Quantum and quasiclassical state-selected O(1D)+HF reaction dynamics and kinetics on a new MRCI ground singlet potential energy surface

About 20 000 MRCI single point energies for the O(D-1) + HF -> F((2)p) + OH reaction have been calculated and fitted to obtain the ground (1)A' potential energy surface (PES). After successfully comparing with spectroscopic data related to the deep HOF molecular well the more demanding tests involving the whole surface with quasiclassical trajectory calculations (QCT)-first 'validated' by comparison to quantum (wavepacket) results-were performed. A reasonable agreement of the room temperature reaction rate coefficient with the more reliable existing kinetic experiment as well as the way the rate coefficient, k(T), changes with temperature and the shape of the products angular distribution in detailed dynamical calculations are reasonable guarantees of the PES quality. (c) 2007 Elsevier B.V. All rights reserved.