State-to-state photodissociation dynamics of t r a n s-glyoxal

Abstract

The photodissociation of glyoxal has been investigated by monitoring the CO internal energy distribution using tunable vacuum ultraviolet laser‐induced fluorescence on the A←X system. Appearance times for the CO are in excellent agreement with the glyoxal fluorescence decay times, indicating that there is no long‐lived intermediate in the dissociation. The quantum yield for CO production is independent of the K quantum number describing the glyoxal rotation. The CO is formed almost entirely in v=0 but is spread over a broadly excited rotational distribution peaking at J≂42. Analysis of the CO Doppler profiles shows that the velocity of the CO increases with increasing rotational level and that the CO recoil velocity vector is oriented predominantly perpendicular to its angular momentum vector. These observations, which are in agreement with both previous time‐of‐flight data and molecular orbital calculations, are consistent with a model for the dissociation involving planar intermediates for the two channels leading to CO+H₂CO or to 2 CO+H₂. It appears that the highest rotational levels of CO are produced in coincidence with the H₂CO channel.