Photodissociation Dynamics of a Triatomic Pseudo-Dihalide Absorption Cross Section and Dynamics of Solvated ICN-

Details Photodissociation Dynamics of a Triatomic Pseudo-Dihalide Absorption Cross Section and Dynamics of Solvated ICN- Photodissociation Dynamics of a Triatomic Pseudo-Dihalide Absorption Cross Section and Dynamics of Solvated ICN-

Jun 2011

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..confere10m&link_type=abstract

"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec

Computer Science

Dynamics

Scientific paper

We report the photoabsorption cross section and photoproduct branching ratios of mass-selected bare {ICN-} and {ICN-(CO2)} following excitation to the A' 2Π1/2 electronic excited state. Previous studies of {CO2} solvated-heteronuclear dihalides, {IX-(CO2)N} (X=Cl, Br), reported three excited state selective classes of photoproducts: {I-}, {X-}, and {IX-} based clusters. Photoabsorption of bare {ICl-} and {IBr-} that leads to population in the A' 2Π1/2 state have maxima near 680 nm and 740 nm, respectively, and result in {I-} photoproducts exclusively over the entire band corresponding to A' 2Π1/2 ← X 2Σ1/2 excitation. Interestingly, following excitation of bare {ICN-} to the comparable state (430-650 nm, maximum at 490 nm), {I-} is the dominant ionic photoproduct, but {CN-} photoproducts are observed as well. When a single {CO2} solvent molecule is added to {ICN-}, the same A' 2Π1/2 ← X 2Σ1/2 excitation results in apparent charge transfer within the complex. Therefore, the observed ionic photoproducts are not just the expected {I-} and {I-(CO2)}, but {CN-} and solvated {CN-(CO2)} photoproducts are also significant products. Analysis of the experimental results using calculated potential energy curves of {ICN-} reveals intriguing dynamics of the photoexcited triatomic pseudo-dihalide. Supported by NSF and AFOSR.

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