Issue 12, 2014

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

Abstract

The 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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
29 Jul 2014
Accepted
22 Aug 2014
First published
22 Aug 2014

Chem. Sci., 2014,5, 4633-4638

Author version available

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

K. L. K. Lee, M. S. Quinn, A. T. Maccarone, K. Nauta, P. L. Houston, S. A. Reid, M. J. T. Jordan and S. H. Kable, Chem. Sci., 2014, 5, 4633 DOI: 10.1039/C4SC02266A

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