Dynamics of the O(1D)+D2 reaction: a comparison between crossed molecular beam experiments and quasiclassical trajectory calculations on the lowest three potential energy surfaces

This paper describes crossed beam experiments and quasiclassical trajectory (QCT) calculations for the ‘insertion’ reaction O(1D)þD2 at a collision energy (Ec¼25.9 kJ mol1) much higher than the calculated barrier (s8.4 kJ mol1) for the competitive ‘abstraction’ mechanism, which takes place along the excited state potential energy surfaces (PES). Adiabatic QCT calculations were carried out on the ground 11A0 and first excited 11A00 PESs developed by Dobbyn and Knowles. Non-adiabatic contributions from the excited 21A0 PES to the reaction were considered by means of a trajectory surface hopping method. QCT calculations were also performed at Ec¼22.2 kJ mol1 to compare with previous experimental results. Excellent agreement was found between experiment and QCT predictions at Ec¼22.2 kJ mol1, while at the higher Ec of 25.9 kJ mol1 only a qualitative agreement was noted. In all cases, the comparison was significantly improved with respect to QCT calculations on a previous version of the ground state PES.