Resonant versus off-resonant quantum reaction dynamics in quantum solids: Model simulations for Cl+H2→ClH2∗→HCl+H in solid para-hydrogen

Previous quantum dynamical investigations of resonant versus off-resonant reactivity are extended from the gas phase to a quantum solid, using the simple model of Korolkov et al. [M.V. Korolkov, J. Manz, A. Schild, J. Phys. Chem. A 113 (2009) 7630] for the title reaction. Systematic empirical simulations discover that the different reaction mechanisms cause formations of the products with different “universal” i.e., exponential versus error-function type time evolutions, respectively. The wavepacket dynamics suggests that rich additional patterns of the time-dependent yields are caused by interferences of resonant plus non-resonant components. At long times, the resonance remains as exclusive source feeding product formation. By analogy with work of Eli Pollak for resonances in the gas phase, the resonance wavefunctions correspond to unstable classical periodic orbits describing hydrogen transfer Cl·H2∗⇋ClH·H∗ in the resonant collision complex.