Ab Initio Kinetics for the Unimolecular Reaction C6H5OH → CO + C5H6

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2006-02, Vol.110 (4), p.1672-1677
• Main Authors: Xu, Z. F, Lin, M. C
• Format: Article
• Language: English
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp055241d

The unimolecular decomposition of C6H5OH on its singlet-state potential energy surface has been studied at the G2M//B3LYP/6-311G(d,p) level of theory. The result shows that the most favorable reaction channel involves the isomerization and decomposition of phenol via 2,4-cyclohexadienone and other low-lying isomers prior to the fragmentation process, producing cyclo-C5H6 + CO as major products, supporting the earlier assumption of the important role of the 2,4-cyclohexadienone intermediate. The rate constant predicted by the microcanonical RRKM theory in the temperature range 800−2000 K at 1 Torr − 100 atm of Ar pressure for CO production agrees very well with available experimental data in the temperature range studied. The rate constants for the production of CO and the H atom by O−H dissociation at atmospheric Ar pressure can be represented by k CO = 8.62 × 1015 T -0.61 exp(−37 300/T) s-1 and k H = 1.01 × 1071 T -15.92 exp(−62 800/T) s-1. The latter process is strongly P-dependent above 1000 K; its high- and low-pressure limits are given.