dc.creator Briney, Kristin A. en_US dc.creator Herman, Leslie V. en_US dc.creator Boucher, Dave S. en_US dc.creator Crim, F. Fleming en_US dc.date.accessioned 2010-07-12T14:08:13Z dc.date.available 2010-07-12T14:08:13Z dc.date.issued 2010 en_US dc.identifier 2010-TA-06 en_US dc.identifier.uri http://hdl.handle.net/1811/46221 dc.description Author Institution: The University of Wisconsin-Madison, Department of Chemistry, 1101 University Avenue, Madison, WI 53706 en_US dc.description.abstract We study the effect of vibrational energy on the isomerization reaction of \textit{trans}-stilbene in deuterated chloroform. We first excite a ground-state C-H stretch overtone or a stretch-bend combination and allow vibrational relaxation to occur within the molecule before photoinitiating the excited-state isomerization with an ultraviolet photon. Once the stilbene molecule is on the excited state, we monitor the isomerization dynamics via broadband transient absorption spectroscopy. We measure an excited-state lifetime of 55 $\pm$ 9 ps when exciting through the C-H stretch overtone and a lifetime of 56 $\pm$ 7 ps for excitation through the stretch-bend combination. The \textit{trans}-stilbene excited-state lifetime after single photon vertical excitation is 52 $\pm$ 6 ps with the total added energy being the same for all measurements. Unlike in gas phase studies, where vibrational motion can change the outcome of a chemical reaction, there is no observed difference in the reaction dynamics when exciting this condensed phase system with a single photon versus exciting through a ground-state vibrational mode. Interactions with the solvent cause fast vibrational relaxation on the excited state, though the insensitivity of the rate to vibrational energy may also be due to excess vibrational energy not being promptly partitioned into modes along the isomerization coordinate. en_US dc.language.iso en en_US dc.publisher Ohio State University en_US dc.title THE EFFECT OF VIBRATIONAL ENERGY ON THE ISOMERIZATION REACTION OF TRANS-STILBENE IN THE CONDENSED PHASE en_US dc.type Article en_US dc.type Image en_US dc.type Presentation en_US
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