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, CH2CHCHO) at 157 nm in a molecular beam and of migration and elimination of hydrogen atoms in systems C3H4O and C3H3O using quantum-chemical calculations. Compared with the previous results of photodissociation of propenal at 193 nm, the major difference is that the C3H3O fragment present at the 193-nm photolysis disappears at the 157-nm photolysis whereas the C3H2O fragment absent at 193 nm appears at 157 nm. Optimized structures and harmonic vibrational frequencies of molecular species with gross formula C3H2-4O 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 C3H3O fragment observed in the photolysis of propenal at 193 nm is probably CHCCHOH ((2)A '') and/or CH2CCOH ((2)A '') produced from an intermediate hydroxyl propadiene (CH2CCHOH) following isomerization. Adiabatic and vertical ionization potentials of eight isomers of C3H3O and two isomers of C3H2O were calculated; CHCCHOH ((2)A '') and CH2CCOH ((2)A '') have ionization potentials in good agreement with the experimental value of similar to 7.4 eV. We also deduce that all the nascent C3H3O fragments from the photolysis of propenal at 157 nm spontaneously decompose mainly to C2H3 + CO and C3H2O + 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. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3613636]