dc.creator Martin, Joshua P. en_US dc.creator Gu, Quanli en_US dc.creator Darr, Joshua P. en_US dc.creator McCoy, Anne B. en_US dc.creator Lineberger, W. Carl en_US dc.date.accessioned 2011-07-12T17:27:18Z dc.date.available 2011-07-12T17:27:18Z dc.date.issued 2011 en_US dc.identifier 2011-RE-10 en_US dc.identifier.uri http://hdl.handle.net/1811/49323 dc.description Supported by NSF and AFOSR. en_US dc.description Author Institution: JILA, Department of Chemistry and Biochemistry University of Colorado at Boulder, Boulder, CO 80309; Department of Chemistry, The Ohio State University, Columbus, OH 43210; JILA, Department of Chemistry and Biochemistry, University of Colorado at Boulder, Boulder, CO 80309 en_US dc.description.abstract We report the photoabsorption cross section and photoproduct branching ratios of mass-selected bare $\chem{ICN^{-}}$ and $\chem{ICN^{-}(CO_{2})}$ following excitation to the $A^{\prime}$ $^{2}$\Pi$_{1/2}$ electronic excited state. Previous studies of $\chem{CO_{2}}$ solvated-heteronuclear dihalides, $\chem{IX^{-}(CO_{2})_{n}}$ (X=Cl, Br), reported three excited state selective classes of photoproducts: $\chem{I^{-}}$, $\chem{X^{-}}$, and $\chem{IX^{-}}$ based clusters. Photoabsorption of bare $\chem{ICl^{-}}$ and $\chem{IBr^{-}}$ that leads to population in the $A^{\prime}$ $^{2}$\Pi$_{1/2}$ state have maxima near 680 nm and 740 nm, respectively, and result in $\chem{I^{-}}$ photoproducts exclusively over the entire band corresponding to $A^{\prime}$ $^{2}$\Pi$_{1/2}$ \leftarrow X $^{2}$\Sigma$_{1/2}$ excitation. Interestingly, following excitation of bare $\chem{ICN^{-}}$ to the comparable state (430-650 nm, maximum at 490 nm), $\chem{I^{-}}$ is the dominant ionic photoproduct, but $\chem{CN^{-}}$ photoproducts are observed as well. When a single $\chem{CO_{2}}$ solvent molecule is added to $\chem{ICN^{-}}$, the same $A^{\prime}$ $^{2}$\Pi$_{1/2}$ \leftarrow X $^{2}$\Sigma$_{1/2}$ excitation results in apparent charge transfer within the complex. Therefore, the observed ionic photoproducts are not just the expected $\chem{I^{-}}$ and $\chem{I^{-}(CO_{2})}$, but $\chem{CN^{-}}$ and solvated $\chem{CN^{-}(CO_{2})}$ photoproducts are also significant products. Analysis of the experimental results using calculated potential energy curves of $\chem{ICN^{-}}$ reveals intriguing dynamics of the photoexcited triatomic pseudo-dihalide. en_US dc.language.iso en en_US dc.publisher Ohio State University en_US dc.title PHOTODISSOCIATION DYNAMICS OF A TRIATOMIC PSEUDO-DIHALIDE: ABSORPTION CROSS SECTION AND DYNAMICS OF SOLVATED ICN$^{-}$ en_US dc.type Article en_US
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