Photodissociation of Methyl Iodide via Selected Vibrational Levels of the $$\tilde{B}$$ ( 2 E 3/2 )6s Rydberg State
We have determined the I 2P3/2 and 2P1/2 branching fractions following the photodissociation of methyl iodide (CH3I) via a number of vibronic bands associated with the $$\tilde{B}$$ (2E3/2)6s Rydberg state at excitation wavelengths between 201.2 and 192.7 nm. Vacuum ultraviolet light at 118.2 nm was used to ionize both the product iodine atoms and the methyl radical cofragments, and velocity map ion imaging was used to determine the product translational energy distributions and angular distributions. The known relative photoionization cross sections for I 2P3/2 and 2P1/2 at 118.2 nm were used to determine the corresponding branching fractions. The results extend our earlier work at 193 nm by Xu et al. (J. Chem. Phys. 2013, 139, 214310), and complement the closely related work of González et al. (J. Chem. Phys. 2011, 135, 021102). We find that for most of the excited vibronic levels of the $$\tilde{B}$$ state studied, the I 2P3/2 branching ratio is small, but nonzero, and that this channel is associated with internally excited CH3 radicals. The results are discussed in relation to the recent theoretical results of Alekseyev et al. (J. Chem. Phys. 2011, 134, 044303).
- Research Organization:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1392607
- Journal Information:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 28; ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
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