Insights into mechanistic photodissociation of chloroacetone from a combination of electronic structure calculation and molecular dynamics simulation

Abstract

The stationary and intersection structures on the S(0) and S(1) potential energy surfaces of CH(3)COCH(2)Cl have been determined by the CAS(10,8)/cc-pVDZ optimizations and their relative energies are refined by the CASPT2//CAS(10,8)/cc-pVDZ single-point calculations. Non-adiabatic molecular dynamics simulations were performed on the basis of the state-averaged CAS(10,8)/cc-pVDZ calculated energies, energy gradients, and Hessian matrix for the S(0) and S(1) states. It is found that the features of the S(1) potential energy surface and non-adiabatic effect control the selectivity of the two α-C-C bond fissions, which provides a reasonable explanation why one α-C-C bond was observed as a primary channel and the other is ruled out even if CH(3)COCH(2)Cl is excited at 193 nm. The β-C-Cl fission is determined to be a dominant channel once the CH(3)COCH(2)Cl molecule is excited to the S(1) state and the β-C-Cl:α-C-C branching ratio is estimated by the RRKM rate theory to be 15:1 at 193 nm, which is overestimated in comparison with the value of ~11:1 inferred experimentally. The present calculation reveals that the α-C-C fission might take place in the ground electronic state as a result of the S(1) → S(0) internal conversion upon photolysis at 308 nm. However, the measured kinetic energy distributions of the α-C-C fission products suggest that the fission does not involve internal conversion to the ground state. To solve this issue, we need to perform non-adiabatic quantum dynamics simulation on accurate S(0), S(1), and S(2) potential energy surfaces, which is still a challenging task currently.