Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ(∗) states
Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PF...
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| Veröffentlicht in: | The Journal of chemical physics 2015-05, Vol.142 (18), p.184303-184303 |
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| creator | Karmakar, Shreetama Mukhopadhyay, Deb Pratim Chakraborty, Tapas |
| description | Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ(∗) character in the vicinity of the lowest valence ππ(∗) state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ(∗) and a nearby dissociative πσ(∗) state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H2O)n clusters (n = 1-11), intensities of a number of πσ(∗) states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the observed photophysical behavior. |
| doi_str_mv | 10.1063/1.4919950 |
| format | Article |
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It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ(∗) character in the vicinity of the lowest valence ππ(∗) state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ(∗) and a nearby dissociative πσ(∗) state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H2O)n clusters (n = 1-11), intensities of a number of πσ(∗) states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the observed photophysical behavior.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.4919950</identifier><identifier>PMID: 25978887</identifier><language>eng</language><publisher>United States: American Institute of Physics</publisher><subject>ATOMS ; Chromophores ; Decay ; Electron states ; Electronic spectra ; ELECTRONIC STRUCTURE ; ENERGY DEPENDENCE ; EXCITATION ; Excitation spectra ; EXCITED STATES ; FLUORESCENCE ; FLUORESCENCE SPECTROSCOPY ; FLUORINE ; HYDROCARBONS ; HYDROGEN ; Hydrogen bonding ; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY ; LIQUIDS ; Luminous intensity ; METHANOL ; MOLECULES ; Organic chemistry ; PHENOL ; Phenols ; Physics ; Reference systems ; SOLUTES ; SOLUTIONS ; SOLVENTS ; VALENCE ; WATER ; YIELDS</subject><ispartof>The Journal of chemical physics, 2015-05, Vol.142 (18), p.184303-184303</ispartof><rights>2015 AIP Publishing LLC.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c256t-873adf0c528ce308252617eaa5b381bc93a447d8ede1aca3aeee8e23699508b13</citedby><cites>FETCH-LOGICAL-c256t-873adf0c528ce308252617eaa5b381bc93a447d8ede1aca3aeee8e23699508b13</cites><orcidid>0000-0002-5292-3873</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,314,776,780,881,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/25978887$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/biblio/22415767$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Karmakar, Shreetama</creatorcontrib><creatorcontrib>Mukhopadhyay, Deb Pratim</creatorcontrib><creatorcontrib>Chakraborty, Tapas</creatorcontrib><title>Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ(∗) states</title><title>The Journal of chemical physics</title><addtitle>J Chem Phys</addtitle><description>Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ(∗) character in the vicinity of the lowest valence ππ(∗) state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ(∗) and a nearby dissociative πσ(∗) state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H2O)n clusters (n = 1-11), intensities of a number of πσ(∗) states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the observed photophysical behavior.</description><subject>ATOMS</subject><subject>Chromophores</subject><subject>Decay</subject><subject>Electron states</subject><subject>Electronic spectra</subject><subject>ELECTRONIC STRUCTURE</subject><subject>ENERGY DEPENDENCE</subject><subject>EXCITATION</subject><subject>Excitation spectra</subject><subject>EXCITED STATES</subject><subject>FLUORESCENCE</subject><subject>FLUORESCENCE SPECTROSCOPY</subject><subject>FLUORINE</subject><subject>HYDROCARBONS</subject><subject>HYDROGEN</subject><subject>Hydrogen bonding</subject><subject>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</subject><subject>LIQUIDS</subject><subject>Luminous intensity</subject><subject>METHANOL</subject><subject>MOLECULES</subject><subject>Organic chemistry</subject><subject>PHENOL</subject><subject>Phenols</subject><subject>Physics</subject><subject>Reference systems</subject><subject>SOLUTES</subject><subject>SOLUTIONS</subject><subject>SOLVENTS</subject><subject>VALENCE</subject><subject>WATER</subject><subject>YIELDS</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNpFkc9O20AQxleoiKTAoS9QrcQFDqY7u_b-4YZQ2iJF4kLPq8163Dhydl2vLcgNiUvfoI_FO_RJcJpATzPS_ObTfPMR8gnYJTApvsBlbsCYgh2QKTBtMiUN-0CmjHHIjGRyQj6mtGKMgeL5EZnwwiittZqSetag77sYak9Tu20ddaGk-OjrHkuaetcjLTfBrWufaKxoi6F3VTPELrZLDLG5orOqGjf_TZv4kDWbOvykL08vz-d_f_-52GmkE3JYuSbh6b4ekx9fZ_c337P53bfbm-t55nkh-0wr4cqK-YJrj4JpXnAJCp0rFkLDwhvh8lyVGksE551wiKiRC7n1rxcgjsnZTjemvrZpa8MvfQxhPNFynkOhpBqp8x3VdvHXgKm36zp5bBoXMA7JgtRgALQQ_wXf0VUcujB6sBx4rsZnF3qkLnaU72JKHVa27eq16zYWmN2mZMHuUxrZz3vFYbHG8p18i0W8AtH0jYg</recordid><startdate>20150514</startdate><enddate>20150514</enddate><creator>Karmakar, Shreetama</creator><creator>Mukhopadhyay, Deb Pratim</creator><creator>Chakraborty, Tapas</creator><general>American Institute of Physics</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0002-5292-3873</orcidid></search><sort><creationdate>20150514</creationdate><title>Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ(∗) states</title><author>Karmakar, Shreetama ; Mukhopadhyay, Deb Pratim ; Chakraborty, Tapas</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c256t-873adf0c528ce308252617eaa5b381bc93a447d8ede1aca3aeee8e23699508b13</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>ATOMS</topic><topic>Chromophores</topic><topic>Decay</topic><topic>Electron states</topic><topic>Electronic spectra</topic><topic>ELECTRONIC STRUCTURE</topic><topic>ENERGY DEPENDENCE</topic><topic>EXCITATION</topic><topic>Excitation spectra</topic><topic>EXCITED STATES</topic><topic>FLUORESCENCE</topic><topic>FLUORESCENCE SPECTROSCOPY</topic><topic>FLUORINE</topic><topic>HYDROCARBONS</topic><topic>HYDROGEN</topic><topic>Hydrogen bonding</topic><topic>INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY</topic><topic>LIQUIDS</topic><topic>Luminous intensity</topic><topic>METHANOL</topic><topic>MOLECULES</topic><topic>Organic chemistry</topic><topic>PHENOL</topic><topic>Phenols</topic><topic>Physics</topic><topic>Reference systems</topic><topic>SOLUTES</topic><topic>SOLUTIONS</topic><topic>SOLVENTS</topic><topic>VALENCE</topic><topic>WATER</topic><topic>YIELDS</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Karmakar, Shreetama</creatorcontrib><creatorcontrib>Mukhopadhyay, Deb Pratim</creatorcontrib><creatorcontrib>Chakraborty, Tapas</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Karmakar, Shreetama</au><au>Mukhopadhyay, Deb Pratim</au><au>Chakraborty, Tapas</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ(∗) states</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2015-05-14</date><risdate>2015</risdate><volume>142</volume><issue>18</issue><spage>184303</spage><epage>184303</epage><pages>184303-184303</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><abstract>Multiple fluorine atom substitution effect on photophysics of an aromatic chromophore has been investigated using phenol as the reference system. It has been noticed that the discrete vibronic structure of the S1←S0 absorption system of phenol vapor is completely washed out for pentafluorophenol (PFP), and the latter also shows very large Stokes shift in the fluorescence spectrum. For excitations beyond S1 origin, the emission yield of PFP is reduced sharply with increase in excess vibronic energy. However, in a collisional environment like liquid hydrocarbon, the underlying dynamical process that drives the non-radiative decay is hindered drastically. Electronic structure theory predicts a number of low-lying dark electronic states of πσ(∗) character in the vicinity of the lowest valence ππ(∗) state of this molecule. Tentatively, we have attributed the excitation energy dependent non-radiative decay of the molecule observed only in the gas phase to an interplay between the lowest ππ(∗) and a nearby dissociative πσ(∗) state. Measurements in different liquids reveal that some of the dark excited states light up with appreciable intensity only in protic liquids like methanol and water due to hydrogen bonding between solute and solvents. Electronic structure theory methods indeed predict that for PFP-(H2O)n clusters (n = 1-11), intensities of a number of πσ(∗) states are enhanced with increase in cluster size. In contrast with emitting behavior of the molecule in the gas phase and solutions of nonpolar and polar aprotic liquids, the fluorescence is completely switched off in polar protic liquids. This behavior is a chemically significant manifestation of perfluoro effect, because a very opposite effect occurs in the case of unsubstituted phenol for which fluorescence yield undergoes a very large enhancement in protic liquids. Several dynamical mechanisms have been suggested to interpret the observed photophysical behavior.</abstract><cop>United States</cop><pub>American Institute of Physics</pub><pmid>25978887</pmid><doi>10.1063/1.4919950</doi><tpages>1</tpages><orcidid>https://orcid.org/0000-0002-5292-3873</orcidid></addata></record> |
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| subjects | ATOMS Chromophores Decay Electron states Electronic spectra ELECTRONIC STRUCTURE ENERGY DEPENDENCE EXCITATION Excitation spectra EXCITED STATES FLUORESCENCE FLUORESCENCE SPECTROSCOPY FLUORINE HYDROCARBONS HYDROGEN Hydrogen bonding INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY LIQUIDS Luminous intensity METHANOL MOLECULES Organic chemistry PHENOL Phenols Physics Reference systems SOLUTES SOLUTIONS SOLVENTS VALENCE WATER YIELDS |
| title | Electronic spectra and excited state dynamics of pentafluorophenol: Effects of low-lying πσ(∗) states |
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