Accurate quantum-mechanical rate constants for a linear response Azzouz-Borgis proton transfer model employing the multilayer multiconfiguration time-dependent Hartree approach

摘要

The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is applied to sim-nulate the quantum dynamics and thermal rate constant of the Azzouz-Borgis model of proton transfernin a polar solvent. To this end, the original atomistic potential is mapped to a system-bath model. Em-nploying the flux correlation function formalism and importance sampling techniques, accurate quan-ntum mechanical rate constants are obtained, which provide a benchmark for evaluating approximatenapproaches to study the quantum dynamics of condensed-phase chemical reactions. Furthermore, thenvalidity of the mapping procedure is discussed based on the comparison of the classical dynamics ofnthe original atomistic Azzouz-Borgis model and the mapped system-bath model. © 2011 AmericannInstitute of Physics. [doi:10.1063/1.3624342]