Quasiclassical trajectory calculations of CD3CHO dissociation to CD2H + DCO on a global potential energy surface

Abstract

We present a quasiclassical trajectory study of the photodissociation of CD3CHO based on a global ab initio-based potential energy surface. Calculations are performed at the total energy corresponding to the photolysis wavelength of 280[Formula: see text]nm. In addition to the major radical and molecular products, CD[Formula: see text] and CD3H [Formula: see text] CO, respectively, this paper focuses on the unusual radical channel CD2H [Formula: see text] DCO, which requires a D/H exchange process before the conventional C–C bond cleavage. Five D/H exchange mechanisms are reported, which are related to the isomerizations from acetaldehyde to vinyl alcohol and back, to oxirane and back, and to the intermediate (CD–CHD–OD) and back. These D/H exchange mechanisms are in good agreement with the experimental findings [Heazlewood BR, Maccarone AT, Andrews DU, Osborn DL, Harding LB, Klippenstein SJ, Jordan MJT, Kable SH, Nat Chem 3:443, 2011].