PREDISSOCIATION DYNAMICS OF THE $A^{2}\Sigma^{+}$ STATE OF THE SH RADICAL

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Velocity map imaging of the S(3PJ=0,1,2) fragments from the predissociation of selected ro-vibrational levels of the A2Σ+ state of SH has been used to determine photofragment recoil anisotropies, branching into spin-orbit levels, and the electronic angular momentum polarization of the S atoms. The photofragment recoil anisotropies will be compared with predictions from a model by Houston and coworkers}, \underline{125}, 133316 (2006).} that accounts for the effects of excited state lifetimes. These vibrational and rotational level dependent lifetimes were previously measured by cavity ring-down spectroscopy and modelled using Fermi Golden rule calculations.}, \underline{107}, 7591 (1997).} The spin-orbit level branching and populations of mJ states, derived from the angular momentum polarization measurements, depend on the correlation of the repulsive states responsible for the A2Σ+ state predissociation to the asymptotic H(2S1/2)+S(3PJ) limits and non-adiabatic dynamics during the fragmentation.

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H. Kim, K.S. Dooley, S.W. North, G.E. Hall and P.L. Houston, J. Chem. Phys.M.D. Wheeler, A.J. Orr-Ewing and M.N.R. Ashfold, J. Chem. Phys.


Author Institution: School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K.; Institute for Molecules and Materials, University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, the Netherlands

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