Theoretische Chemie, Department Chemie, Technische Universität München, 85748 Garching, Germany.
J Chem Phys. 2011 Aug 14;135(6):064504. doi: 10.1063/1.3624342.
The multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method is applied to simulate the quantum dynamics and thermal rate constant of the Azzouz-Borgis model of proton transfer in a polar solvent. To this end, the original atomistic potential is mapped to a system-bath model. Employing the flux correlation function formalism and importance sampling techniques, accurate quantum mechanical rate constants are obtained, which provide a benchmark for evaluating approximate approaches to study the quantum dynamics of condensed-phase chemical reactions. Furthermore, the validity of the mapping procedure is discussed based on the comparison of the classical dynamics of the original atomistic Azzouz-Borgis model and the mapped system-bath model.
多层多组态含时哈特里（ML-MCTDH）方法被应用于模拟在极性溶剂中质子转移的 Azzouz-Borgis 模型的量子动力学和热速率常数。为此，原始原子势被映射到体系-溶剂模型。通过通量关联函数形式和重要抽样技术，得到了精确的量子力学速率常数，为评估研究凝聚相化学反应量子动力学的近似方法提供了基准。此外，基于原始原子 Azzouz-Borgis 模型的经典动力学与映射的体系-溶剂模型的比较，讨论了映射过程的有效性。
