Rotational state distributions of NH(<i>a</i> 1Δ) from HNCO photodissociation

Abstract

We have examined the photofragmentation HNCO→NH(a 1Δ)+CO using radiation at wavelengths shorter than 230 nm. Nascent NH(a 1Δ) shows relatively little rotational excitation, accounting for less than 12% of the energy in excess of the dissociation energy. The rotational state distributions evidence less population in high rotational states than predicted by statistical theories but more than expected on the basis of a simple impulsive dissociation. A semiclassical impulsive model that describes photoproduct rotation as developing during fragmentation successfully describes the rotational state distributions of NH(a 1Δ) produced by HNCO photodissociation over a wide range of wavelengths. The success of this model in describing the NH rotational state distributions and previously measured CO rotational state distributions suggests that the excited state potential energy surface may be repulsive with minima in HNC and NCO bond angles each near 120°.