Probing Curve Crossing by Wavelength-Dependent Recoil Anisotropy: The Photodissociation of CF3I at 275−303 nm Studied by Photofragment Translational Spectroscopy
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Abstract
Polarized photofragment translational spectroscopy was used to investigate the photodissociation process CF3I → CF3 + I(2P3/2) and CF3I → CF3 + I*(2P1/2) in the A absorption band between 275 and 303 nm. We determined the fragment recoil anisotropies β(I) and β(I*) and the branching ratio of the products I and I* as a function of the excitation wavelength λexc which covers most of the overlapping transitions 3Q1 ← X and 3Q0 ← X. The results are interpreted within the mechanistic scheme that involves three potential energy surfaces 3Q1, 3Q0, and 1Q1. The variation in the anisotropy β(I*) and the product-yield ratio I/I* with λexc is shown to reflect the variation of mixed 3Q0 and 1Q1 character of the adiabatic states when excited near the avoided curve crossing.
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