The Cl + H2 --> HCl + H reaction induced by IR + UV irradiation of Cl2 in solid para-H2: quantum model simulation.

Recent experimental investigations by the group of D. T. Anderson (Kettwich, S. C.; Raston, P. L.; Anderson, D. T. J. Phys. Chem. A 2009, 113, DOI 10.1021/jp811206a) show that the reaction Cl + H(2) --> HCl + H in the para-H(2) crystal can be induced by infrared (IR) + ultraviolet (UV) coirradiations causing vibrational pre-excitation of the molecular reactant, H(2)(v=1), and generation of the atomic reactant, Cl((2)P(3/2)), by near-resonant photodissociation of a matrix-isolated Cl(2) molecule in the C (1)Pi(u) state, respectively. The corresponding reaction probability P(v=1) for the reactants Cl + H(2)(v=1) is approximately 0.15; this is approximately 25 times larger than P(v=0) for Cl + H(2)(v=0) (as initiated by pure UV irradiation). We present a simple three-step quantum model which accounts for some important parts of the experimental results and allows predictions for other scenarios, for example, UV photodissociation of the Cl(2) molecule by a laser pulse. The first step, vibrational pre-excitation of H(2), yields the molecular initial state which is described using the Einstein model of the para-H(2) crystal. The second step, photodissociation of Cl(2), generates the Cl((2)P(3/2)) atom approaching H(2)(v=1). In the third step, Cl reacts with H(2)(v=1) much more efficiently than with H(2)(v=0) close to threshold. The ultrashort time domains (approximately 100 fs) of steps 2 plus 3 support one- and then two-dimensional models of photodissociation of Cl(2) by short laser pulses and of the subsequent reaction of the system Cl-H-H embedded in frozen environments. The widths of the corresponding wave function describing the translational motion of the reactants is revealed as a significant parameter which is determined not only by the duration of the laser pulse but, even more importantly, by the width of the Gaussian-type distribution of the center of mass of the H(2) molecule in its Einstein cell. As a consequence, the resulting P(v) are quite robust versus variations of the UV pulse durations, allowing extrapolations to continuous wave irradiation. Quantum dynamics simulations of the reaction reveal that the experimental results are due to energetic and dynamical effects.