Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols
The fluorescence lifetime of rhodamine B in a series of normal alcohols (C/sub n/H/sub 2n-1/OH, n = 1-6) was measured as a function of temperature. The nonradiative rate constants were calculated from the fluorescence lifetimes and quantum yields. Activation energies were obtained from Arrhenius plo...
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| Veröffentlicht in: | J. Phys. Chem.; (United States) 1988-11, Vol.92 (23), p.6590-6594 |
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| container_title | J. Phys. Chem.; (United States) |
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| creator | Casey, Kelly G Quitevis, Edward L |
| description | The fluorescence lifetime of rhodamine B in a series of normal alcohols (C/sub n/H/sub 2n-1/OH, n = 1-6) was measured as a function of temperature. The nonradiative rate constants were calculated from the fluorescence lifetimes and quantum yields. Activation energies were obtained from Arrhenius plots of the nonradiative rate constant. The variation of the nonradiative rate constant with solvent polarity and temperature was consistent with a photophysical mechanism that involves equilibrium between the planar and twisted configurations of the diethylamino groups on the xanthene ring of rhodamine B and internal conversion from the twisted configuration. The activation energy is equal to the free energy difference between the twisted and planar configurations. The solvent polarity dependence of the free energy difference and of the rate constant for internal conversion from the twisted configuration determines the variation of the nonradiative rate constant with solvent. When solvent polarity effects are taken into account by using the parameter E/sub T/(30), the nonradiative rate constant shows weak or no dependence on the solvent viscosity. |
| doi_str_mv | 10.1021/j100334a023 |
| format | Article |
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The nonradiative rate constants were calculated from the fluorescence lifetimes and quantum yields. Activation energies were obtained from Arrhenius plots of the nonradiative rate constant. The variation of the nonradiative rate constant with solvent polarity and temperature was consistent with a photophysical mechanism that involves equilibrium between the planar and twisted configurations of the diethylamino groups on the xanthene ring of rhodamine B and internal conversion from the twisted configuration. The activation energy is equal to the free energy difference between the twisted and planar configurations. The solvent polarity dependence of the free energy difference and of the rate constant for internal conversion from the twisted configuration determines the variation of the nonradiative rate constant with solvent. When solvent polarity effects are taken into account by using the parameter E/sub T/(30), the nonradiative rate constant shows weak or no dependence on the solvent viscosity.</description><identifier>ISSN: 0022-3654</identifier><identifier>EISSN: 1541-5740</identifier><identifier>DOI: 10.1021/j100334a023</identifier><identifier>CODEN: JPCHAX</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>400500 - Photochemistry ; 420300 - Engineering- Lasers- (-1989) ; ALCOHOLS ; AMINES ; Applied sciences ; CARBOXYLIC ACIDS ; Chemical industry and chemicals ; CHEMICAL REACTIONS ; DATA ; DE-EXCITATION ; DYE LASERS ; DYES ; Dyes, pigments ; ENERGY TRANSFER ; ENERGY-LEVEL TRANSITIONS ; ENGINEERING ; Exact sciences and technology ; EXPERIMENTAL DATA ; FLUORESCENCE ; HETEROCYCLIC ACIDS ; HETEROCYCLIC COMPOUNDS ; HYDROXY COMPOUNDS ; Industrial chemicals ; INFORMATION ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; LASERS ; LIFETIME ; LIQUID LASERS ; LUMINESCENCE ; NUMERICAL DATA ; ORGANIC ACIDS ; ORGANIC COMPOUNDS ; ORGANIC OXYGEN COMPOUNDS ; PHOTOCHEMICAL REACTIONS ; RADIATIONLESS DECAY ; REAGENTS ; RHODAMINES ; SOLVENT PROPERTIES ; TEMPERATURE DEPENDENCE</subject><ispartof>J. 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Chem.; (United States), 1988-11, Vol.92 (23), p.6590-6594</ispartof><rights>1990 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a423t-5a7d8fb11d3007ef135892da2640dc15ec6fd5015c62879d0885a50bebd3b7233</citedby></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/j100334a023$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/j100334a023$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,776,780,881,2752,27053,27901,27902,56713,56763</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=6813584$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/6220180$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Casey, Kelly G</creatorcontrib><creatorcontrib>Quitevis, Edward L</creatorcontrib><creatorcontrib>Texas Tech Univ., Lubbock (USA)</creatorcontrib><title>Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols</title><title>J. Phys. Chem.; (United States)</title><addtitle>J. Phys. Chem</addtitle><description>The fluorescence lifetime of rhodamine B in a series of normal alcohols (C/sub n/H/sub 2n-1/OH, n = 1-6) was measured as a function of temperature. The nonradiative rate constants were calculated from the fluorescence lifetimes and quantum yields. Activation energies were obtained from Arrhenius plots of the nonradiative rate constant. The variation of the nonradiative rate constant with solvent polarity and temperature was consistent with a photophysical mechanism that involves equilibrium between the planar and twisted configurations of the diethylamino groups on the xanthene ring of rhodamine B and internal conversion from the twisted configuration. The activation energy is equal to the free energy difference between the twisted and planar configurations. The solvent polarity dependence of the free energy difference and of the rate constant for internal conversion from the twisted configuration determines the variation of the nonradiative rate constant with solvent. When solvent polarity effects are taken into account by using the parameter E/sub T/(30), the nonradiative rate constant shows weak or no dependence on the solvent viscosity.</description><subject>400500 - Photochemistry</subject><subject>420300 - Engineering- Lasers- (-1989)</subject><subject>ALCOHOLS</subject><subject>AMINES</subject><subject>Applied sciences</subject><subject>CARBOXYLIC ACIDS</subject><subject>Chemical industry and chemicals</subject><subject>CHEMICAL REACTIONS</subject><subject>DATA</subject><subject>DE-EXCITATION</subject><subject>DYE LASERS</subject><subject>DYES</subject><subject>Dyes, pigments</subject><subject>ENERGY TRANSFER</subject><subject>ENERGY-LEVEL TRANSITIONS</subject><subject>ENGINEERING</subject><subject>Exact sciences and technology</subject><subject>EXPERIMENTAL DATA</subject><subject>FLUORESCENCE</subject><subject>HETEROCYCLIC ACIDS</subject><subject>HETEROCYCLIC COMPOUNDS</subject><subject>HYDROXY COMPOUNDS</subject><subject>Industrial chemicals</subject><subject>INFORMATION</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>LASERS</subject><subject>LIFETIME</subject><subject>LIQUID LASERS</subject><subject>LUMINESCENCE</subject><subject>NUMERICAL DATA</subject><subject>ORGANIC ACIDS</subject><subject>ORGANIC COMPOUNDS</subject><subject>ORGANIC OXYGEN COMPOUNDS</subject><subject>PHOTOCHEMICAL REACTIONS</subject><subject>RADIATIONLESS DECAY</subject><subject>REAGENTS</subject><subject>RHODAMINES</subject><subject>SOLVENT PROPERTIES</subject><subject>TEMPERATURE DEPENDENCE</subject><issn>0022-3654</issn><issn>1541-5740</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>1988</creationdate><recordtype>article</recordtype><recordid>eNpt0N9rFDEQB_AgFjxbn_wHggg-yOok2exufbNH9YRCi63UtzCXH1zOveTIxNL7791jpfjg0xDmk2Hmy9hrAR8ESPFxKwCUahGkesYWQrei0X0Lz9kCQMpGdbp9wV4SbQFAKCUWzF-G4G3lOXDK44NPle_ziCXWA8-Jp5wKuog1Pni-L9l6Ik88Jv6IqW588twdPH3i3zfZ4S5O74tjN-Wyw5HjaPMmj3TGTgKO5F_9rafsx5fLu-Wqubr--m35-arBVqraaOzdENZCOAXQ-yCUHs6lQ9m14KzQ3nbBaRDadnLozx0Mg0YNa792at1LpU7Zm3luphoN2Vi93dic0nSi6aQEMcCE3s_IlkxUfDD7EndYDkaAOcZo_olx0m9nvUeyOIaCyUZ6-tINxyXbiTUzi1T941Mbyy_T9arX5u7m1vTq_uf97WppVpN_N3u0ZLb5d0lTLv9d4A_fxIz3</recordid><startdate>198811</startdate><enddate>198811</enddate><creator>Casey, Kelly G</creator><creator>Quitevis, Edward L</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>OTOTI</scope></search><sort><creationdate>198811</creationdate><title>Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols</title><author>Casey, Kelly G ; Quitevis, Edward L</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a423t-5a7d8fb11d3007ef135892da2640dc15ec6fd5015c62879d0885a50bebd3b7233</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>1988</creationdate><topic>400500 - Photochemistry</topic><topic>420300 - Engineering- Lasers- (-1989)</topic><topic>ALCOHOLS</topic><topic>AMINES</topic><topic>Applied sciences</topic><topic>CARBOXYLIC ACIDS</topic><topic>Chemical industry and chemicals</topic><topic>CHEMICAL REACTIONS</topic><topic>DATA</topic><topic>DE-EXCITATION</topic><topic>DYE LASERS</topic><topic>DYES</topic><topic>Dyes, pigments</topic><topic>ENERGY TRANSFER</topic><topic>ENERGY-LEVEL TRANSITIONS</topic><topic>ENGINEERING</topic><topic>Exact sciences and technology</topic><topic>EXPERIMENTAL DATA</topic><topic>FLUORESCENCE</topic><topic>HETEROCYCLIC ACIDS</topic><topic>HETEROCYCLIC COMPOUNDS</topic><topic>HYDROXY COMPOUNDS</topic><topic>Industrial chemicals</topic><topic>INFORMATION</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>LASERS</topic><topic>LIFETIME</topic><topic>LIQUID LASERS</topic><topic>LUMINESCENCE</topic><topic>NUMERICAL DATA</topic><topic>ORGANIC ACIDS</topic><topic>ORGANIC COMPOUNDS</topic><topic>ORGANIC OXYGEN COMPOUNDS</topic><topic>PHOTOCHEMICAL REACTIONS</topic><topic>RADIATIONLESS DECAY</topic><topic>REAGENTS</topic><topic>RHODAMINES</topic><topic>SOLVENT PROPERTIES</topic><topic>TEMPERATURE DEPENDENCE</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Casey, Kelly G</creatorcontrib><creatorcontrib>Quitevis, Edward L</creatorcontrib><creatorcontrib>Texas Tech Univ., Lubbock (USA)</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>CrossRef</collection><collection>OSTI.GOV</collection><jtitle>J. Phys. Chem.; (United States)</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Casey, Kelly G</au><au>Quitevis, Edward L</au><aucorp>Texas Tech Univ., Lubbock (USA)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols</atitle><jtitle>J. Phys. Chem.; (United States)</jtitle><addtitle>J. Phys. Chem</addtitle><date>1988-11</date><risdate>1988</risdate><volume>92</volume><issue>23</issue><spage>6590</spage><epage>6594</epage><pages>6590-6594</pages><issn>0022-3654</issn><eissn>1541-5740</eissn><coden>JPCHAX</coden><abstract>The fluorescence lifetime of rhodamine B in a series of normal alcohols (C/sub n/H/sub 2n-1/OH, n = 1-6) was measured as a function of temperature. The nonradiative rate constants were calculated from the fluorescence lifetimes and quantum yields. Activation energies were obtained from Arrhenius plots of the nonradiative rate constant. The variation of the nonradiative rate constant with solvent polarity and temperature was consistent with a photophysical mechanism that involves equilibrium between the planar and twisted configurations of the diethylamino groups on the xanthene ring of rhodamine B and internal conversion from the twisted configuration. The activation energy is equal to the free energy difference between the twisted and planar configurations. The solvent polarity dependence of the free energy difference and of the rate constant for internal conversion from the twisted configuration determines the variation of the nonradiative rate constant with solvent. When solvent polarity effects are taken into account by using the parameter E/sub T/(30), the nonradiative rate constant shows weak or no dependence on the solvent viscosity.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><doi>10.1021/j100334a023</doi><tpages>5</tpages></addata></record> |
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| ispartof | J. Phys. Chem.; (United States), 1988-11, Vol.92 (23), p.6590-6594 |
| issn | 0022-3654 1541-5740 |
| language | eng |
| recordid | cdi_crossref_primary_10_1021_j100334a023 |
| source | American Chemical Society Journals |
| subjects | 400500 - Photochemistry 420300 - Engineering- Lasers- (-1989) ALCOHOLS AMINES Applied sciences CARBOXYLIC ACIDS Chemical industry and chemicals CHEMICAL REACTIONS DATA DE-EXCITATION DYE LASERS DYES Dyes, pigments ENERGY TRANSFER ENERGY-LEVEL TRANSITIONS ENGINEERING Exact sciences and technology EXPERIMENTAL DATA FLUORESCENCE HETEROCYCLIC ACIDS HETEROCYCLIC COMPOUNDS HYDROXY COMPOUNDS Industrial chemicals INFORMATION INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY LASERS LIFETIME LIQUID LASERS LUMINESCENCE NUMERICAL DATA ORGANIC ACIDS ORGANIC COMPOUNDS ORGANIC OXYGEN COMPOUNDS PHOTOCHEMICAL REACTIONS RADIATIONLESS DECAY REAGENTS RHODAMINES SOLVENT PROPERTIES TEMPERATURE DEPENDENCE |
| title | Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols |
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