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J Chem Phys. 2012 Oct 14;137(14):144302. doi: 10.1063/1.4757019.

Photofragment translational spectroscopy of CH3I at 225 nm--with the high excitation of the symmetric stretch vibration of CH3 fragment.

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National Laboratory of Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.


The photodissociation dynamics of CH(3)I at 225 nm is studied on our high resolution mini-TOF photofragment translational spectrometer. The photofragment translational spectra of the I* and the I channels via parallel (∥) and perpendicular (⊥) transitions, i.e., of the four pathways (3)Q(0), (3)Q(0) ← (1)Q(1), (1)Q(1), and (1)Q(1) ← (3)Q(0), are obtained with both the symmetric stretch (ν(1)) and the umbrella (ν(2)) vibrational modes of the CH(3) fragments partially resolved. The strong excitation of the symmetric stretch mode (ν(1)) is revealed in both the I and the I* channels. The branching fractions for the four pathways (0.09 for (3)Q(0), 0.03 for (3)Q(0) ← (1)Q(1), 0.34 for (1)Q(1), and 0.54 for (1)Q(1) ← (3)Q(0)) show that the parallel transition ((3)Q(0) ← X) is the major and the I channel is dominant in the photodissociation of CH(3)I at 225 nm. The curve-crossing probability is found to be 0.86 for (1)Q(1) ← (3)Q(0) but 0.08 for (3)Q(0) ← (1)Q(1).

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