Vibrational State-to-State Scattering of Water from Cu(111): Comparison of Quantum and Quasiclassical Methods with Normal Mode and Adiabatic Switching Sampling
Liang Zhang, Jialu Chen, Bin Jiang
Abstract
Vibrational energy transfer of a polyatomic molecule upon collision at a solid surface is of fundamental importance in surface chemistry. As a full quantum treatment of this process is extremely challenging in theory, affordable approximate methods need to be developed and validated. Herein, we report a comparative investigation of vibrational state-to-state scattering dynamics of water from a flat Cu(111) surface, with quasiclassical trajectory (QCT) and fully coupled quantum dynamics (QD) methods, based on a first-principles-determined potential energy surface. In particular, the initial conditions of quasiclassical trajectories are generated by either standard normal mode (NM) sampling or the more rigorous semiclassical adiabatic switching (AS) sampling, while the final state distributions are obtained with either the standard histogram binning or the energy-based Gaussian binning (1GB) schemes. Through systematic comparison of state-to-state scattering probabilities of H2O/HOD from Cu(111) obtained by various QCT implementations with the benchmark QD results, we find that the AS sampling moderately outperforms the NM sampling, and the 1GB scheme is most crucial to yield reliable state-to-state scattering probabilities. Encouragingly, the QCT method with the AS sampling and 1GB can largely capture the mode-specific vibrational energy transfer in this polyatomic molecule–surface scattering process. Our results in this representative system of polyatomic scattering from metal surfaces can shed valuable light on the applicability of the QCT method in describing the state-to-state vibrational energy transfer in gas phase and gas–surface systems involving polyatomic molecules.