Competition between photochemistry and energy transfer in UV-excited diazabenzenes. 4. UV photodissociation of 2,3-, 2,5-, and 2,6-dimethylpyrazine.

The quantum yield for HCN formation via 248 nm photodissociation of 2,3-, 2,5-, and 2,6-dimethylpyrazine (DMP, C6N2H8) was measured using diode laser probing of the HCN photoproduct. The total quantum yield is phi = 0.039 +/- 0.07, 0.14 +/- 0.02, and 0.30 +/- 0.06 for 248 nm excitation of 2,3-, 2,5- and 2,6-DMP, respectively. Analysis of the quenching data within the context of a gas kinetic, strong collision model allows an estimate of the rate constant for HCN production via DMP photodissociation, ks = 4.1 x 10(3), 1.0 x 10(3), and 1.3 x 10(4) s(-1) for 2,3-, 2,5- and 2,6-DMP, respectively. Unlike HCN produced from the photodissociation of pyrazine and methylpyrazine, the amount of HCN produced via a prompt, unquenched dissociation channel was essentially zero, suggesting little multiphoton UV absorption. The rate constants for HCN formation together with previously measured rate constants for HCN production from photodissociation of pyrazine and methylpyrazine have been used to investigate possible reaction mechanisms. The position of the methyl group affects the HCN rate constant, suggesting that the mechanism for pyrazine dissociation involves an initial step that is hindered by the addition of the methyl groups. The proposed initial molecular motion of the mechanism, an out-of-plane H atom migration across a N atom, is consistent with (1) the position of the methyl groups, (2) the dissociation lifetime of the various pyrazine molecules studied, and (3) the observed large energy transfer magnitudes from pyrazine near dissociation. These so-called "supercollisions" have been linked to low-frequency, out-of-plane motion, suggesting that the molecular motions leading to efficient energy transfer are the same motions involved in dissociation. In addition, the pyrazine (C4N2H4) 248 nm photoproduct (C3H3N) was identified as acrylonitrile using IR spectroscopy, an observation that aids in understanding the dissociation mechanism.