and combined twisting and wagging (b). The optimal values of δ are given in Fig. 1. Triangles refer to the Lb-like LE state, squares to the La-like CT state, and circles to the ground state. Solid lines refer to a single-state optimized wavefunction at a geometry optimized for the same state, dashed lines refer to a single-state optimized wavefunction at a geometry optimized for the corresponding CT state, and dotted lines refer to a state-averaged wavefunction.</note><note type="content">Fig. 6: CASPT2 potential-energy functions for the lowest excited singlet states of DMABN calculated along the twisting coordinate (a) and the wagging coordinate (b) with all other coordinates frozen. Triangles denote the Lb-like LE state, squares the La-like CT state. Energies are given relatively to the CASPT2 ground-state energy calculated at the MP2 C2v minimum of the ground state.</note><note type="content">Table 1: Definition of active electrons and frozen, inactive and active orbitals in the CASSCF single-point calculations of DMABN following the different reaction paths along the twisting and wagging coordinates</note><note type="content">Table 2: Assignment of the lowest excited singlet states of DMABN in each point group to the Lb-like LE and La-like CT states following the different reaction paths along the twisting and wagging coordinates</note><relatedItem type="host"><titleInfo><title>Chemical Physics</title></titleInfo><titleInfo type="abbreviated"><title>CHEMPH</title></titleInfo><genre type="Journal">journal</genre><originInfo><dateIssued encoding="w3cdtf">19990101</dateIssued></originInfo><identifier type="ISSN">0301-0104</identifier><identifier type="PII">S0301-0104(00)X0702-1</identifier><part><date>19990101</date><detail type="volume"><number>240</number><caption>vol.</caption></detail><detail type="issue"><number>1–2</number><caption>no.</caption></detail><extent unit="issue pages"><start>1</start><end>312</end></extent><extent unit="pages"><start>9</start><end>18</end></extent></part></relatedItem><identifier type="istex">DC1FA6F5EDCAA94238E255344BDF6B768E44C01B</identifier><identifier type="DOI">10.1016/S0301-0104(98)00368-1</identifier><identifier type="PII">S0301-0104(98)00368-1</identifier><accessCondition type="use and reproduction" contentType="">© 1999Elsevier Science B.V.</accessCondition><recordInfo><recordContentSource>ELSEVIER</recordContentSource><recordOrigin>Elsevier Science B.V., ©1999</recordOrigin></recordInfo></mods></metadata><enrichments><istex:catWosTEI uri="https://api.istex.fr/document/DC1FA6F5EDCAA94238E255344BDF6B768E44C01B/enrichments/catWos"><teiHeader><profileDesc><textClass><classCode scheme="WOS">PHYSICS, ATOMIC, MOLECULAR & CHEMICAL</classCode><classCode scheme="WOS">CHEMISTRY, PHYSICAL</classCode></textClass></profileDesc></teiHeader></istex:catWosTEI></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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