Experimental and Theoretical UV Characterizations of Acetylacetone and Its Isomers
Cryogenic matrix isolation experiments have allowed the measurement of the UV absorption spectra of the high-energy non-chelated isomers of acetylacetone, these isomers being produced by UV irradiation of the stable chelated form. Their identification has been done by coupling selective UV-induced i...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2006-03, Vol.110 (11), p.3920-3926 |
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creator | Coussan, S Ferro, Y Trivella, A Rajzmann, M Roubin, P Wieczorek, R Manca, C Piecuch, P Kowalski, K Włoch, M Kucharski, S. A Musiał, M |
description | Cryogenic matrix isolation experiments have allowed the measurement of the UV absorption spectra of the high-energy non-chelated isomers of acetylacetone, these isomers being produced by UV irradiation of the stable chelated form. Their identification has been done by coupling selective UV-induced isomerization, infrared spectroscopy, and harmonic vibrational frequency calculations using density functional theory. The relative energies of the chelated and non-chelated forms of acetylacetone in the S0 state have been obtained using density functional theory and coupled-cluster methods. For each isomer of acetylacetone, we have calculated the UV transition energies and dipole oscillator strengths using the excited-state coupled-cluster methods, including EOMCCSD (equation-of-motion coupled-cluster method with singles and doubles) and CR-EOMCCSD(T) (the completely renormalized EOMCC approach with singles, doubles, and non-iterative triples). For dipole-allowed transition energies, there is a very good agreement between experiment and theory. In particular, the CR-EOMCCSD(T) approach explains the blue shift in the electronic spectrum due to the formation of the non-chelated species after the UV irradiation of the chelated form of acetylacetone. Both experiment and CR-EOMCCSD(T) theory identify two among the seven non-chelated forms to be characterized by red-shifted UV transitions relative to the remaining five non-chelated isomers. |
doi_str_mv | 10.1021/jp056834r |
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A ; Musiał, M</creator><creatorcontrib>Coussan, S ; Ferro, Y ; Trivella, A ; Rajzmann, M ; Roubin, P ; Wieczorek, R ; Manca, C ; Piecuch, P ; Kowalski, K ; Włoch, M ; Kucharski, S. A ; Musiał, M</creatorcontrib><description>Cryogenic matrix isolation experiments have allowed the measurement of the UV absorption spectra of the high-energy non-chelated isomers of acetylacetone, these isomers being produced by UV irradiation of the stable chelated form. Their identification has been done by coupling selective UV-induced isomerization, infrared spectroscopy, and harmonic vibrational frequency calculations using density functional theory. The relative energies of the chelated and non-chelated forms of acetylacetone in the S0 state have been obtained using density functional theory and coupled-cluster methods. For each isomer of acetylacetone, we have calculated the UV transition energies and dipole oscillator strengths using the excited-state coupled-cluster methods, including EOMCCSD (equation-of-motion coupled-cluster method with singles and doubles) and CR-EOMCCSD(T) (the completely renormalized EOMCC approach with singles, doubles, and non-iterative triples). For dipole-allowed transition energies, there is a very good agreement between experiment and theory. In particular, the CR-EOMCCSD(T) approach explains the blue shift in the electronic spectrum due to the formation of the non-chelated species after the UV irradiation of the chelated form of acetylacetone. Both experiment and CR-EOMCCSD(T) theory identify two among the seven non-chelated forms to be characterized by red-shifted UV transitions relative to the remaining five non-chelated isomers.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp056834r</identifier><identifier>PMID: 16539413</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Models, Chemical ; Molecular Structure ; Pentanones - chemistry ; Pentanones - radiation effects ; Sensitivity and Specificity ; Spectrophotometry, Ultraviolet - methods ; Stereoisomerism ; Ultraviolet Rays</subject><ispartof>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2006-03, Vol.110 (11), p.3920-3926</ispartof><rights>Copyright © 2006 American Chemical Society</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a351t-fe556e83fbe54fad8cbdfbcabc9c81978ba833c366ce24f1aede6a37194f47c23</citedby><cites>FETCH-LOGICAL-a351t-fe556e83fbe54fad8cbdfbcabc9c81978ba833c366ce24f1aede6a37194f47c23</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/jp056834r$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jp056834r$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/16539413$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Coussan, S</creatorcontrib><creatorcontrib>Ferro, Y</creatorcontrib><creatorcontrib>Trivella, A</creatorcontrib><creatorcontrib>Rajzmann, M</creatorcontrib><creatorcontrib>Roubin, P</creatorcontrib><creatorcontrib>Wieczorek, R</creatorcontrib><creatorcontrib>Manca, C</creatorcontrib><creatorcontrib>Piecuch, P</creatorcontrib><creatorcontrib>Kowalski, K</creatorcontrib><creatorcontrib>Włoch, M</creatorcontrib><creatorcontrib>Kucharski, S. A</creatorcontrib><creatorcontrib>Musiał, M</creatorcontrib><title>Experimental and Theoretical UV Characterizations of Acetylacetone and Its Isomers</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>Cryogenic matrix isolation experiments have allowed the measurement of the UV absorption spectra of the high-energy non-chelated isomers of acetylacetone, these isomers being produced by UV irradiation of the stable chelated form. Their identification has been done by coupling selective UV-induced isomerization, infrared spectroscopy, and harmonic vibrational frequency calculations using density functional theory. The relative energies of the chelated and non-chelated forms of acetylacetone in the S0 state have been obtained using density functional theory and coupled-cluster methods. For each isomer of acetylacetone, we have calculated the UV transition energies and dipole oscillator strengths using the excited-state coupled-cluster methods, including EOMCCSD (equation-of-motion coupled-cluster method with singles and doubles) and CR-EOMCCSD(T) (the completely renormalized EOMCC approach with singles, doubles, and non-iterative triples). For dipole-allowed transition energies, there is a very good agreement between experiment and theory. In particular, the CR-EOMCCSD(T) approach explains the blue shift in the electronic spectrum due to the formation of the non-chelated species after the UV irradiation of the chelated form of acetylacetone. Both experiment and CR-EOMCCSD(T) theory identify two among the seven non-chelated forms to be characterized by red-shifted UV transitions relative to the remaining five non-chelated isomers.</description><subject>Models, Chemical</subject><subject>Molecular Structure</subject><subject>Pentanones - chemistry</subject><subject>Pentanones - radiation effects</subject><subject>Sensitivity and Specificity</subject><subject>Spectrophotometry, Ultraviolet - methods</subject><subject>Stereoisomerism</subject><subject>Ultraviolet Rays</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2006</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0EtPAyEQB3BiNLY-Dn4BsxdNPKzCsuzj2DSt1viKVq9klh3SrdulAk3UTy_aRi9egAk_ZsKfkCNGzxlN2MV8SUVW8NRukT4TCY1FwsR2ONOijEXGyx7Zc25OKWU8SXdJj2WClynjffI4el-ibRbYeWgj6OpoOkNj0Tcq1M8v0XAGFpQP5hN8YzoXGR0NFPqPFsJqOvx5NfEumjizQOsOyI6G1uHhZt8nz-PRdHgV39xfToaDmxi4YD7WKESGBdcVilRDXaiq1pWCSpWqYGVeVFBwrniWKUxSzQBrzIDnrEx1mquE75PTdd-lNW8rdF4uGqewbaFDs3Iyy3MhRJ4HeLaGyhrnLGq5DD8G-yEZld8Byt8Agz3eNF1VC6z_5CaxAOI1aJzH9997sK9hIM-FnD48ycvH8e34elrKu-BP1h6Uk3Ozsl3I5J_BX7y-iFQ</recordid><startdate>20060323</startdate><enddate>20060323</enddate><creator>Coussan, S</creator><creator>Ferro, Y</creator><creator>Trivella, A</creator><creator>Rajzmann, M</creator><creator>Roubin, P</creator><creator>Wieczorek, R</creator><creator>Manca, C</creator><creator>Piecuch, P</creator><creator>Kowalski, K</creator><creator>Włoch, M</creator><creator>Kucharski, S. 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A</au><au>Musiał, M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Experimental and Theoretical UV Characterizations of Acetylacetone and Its Isomers</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2006-03-23</date><risdate>2006</risdate><volume>110</volume><issue>11</issue><spage>3920</spage><epage>3926</epage><pages>3920-3926</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>Cryogenic matrix isolation experiments have allowed the measurement of the UV absorption spectra of the high-energy non-chelated isomers of acetylacetone, these isomers being produced by UV irradiation of the stable chelated form. Their identification has been done by coupling selective UV-induced isomerization, infrared spectroscopy, and harmonic vibrational frequency calculations using density functional theory. The relative energies of the chelated and non-chelated forms of acetylacetone in the S0 state have been obtained using density functional theory and coupled-cluster methods. For each isomer of acetylacetone, we have calculated the UV transition energies and dipole oscillator strengths using the excited-state coupled-cluster methods, including EOMCCSD (equation-of-motion coupled-cluster method with singles and doubles) and CR-EOMCCSD(T) (the completely renormalized EOMCC approach with singles, doubles, and non-iterative triples). For dipole-allowed transition energies, there is a very good agreement between experiment and theory. In particular, the CR-EOMCCSD(T) approach explains the blue shift in the electronic spectrum due to the formation of the non-chelated species after the UV irradiation of the chelated form of acetylacetone. 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subjects | Models, Chemical Molecular Structure Pentanones - chemistry Pentanones - radiation effects Sensitivity and Specificity Spectrophotometry, Ultraviolet - methods Stereoisomerism Ultraviolet Rays |
title | Experimental and Theoretical UV Characterizations of Acetylacetone and Its Isomers |
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