Dissociation Dynamics of the IBr^{-}(CO_{2}) Van Der Waals Cluster: a Direct View of Solvent-Driven Non-Adiabatic Transitions

Details Dissociation Dynamics of the IBr^{-}(CO_{2}) Van Der Waals Cluster: a Direct View of Solvent-Driven Non-Adiabatic Transitions Dissociation Dynamics of the IBr^{-}(CO_{2}) Van Der Waals Cluster: a Direct View of Solvent-Driven Non-Adiabatic Transitions

Jun 2009

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..confewf03s&link_type=abstract

"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec

Computer Science

Dynamics

Scientific paper

We present the results of several time-resolved pump-probe experiments that explore the photodissociation of a simple dihalide anion, IBr^{-}, clustered with a single CO_{2} solvent molecule. A 100-fs pump laser pulse (λ=800 or 400 nm) initiates the dissociation of IBr^{-} on either the A'^{2}Π_{1/2} or the higher-lying B^{2}Σ^{+}_{1/2} state of the anion. A second, time-delayed, tunable 100-fs laser pulse probes the subsequent dynamics by photoelectron spectroscopy. In the bare anion the A' and B states correlate exclusively to the I^{-} or the Br^{-} photoproducts, respectively. However, the addition of a single solvent molecule induces charge switching in a subset of the excited molecules midway through the dissociation, resulting in mixed photoproduct distributions (both I^{-} and Br^{-}) from both states. In the case of dissociation on the A' state (which correlates asymptotically to I^{-}), the CO_{2} solvent molecule produces charge switching to Br^{-} in about 3% of the products, even though it cannot induce potential curve crossings. Electronic structure calculations and MD simulations point to a subtle mechanism for these non-adiabatic charge hops, involving the effects of the CO_{2} bending vibration to bridge the energetic gap of the charge transfer. Conversely, for dissociation on the higher-lying B state (which correlates asymptotically to Br^{-}), the photoproduct ratio is about 60% Br^{-}:40% I^{-}, indicating large amounts of charge switching. In this case it is energetically possible for the CO_{2} molecule to cause the B state to cross with the nearby a'^{2}Π_{1/2} state, which correlates with I^{-}. The charge switching mechanism, which is likely to be more complex than for the A' state, will be discussed in detail.

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