Molecular-beam experiments for photodissociation of propenal at 157 nm and quantum-chemical calculations for migration and elimination of hydrogen atoms in systems C3H4O and C3H3O

We investigated the dynamics of photodissociation of propenal (acrolein, CH(2)CHCHO) at 157 nm in a molecular beam and of migration and elimination of hydrogen atoms in systems C(3)H(4)O and C(3)H(3)O using quantum-chemical calculations. Compared with the previous results of photodissociation of propenal at 193 nm, the major difference is that the C(3)H(3)O fragment present at the 193-nm photolysis disappears at the 157-nm photolysis whereas the C(3)H(2)O fragment absent at 193 nm appears at 157 nm. Optimized structures and harmonic vibrational frequencies of molecular species with gross formula C(3)H(2-4)O were computed at the level of B3LYP/6-311G(d,p) and total energies of those molecules at optimized structures were computed at the level of CCSD(T)/6-311+G(3df,2p). Based on the calculated potential-energy surfaces, we deduce that the C(3)H(3)O fragment observed in the photolysis of propenal at 193 nm is probably CHCCHOH ((2)A") and/or CH(2)CCOH ((2)A") produced from an intermediate hydroxyl propadiene (CH(2)CCHOH) following isomerization. Adiabatic and vertical ionization potentials of eight isomers of C(3)H(3)O and two isomers of C(3)H(2)O were calculated; CHCCHOH ((2)A") and CH(2)CCOH ((2)A") have ionization potentials in good agreement with the experimental value of ～7.4 eV. We also deduce that all the nascent C(3)H(3)O fragments from the photolysis of propenal at 157 nm spontaneously decompose mainly to C(2)H(3) + CO and C(3)H(2)O + H because of the large excitation energy. This work provides profound insight into the dynamics of migration and elimination of hydrogen atoms of propenal optically excited in the vacuum-ultraviolet region.