Theoretical study of isomerization and decomposition of propenal

We investigated the dynamics of isomerization and multi-channel dissociation of propenal (CH(2)CHCHO), methyl ketene (CH(3)CHCO), hydroxyl propadiene (CH(2)CH(2)CHOH), and hydroxyl cyclopropene (cyclic-C(3)H(3)-OH) in the ground potential-energy surface using quantum-chemical calculations. Optimized structures and vibrational frequencies of molecular species were computed with method B3LYP∕6-311G(d,p). Total energies of molecules at optimized structures were computed at the CCSD(T)∕6-311+G(3df,2p) level of theory. We established the potential-energy surface for decomposition to CH(2)CHCO + H, CH(2)CH + HCO, CH(2)CH(2)∕CH(3)CH + CO, CHCH∕CH(2)C + H(2)CO, CHCCHO∕CH(2)CCO + H(2), CHCH + CO + H(2), CH(3) + HCCO, CH(2)CCH + OH, and CH(2)CC∕cyclic-C(3)H(2) + H(2)O. Microcanonical rate coefficients of various reactions of trans-propenal with internal energies 148 and 182 kcal mol(-1) were calculated using Rice-Ramsperger-Kassel-Marcus and Variational transition state theories. Product branching ratios were derivable using numerical integration of kinetic master equations and the steady-state approximation. The concerted three-body dissociation of trans-propenal to fragments C(2)H(2) + CO + H(2) is the prevailing channel in present calculations. In contrast, C(3)H(3)O + H, C(2)H(3) + HCO and C(2)H(4) + CO were identified as major channels in the photolysis of trans-propenal. The discrepancy between calculations and experiments in product branching ratios indicates that the three major photodissociation channels occur mainly on an excited potential-energy surface whereas the other channels occur mainly on the ground potential-energy surface. This work provides profound insight in the mechanisms of isomerization and multichannel dissociation of the system C(3)H(4)O.