Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment
Identifieur interne : 000665 ( Istex/Corpus ); précédent : 000664; suivant : 000666Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment
Auteurs : J. Saltiel ; O. Dmitrenko ; Z. S. Pillai ; R. Klima ; S. Wang ; T. Wharton ; Z.-N. Huang ; L. J. Van De Burgt ; J. ArranzSource :
- Photochemical & Photobiological Sciences [ 1474-905X ] ; 2008.
Abstract
Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O2, lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt → ct direction, as had been observed for the ct → tt direction, and suggesting an energy minimum at the 3ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (kd) from twisted geometries. Starting from cc-DPB, ϕcc→tt increases with increasing [cc-DPB] whereas ϕcc→ct is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental ΔH between 3tt-DPB* and 3tp-DPB*, 2.7 kcal mol−1, is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated ΔS = 4.04 eu between the two triplets gives kd = (2.4–6.4) × 107 s−1, close to 1.70 × 107 s−1, the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.
Url:
DOI: 10.1039/b801075g
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Dmitrenko</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Delaware, 19716, Newark Delaware</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Pillai, Z S" sort="Pillai, Z S" uniqKey="Pillai Z" first="Z. S." last="Pillai">Z. S. Pillai</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Klima, R" sort="Klima, R" uniqKey="Klima R" first="R." last="Klima">R. 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Arranz</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">ISTEX</idno><idno type="RBID">ISTEX:8138D1BF65417EF68FED40E7253596D51E2E14D6</idno><date when="2008" year="2008">2008</date><idno type="doi">10.1039/b801075g</idno><idno type="url">https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/fulltext/pdf</idno><idno type="wicri:Area/Istex/Corpus">000665</idno></publicationStmt><sourceDesc><biblStruct><analytic><title level="a">Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title><author wicri:is="90%"><name sortKey="Saltiel, J" sort="Saltiel, J" uniqKey="Saltiel J" first="J." last="Saltiel">J. Saltiel</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Dmitrenko, O" sort="Dmitrenko, O" uniqKey="Dmitrenko O" first="O." last="Dmitrenko">O. Dmitrenko</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, University of Delaware, 19716, Newark Delaware</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Pillai, Z S" sort="Pillai, Z S" uniqKey="Pillai Z" first="Z. S." last="Pillai">Z. S. Pillai</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Klima, R" sort="Klima, R" uniqKey="Klima R" first="R." last="Klima">R. Klima</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Wang, S" sort="Wang, S" uniqKey="Wang S" first="S." last="Wang">S. Wang</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Wharton, T" sort="Wharton, T" uniqKey="Wharton T" first="T." last="Wharton">T. Wharton</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Huang, Z N" sort="Huang, Z N" uniqKey="Huang Z" first="Z.-N." last="Huang">Z.-N. Huang</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Van De Burgt, L J" sort="Van De Burgt, L J" uniqKey="Van De Burgt L" first="L. J." last="Van De Burgt">L. J. Van De Burgt</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author><author wicri:is="90%"><name sortKey="Arranz, J" sort="Arranz, J" uniqKey="Arranz J" first="J." last="Arranz">J. Arranz</name><affiliation><mods:affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: saltiel@chem.fsu.edu</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Photochemical & Photobiological Sciences</title><title level="j" type="abbrev">Photochem. Photobiol. Sci.</title><idno type="ISSN">1474-905X</idno><idno type="eISSN">1474-9092</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="2008">2008</date><biblScope unit="volume"></biblScope><biblScope unit="issue">5</biblScope><biblScope unit="page" from="566">566</biblScope><biblScope unit="page" to="577">577</biblScope></imprint><idno type="ISSN">1474-905X</idno></series><idno type="istex">8138D1BF65417EF68FED40E7253596D51E2E14D6</idno><idno type="DOI">10.1039/b801075g</idno><idno type="ms-id">b801075g</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">1474-905X</idno></seriesStmt></fileDesc><profileDesc><textClass></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract">Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O2, lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt → ct direction, as had been observed for the ct → tt direction, and suggesting an energy minimum at the 3ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (kd) from twisted geometries. Starting from cc-DPB, ϕcc→tt increases with increasing [cc-DPB] whereas ϕcc→ct is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental ΔH between 3tt-DPB* and 3tp-DPB*, 2.7 kcal mol−1, is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated ΔS = 4.04 eu between the two triplets gives kd = (2.4–6.4) × 107 s−1, close to 1.70 × 107 s−1, the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.</div></front></TEI><istex><corpusName>rsc-journals</corpusName><author><json:item><name>J. Saltiel</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>O. Dmitrenko</name><affiliations><json:string>Department of Chemistry and Biochemistry, University of Delaware, 19716, Newark Delaware</json:string></affiliations></json:item><json:item><name>Z. S. Pillai</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>R. Klima</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>S. Wang</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>T. Wharton</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>Z.-N. Huang</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>L. J. van de Burgt</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item><json:item><name>J. Arranz</name><affiliations><json:string>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</json:string><json:string>E-mail: saltiel@chem.fsu.edu</json:string></affiliations></json:item></author><language><json:string>eng</json:string></language><originalGenre><json:string>N/A</json:string></originalGenre><abstract>Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O2, lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt → ct direction, as had been observed for the ct → tt direction, and suggesting an energy minimum at the 3ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (kd) from twisted geometries. Starting from cc-DPB, ϕcc→tt increases with increasing [cc-DPB] whereas ϕcc→ct is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental ΔH between 3tt-DPB* and 3tp-DPB*, 2.7 kcal mol−1, is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated ΔS = 4.04 eu between the two triplets gives kd = (2.4–6.4) × 107 s−1, close to 1.70 × 107 s−1, the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.</abstract><qualityIndicators><score>9.5</score><pdfVersion>1.6</pdfVersion><pdfPageSize>595 x 842 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>0</keywordCount><abstractCharCount>1843</abstractCharCount><pdfWordCount>9892</pdfWordCount><pdfCharCount>56552</pdfCharCount><pdfPageCount>13</pdfPageCount><abstractWordCount>272</abstractWordCount></qualityIndicators><title>Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title><genre><json:string>other</json:string></genre><host><pages><total>12</total><last>577</last><first>566</first></pages><issn><json:string>1474-905X</json:string></issn><issue>5</issue><genre><json:string>journal</json:string></genre><language><json:string>unknown</json:string></language><eissn><json:string>1474-9092</json:string></eissn><title>Photochemical & Photobiological Sciences</title></host><publicationDate>2008</publicationDate><copyrightDate>2008</copyrightDate><doi><json:string>10.1039/b801075g</json:string></doi><id>8138D1BF65417EF68FED40E7253596D51E2E14D6</id><score>0.10153237</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/fulltext/pdf</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a">Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>The Royal Society of Chemistry.</publisher><availability><p>This journal is © The Royal Society of Chemistry and Owner Societies</p></availability><date>2008</date></publicationStmt><notesStmt><note>This paper was published as part of the themed issue in honour of Jakob Wirz.</note><note>Electronic supplementary information (ESI) available: Cartesian coordinates, drawings, and total energies of optimized structures and transition states in S0 and T1. See DOI: 10.1039/b801075g</note><note>Idealized potential energy diagrams for twisting about the C1C2 and C3C4 bonds of 1,4-diphenyl-1,3-butadiene in S0 and T1; values given are experimental energies.</note></notesStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a">Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title><author xml:id="author-1"><persName><forename type="first">J.</forename><surname>Saltiel</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-2"><persName><forename type="first">O.</forename><surname>Dmitrenko</surname></persName><affiliation>Department of Chemistry and Biochemistry, University of Delaware, 19716, Newark Delaware</affiliation></author><author xml:id="author-3"><persName><forename type="first">Z. S.</forename><surname>Pillai</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-4"><persName><forename type="first">R.</forename><surname>Klima</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-5"><persName><forename type="first">S.</forename><surname>Wang</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-6"><persName><forename type="first">T.</forename><surname>Wharton</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-7"><persName><forename type="first">Z.-N.</forename><surname>Huang</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-8"><persName><forename type="first">L. J.</forename><surname>van de Burgt</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author><author xml:id="author-9"><persName><forename type="first">J.</forename><surname>Arranz</surname></persName><email>saltiel@chem.fsu.edu</email><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation></author></analytic><monogr><title level="j">Photochemical & Photobiological Sciences</title><title level="j" type="abbrev">Photochem. Photobiol. Sci.</title><idno type="pISSN">1474-905X</idno><idno type="eISSN">1474-9092</idno><imprint><publisher>The Royal Society of Chemistry.</publisher><date type="published" when="2008"></date><biblScope unit="volume"></biblScope><biblScope unit="issue">5</biblScope><biblScope unit="page" from="566">566</biblScope><biblScope unit="page" to="577">577</biblScope></imprint></monogr><idno type="istex">8138D1BF65417EF68FED40E7253596D51E2E14D6</idno><idno type="DOI">10.1039/b801075g</idno><idno type="ms-id">b801075g</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2008</date></creation><langUsage><language ident="en">en</language></langUsage><abstract><p>Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O2, lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt → ct direction, as had been observed for the ct → tt direction, and suggesting an energy minimum at the 3ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (kd) from twisted geometries. Starting from cc-DPB, ϕcc→tt increases with increasing [cc-DPB] whereas ϕcc→ct is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental ΔH between 3tt-DPB* and 3tp-DPB*, 2.7 kcal mol−1, is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated ΔS = 4.04 eu between the two triplets gives kd = (2.4–6.4) × 107 s−1, close to 1.70 × 107 s−1, the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.</p></abstract></profileDesc><revisionDesc><change when="2008">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="corpus rsc-journals not found" wicri:toSee="no header"><istex:xmlDeclaration>version="1.0" encoding="UTF-8"</istex:xmlDeclaration><istex:xmlDeclaration>href="http://www.rsc.org/dtds/styles/rsc_html.xsl" type="text/xsl"</istex:xmlDeclaration><istex:document><!--Arbortext, Inc., 1988-2006, v.4002-->
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</article></istex:document></istex:metadataXml><mods version="3.6"><titleInfo><title>Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title></titleInfo><titleInfo type="alternative" contentType="CDATA"><title>Triplet and ground state potential energy surfaces of 1,4-diphenyl-1,3-butadiene: theory and experiment</title></titleInfo><name type="personal"><namePart type="given">J.</namePart><namePart type="family">Saltiel</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">O.</namePart><namePart type="family">Dmitrenko</namePart><affiliation>Department of Chemistry and Biochemistry, University of Delaware, 19716, Newark Delaware</affiliation></name><name type="personal"><namePart type="given">Z. S.</namePart><namePart type="family">Pillai</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">R.</namePart><namePart type="family">Klima</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">S.</namePart><namePart type="family">Wang</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">T.</namePart><namePart type="family">Wharton</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">Z.-N.</namePart><namePart type="family">Huang</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">L. J.</namePart><namePart type="family">van de Burgt</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><name type="personal"><namePart type="given">J.</namePart><namePart type="family">Arranz</namePart><affiliation>Department of Chemistry and Biochemistry, The Florida State University, 32306-4390, Florida, Tallahassee, USA</affiliation><affiliation>E-mail: saltiel@chem.fsu.edu</affiliation></name><typeOfResource>text</typeOfResource><genre type="other" displayLabel="N/A"></genre><originInfo><publisher>The Royal Society of Chemistry.</publisher><dateIssued encoding="w3cdtf">2008</dateIssued><copyrightDate encoding="w3cdtf">2008</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>Relative energies of the ground state isomers of 1,4-diphenyl-1,3-butadiene (DPB) are determined from the temperature dependence of equilibrium isomer compositions obtained with the use of diphenyl diselenide as catalyst. Temperature and concentration effects on photostationary states and isomerization quantum yields with biacetyl or fluorenone as triplet sensitizers with or without the presence of O2, lead to significant modification of the proposed DPB triplet potential energy surface. Quantum yields for ct-DPB formation from tt-DPB increase with [tt-DPB] revealing a quantum chain process in the tt → ct direction, as had been observed for the ct → tt direction, and suggesting an energy minimum at the 3ct* geometry. They confirm the presence of planar and twisted isomeric triplets in equilibrium (K), with energy transfer from planar or quasi-planar geometries (quantum chain events from tt and ct triplets) and unimolecular decay (kd) from twisted geometries. Starting from cc-DPB, ϕcc→tt increases with increasing [cc-DPB] whereas ϕcc→ct is relatively insensitive to concentration changes. The concentration and temperature dependencies of the decay rate constants of DPB triplets in cyclohexane are consistent with the mechanism deduced from the photoisomerization quantum yields. The experimental ΔH between 3tt-DPB* and 3tp-DPB*, 2.7 kcal mol−1, is compared with the calculated energy difference [DFT with B3LYP/6-31+G(d,p) basis set]. Use of the calculated ΔS = 4.04 eu between the two triplets gives kd = (2.4–6.4) × 107 s−1, close to 1.70 × 107 s−1, the value for twisted stilbene triplet decay. Experimental and calculated relative energies of DPB isomers on the ground and triplet state surfaces agree and theory is relied upon to deduce structural characteristics of the equilibrated conformers in the DPB triplet state.</abstract><note type="footnote" displayLabel="fn1">This paper was published as part of the themed issue in honour of Jakob Wirz.</note><note type="footnote" displayLabel="fn2">Electronic supplementary information (ESI) available: Cartesian coordinates, drawings, and total energies of optimized structures and transition states in S0 and T1. See DOI: 10.1039/b801075g</note><note>Idealized potential energy diagrams for twisting about the C1C2 and C3C4 bonds of 1,4-diphenyl-1,3-butadiene in S0 and T1; values given are experimental energies.</note><relatedItem type="host"><titleInfo><title>Photochemical & Photobiological Sciences</title></titleInfo><titleInfo type="abbreviated"><title>Photochem. Photobiol. Sci.</title></titleInfo><genre type="journal">journal</genre><originInfo><publisher>The Royal Society of Chemistry.</publisher></originInfo><identifier type="ISSN">1474-905X</identifier><identifier type="eISSN">1474-9092</identifier><identifier type="coden">PPSHCB</identifier><identifier type="RSC sercode">PP</identifier><part><date>2008</date><detail type="volume"><caption>vol.</caption><number></number></detail><detail type="issue"><caption>no.</caption><number>5</number></detail><extent unit="pages"><start>566</start><end>577</end><total>12</total></extent></part></relatedItem><identifier type="istex">8138D1BF65417EF68FED40E7253596D51E2E14D6</identifier><identifier type="DOI">10.1039/b801075g</identifier><identifier type="ms-id">b801075g</identifier><accessCondition type="use and reproduction" contentType="copyright">This journal is © The Royal Society of Chemistry and Owner Societies</accessCondition><recordInfo><recordContentSource>RSC Journals</recordContentSource><recordOrigin>The Royal Society of Chemistry</recordOrigin></recordInfo></mods></metadata><enrichments><json:item><type>multicat</type><uri>https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/enrichments/multicat</uri></json:item><json:item><type>refBibs</type><uri>https://api.istex.fr/document/8138D1BF65417EF68FED40E7253596D51E2E14D6/enrichments/refBibs</uri></json:item></enrichments><serie></serie></istex></record>Pour manipuler ce document sous Unix (Dilib)
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