Photodissociation of acetaldehyde: The CH4+CO channel

Ab initio quantum chemical calculations for the molecular dissociation chan nel of acetaldehyde are reported. The enthalpy change for the dissociation of acetaldehyde into methane and carbon monoxide was calculated to be exoer gic by 1.7 kcal/mol. The transition state for this unimolecular dissociatio n, confirmed by normal mode analysis, was found to have an activation energ y of 85.3 kcal/mol. Experimental measurements are reported for the vibratio nal and rotational state distribution of the CO product. No v=1 CO is found and the rotational temperature is 1300 +/- 90 K. The reaction coordinate a t the transition state implies that the CO product is vibrationally cold an d rotationally hot. This conclusion, which requires quantum dynamics calcul ations to confirm definitively, does agree with and aids in explaining the experimental results. (C) 2001 American Institute of Physics.