Release Time:2019-03-13  Hits:

Indexed by: Journal Article

Date of Publication: 2018-11-01

Journal: JOURNAL OF THEORETICAL & COMPUTATIONAL CHEMISTRY

Included Journals: Scopus、SCIE

Volume: 17

Issue: 7

ISSN: 0219-6336

Key Words: Isomerization; acetaldehyde; photodissociaiton; quasiclassical trajectory

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 nm. In addition to the major radical and molecular products, CD3HCO and CD3H + CO, respectively, this paper focuses on the unusual radical channel CD2HDCO, 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].