Environmental Photochemistry of Nitro-PAHs: Direct Observation of Ultrafast Intersystem Crossing in 1-Nitropyrene
Femtosecond broadband transient absorption experiments of 1-nitropyrene, a nitro-polycyclic aromatic hydrocarbon of environmental concern are presented in cyclohexane and hexane solutions. The transient absorption spectra show the presence of three species that are assigned to the Franck−Condon exci...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2008-07, Vol.112 (28), p.6313-6319 |
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| container_title | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
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| creator | Crespo-Hernández, Carlos E Burdzinski, Gotard Arce, Rafael |
| description | Femtosecond broadband transient absorption experiments of 1-nitropyrene, a nitro-polycyclic aromatic hydrocarbon of environmental concern are presented in cyclohexane and hexane solutions. The transient absorption spectra show the presence of three species that are assigned to the Franck−Condon excited lowest singlet (S1) state, the structurally relaxed S1 state, and the lowest excited triplet state. The spectral changes at early times are interpreted in terms of conformational dynamics; primarily due to an ultrafast rotation of the nitro group in the S1 state. This excited state relaxation is followed by intersystem crossing with a time constant of 7 ps. CIS/6-31G(d,p) calculations predict planarization of the nitro-aromatic torsional angle as the major nuclear relaxation coordinate, from 32.8° at the HF/6-31G(d,p) level of theory in the ground state (27.46° at B3LYP/6-31++G(d,p)) to 0.07° in the S1 state. Vertical excitation energies at the TDDFT/6-31++G(d,p) and TDDFT/IEFPCM/6-31++G(d,p) levels of theory predict a small energy gap ( |
| doi_str_mv | 10.1021/jp803847q |
| format | Article |
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The transient absorption spectra show the presence of three species that are assigned to the Franck−Condon excited lowest singlet (S1) state, the structurally relaxed S1 state, and the lowest excited triplet state. The spectral changes at early times are interpreted in terms of conformational dynamics; primarily due to an ultrafast rotation of the nitro group in the S1 state. This excited state relaxation is followed by intersystem crossing with a time constant of 7 ps. CIS/6-31G(d,p) calculations predict planarization of the nitro-aromatic torsional angle as the major nuclear relaxation coordinate, from 32.8° at the HF/6-31G(d,p) level of theory in the ground state (27.46° at B3LYP/6-31++G(d,p)) to 0.07° in the S1 state. Vertical excitation energies at the TDDFT/6-31++G(d,p) and TDDFT/IEFPCM/6-31++G(d,p) levels of theory predict a small energy gap (<0.12 eV) between the S1(ππ*) state and the third excited triplet state T3(nπ*) in the gas phase and in cyclohexane, respectively. The small energy gap suggests a large spin-orbit coupling between the S1(ππ*) and T3(nπ*) states, which explains the ultrafast intersystem crossing of 1-nitropyrene in nonpolar solvents.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp803847q</identifier><identifier>PMID: 18572893</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>A: Kinetics, Spectroscopy ; Environmental Pollutants - chemistry ; Molecular Conformation ; Photochemistry ; Polycyclic Aromatic Hydrocarbons - chemistry ; Pyrenes - chemistry ; Solvents ; Spectrum Analysis</subject><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2008-07, Vol.112 (28), p.6313-6319</ispartof><rights>Copyright © 2008 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a448t-3e5bc917554e5d0f95c12832121c8dbb6078fb87ec51c9e266295b199efed3c03</citedby><cites>FETCH-LOGICAL-a448t-3e5bc917554e5d0f95c12832121c8dbb6078fb87ec51c9e266295b199efed3c03</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jp803847q$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp803847q$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/18572893$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Crespo-Hernández, Carlos E</creatorcontrib><creatorcontrib>Burdzinski, Gotard</creatorcontrib><creatorcontrib>Arce, Rafael</creatorcontrib><title>Environmental Photochemistry of Nitro-PAHs: Direct Observation of Ultrafast Intersystem Crossing in 1-Nitropyrene</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Femtosecond broadband transient absorption experiments of 1-nitropyrene, a nitro-polycyclic aromatic hydrocarbon of environmental concern are presented in cyclohexane and hexane solutions. The transient absorption spectra show the presence of three species that are assigned to the Franck−Condon excited lowest singlet (S1) state, the structurally relaxed S1 state, and the lowest excited triplet state. The spectral changes at early times are interpreted in terms of conformational dynamics; primarily due to an ultrafast rotation of the nitro group in the S1 state. This excited state relaxation is followed by intersystem crossing with a time constant of 7 ps. CIS/6-31G(d,p) calculations predict planarization of the nitro-aromatic torsional angle as the major nuclear relaxation coordinate, from 32.8° at the HF/6-31G(d,p) level of theory in the ground state (27.46° at B3LYP/6-31++G(d,p)) to 0.07° in the S1 state. Vertical excitation energies at the TDDFT/6-31++G(d,p) and TDDFT/IEFPCM/6-31++G(d,p) levels of theory predict a small energy gap (<0.12 eV) between the S1(ππ*) state and the third excited triplet state T3(nπ*) in the gas phase and in cyclohexane, respectively. The small energy gap suggests a large spin-orbit coupling between the S1(ππ*) and T3(nπ*) states, which explains the ultrafast intersystem crossing of 1-nitropyrene in nonpolar solvents.</description><subject>A: Kinetics, Spectroscopy</subject><subject>Environmental Pollutants - chemistry</subject><subject>Molecular Conformation</subject><subject>Photochemistry</subject><subject>Polycyclic Aromatic Hydrocarbons - chemistry</subject><subject>Pyrenes - chemistry</subject><subject>Solvents</subject><subject>Spectrum Analysis</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2008</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkE1v1DAQhi1ERUvhwB9AvoDEIdRjx4nNraSFVurHItqz5XgnNEti79reiv33ZNlVufQ0I82jd2YeQt4B-wyMw8liqZhQZb16QY5AclZIDvLl1DOlC1kJfUhep7RgjIHg5StyCErWXGlxRFbn_rGPwY_osx3o7CHk4B5w7FOOGxo6etPnGIrZ6UX6Qs_6iC7T2zZhfLS5D35L3A852s6mTC99xpg2KeNImxhS6v0v2nsKxb-U5SaixzfkoLNDwrf7ekzuv53fNRfF1e33y-b0qrBlqXIhULZOQy1liXLOOi0dcCU4cHBq3rYVq1XXqhqdBKeRVxXXsgWtscO5cEwck4-73GUMqzWmbKanHA6D9RjWyXBgUNWVnMBPO9BtT47YmWXsRxs3BpjZ-jVPfif2_T503Y44_0_uhU5AsQMmgfjnaW7jb1PVopbmbvbTNNdl8-O6PDNfJ_7DjrcumUVYRz85eWbxX3RGkk4</recordid><startdate>20080717</startdate><enddate>20080717</enddate><creator>Crespo-Hernández, Carlos E</creator><creator>Burdzinski, Gotard</creator><creator>Arce, Rafael</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TV</scope><scope>C1K</scope></search><sort><creationdate>20080717</creationdate><title>Environmental Photochemistry of Nitro-PAHs: Direct Observation of Ultrafast Intersystem Crossing in 1-Nitropyrene</title><author>Crespo-Hernández, Carlos E ; Burdzinski, Gotard ; Arce, Rafael</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a448t-3e5bc917554e5d0f95c12832121c8dbb6078fb87ec51c9e266295b199efed3c03</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2008</creationdate><topic>A: Kinetics, Spectroscopy</topic><topic>Environmental Pollutants - chemistry</topic><topic>Molecular Conformation</topic><topic>Photochemistry</topic><topic>Polycyclic Aromatic Hydrocarbons - chemistry</topic><topic>Pyrenes - chemistry</topic><topic>Solvents</topic><topic>Spectrum Analysis</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Crespo-Hernández, Carlos E</creatorcontrib><creatorcontrib>Burdzinski, Gotard</creatorcontrib><creatorcontrib>Arce, Rafael</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Pollution Abstracts</collection><collection>Environmental Sciences and Pollution Management</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Crespo-Hernández, Carlos E</au><au>Burdzinski, Gotard</au><au>Arce, Rafael</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Environmental Photochemistry of Nitro-PAHs: Direct Observation of Ultrafast Intersystem Crossing in 1-Nitropyrene</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2008-07-17</date><risdate>2008</risdate><volume>112</volume><issue>28</issue><spage>6313</spage><epage>6319</epage><pages>6313-6319</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>Femtosecond broadband transient absorption experiments of 1-nitropyrene, a nitro-polycyclic aromatic hydrocarbon of environmental concern are presented in cyclohexane and hexane solutions. The transient absorption spectra show the presence of three species that are assigned to the Franck−Condon excited lowest singlet (S1) state, the structurally relaxed S1 state, and the lowest excited triplet state. The spectral changes at early times are interpreted in terms of conformational dynamics; primarily due to an ultrafast rotation of the nitro group in the S1 state. This excited state relaxation is followed by intersystem crossing with a time constant of 7 ps. CIS/6-31G(d,p) calculations predict planarization of the nitro-aromatic torsional angle as the major nuclear relaxation coordinate, from 32.8° at the HF/6-31G(d,p) level of theory in the ground state (27.46° at B3LYP/6-31++G(d,p)) to 0.07° in the S1 state. Vertical excitation energies at the TDDFT/6-31++G(d,p) and TDDFT/IEFPCM/6-31++G(d,p) levels of theory predict a small energy gap (<0.12 eV) between the S1(ππ*) state and the third excited triplet state T3(nπ*) in the gas phase and in cyclohexane, respectively. The small energy gap suggests a large spin-orbit coupling between the S1(ππ*) and T3(nπ*) states, which explains the ultrafast intersystem crossing of 1-nitropyrene in nonpolar solvents.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>18572893</pmid><doi>10.1021/jp803847q</doi><tpages>7</tpages></addata></record> |
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| subjects | A: Kinetics, Spectroscopy Environmental Pollutants - chemistry Molecular Conformation Photochemistry Polycyclic Aromatic Hydrocarbons - chemistry Pyrenes - chemistry Solvents Spectrum Analysis |
| title | Environmental Photochemistry of Nitro-PAHs: Direct Observation of Ultrafast Intersystem Crossing in 1-Nitropyrene |
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