Two roaming pathways in the photolysis of CH3CHO between 328 and 308 nm

Authors

Kin Long K. Lee, University of New South Wales
Mitchell S. Quinn, University of New South Wales
Alan T. Maccarone, University of SydneyFollow
Klaas Nauta, University of New South Wales
Paul L. Houston, Georgia Institute of Technology
Scott A. Reid, University of Sydney
Matthew Jordan, University of Newcastle
Scott H. Kable, University of New South Wales

RIS ID

95604

Publication Details

Lee, K. K., Quinn, M. S., Maccarone, A. T., Nauta, K., Houston, P. L., Reid, S. A., Jordan, M. J. T. & Kable, S. H. (2014). Two roaming pathways in the photolysis of CH3CHO between 328 and 308 nm. Chemical Science, 5 (12), 4633-4638.

Abstract

he correlated speed and rotational energy distributions of the CO fragment from photodissociation of CH3CHO have been measured at a range of wavelengths from 308 to 328 nm. The distributions are bimodal, showing low J, slow speed, and high J, fast speed components. The cold component disappears for λ > 325 nm. This threshold corresponds to C-H bond cleavage and we assign these CO products as arising from roaming of a H-atom about a CH3CO core. We attribute the hot component to CO formed through CH3-roaming. No evidence was observed for the presence of a transition state mechanism. This is the first time two distinct roaming channels have been observed from the same electronic state. The results support the growing understanding that roaming can be significant in chemical reactions and outweigh traditional pathways.