18 September 1995 Photodissociation dynamics of NO2 at 309.1 nm
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The dynamics of NO2 dissociation at 309.1 nm have been explored by examining the nascent distribution of NO rotational, vibrational, spin-orbit and lambda-doublet states. The NO fragment is produced with a monotonically decreasing vibrational distribution over the energetically accessible vibrational states ((upsilon) equals 0 minus 3), and non-statistical rotational distributions within each vibrational manifold. The distribution within (upsilon) equals 0 and 1 is strongly peaked near J equals 25.5 with a fairly narrow spread; the distribution within (upsilon) equals 2 is fairly flat, terminating at the limit of available energy; and the (upsilon) equals 3 distribution is oscillatory, also terminating at the limit of available energy. The 2(Pi) 1/2 spin-orbit state is more strongly populated than the 2(Pi) 3/2 state by a factor of 1.9 for every vibrational state. The differences in lambda-doublet populations are in general minor; each (Lambda) -state being roughly equally populated, although oscillations are again evident. It is found that the results are intermediate between the previous data at low excess energy and at high available energy; the distributions showing aspects of both regimes. From the data it is inferred that the dissociation dynamics of NO2 vary continuously from a regime where phase space theory considerations with quantum overtones dominate the product state distributions to the regime where dynamics on the exit channel determine the distributions.
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Pamela T. Knepp, Pamela T. Knepp, Andrew C. Terentis, Andrew C. Terentis, Scott H. Kable, Scott H. Kable, "Photodissociation dynamics of NO2 at 309.1 nm", Proc. SPIE 2548, Laser Techniques for State-Selected and State-to-State Chemistry III, (18 September 1995); doi: 10.1117/12.220864; https://doi.org/10.1117/12.220864

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