Influence of the reactants rotational excitation on the H + D2(v = 0, j) reactivity

10 págs.; 10 figs.; 1 tab.; Special Issue: Dynamics of Molecular Collisions XXV: Fifty Years of Chemical Reaction DynamicsWe have analyzed the influence of the rotational excitation on the H + D(v = 0, j) reaction through quantum mechanical (QM) and quasiclassical trajectories (QCT) calculations at a wide range of total energies. The agreement between both types of calculations is excellent. We have found that the rotational excitation largely increases the reactivity at large values of the total energy. Such an increase cannot be attributed to a stereodynamical effect but to the existence of recrossing trajectories that become reactive as the target molecule gets rotationally excited. At low total energies, however, recrossing is not significant and the reactivity evolution is dominated by changes in the collision energy; the reactivity decreases with the collision energy as it shrinks the acceptance cone. When state-to-state results are considered, rotational excitation leads to cold products rovibrational distributions, so that most of the energy is released as recoil energy.The authors acknowledge funding by the Spanish Ministry of Science and Innovation (grant Consolider Ingenio 2010 CSD2009-00038). J.A., F.J.A. and P.G.J. acknowledge also funding by the Spanish Ministry of Economy and Competitiveness (grant CTQ2012-37404-C02), and V.J.H. acknowledges additional funding by the Spanish Ministry of Science and Innovation (FIS2013-48087-C2-1P) and by the European Research Council (ERC-2013-Syg-610256).Peer Reviewe