Treatment of the K-quantum number in unimolecular reaction theory: insights from product correlations.

The connection between the K-quantum number and product correlations in the barrierless unimolecular dissociation of symmetric-top molecules is explored to establish a qualitative diagnostic for the treatment of the K-rotor dynamics in unimolecular reaction theory. We find that fragment scalar and vector correlations can provide guidance in this matter, and the photodissociation dynamics of thermal NCNO to form CN and NO at several dissociation wavelengths are presented to demonstrate the utility of this approach. The "goodness" of the K-quantum number can be related to the amount of energy in the conserved vibrational modes at the inner transition state. On the basis of measured correlated vibrational distributions, the K-quantum number is found to be approximately conserved at the inner transition state for the photodissociation of NCNO at 514, 520, and 526 nm. The methodology, involving a comparison of product distributions from the photodissociation of jet and thermal ensembles at identical wavelengths, is general and may be applied to previously studied systems that dissociate along barrierless potential energy surfaces, CF(3)NO and CH(2)CO. In addition, vector correlations serve as a means to probe the K-mixing at the outer transition state, and measured v-j correlations in the photodissociation of thermal NCNO are presented.