hide
Free keywords:
Molecular dynamics, Path integral molecular dynamics, Classical mechanics, Reaction rate constants, Chemical reaction dynamics, Quantum effects, Instanton, Multi-configuration time-dependent Hartree
Abstract:
We investigate whether making the friction spatially dependent on the reaction coordinate introduces quantum effects into the thermal reaction rates for dissipative reactions. Quantum rates are calculated using the numerically exact multi-configuration time-dependent Hartree method, as well as the approximate ring-polymer molecular dynamics (RPMD), ring-polymer instanton methods, and classical molecular dynamics. By conducting simulations across a wide range of temperatures and friction strengths, we can identify the various regimes that govern the reactive dynamics. At high temperatures, in addition to the spatial-diffusion and energy-diffusion regimes predicted by Kramer’s rate theory, a (coherent) tunneling-dominated regime is identified at low friction. At low temperatures, incoherent tunneling dominates most of Kramer’s curve, except at very low friction, when coherent tunneling becomes dominant. Unlike in classical mechanics, the bath’s influence changes the equilibrium time-independent properties of the system, leading to a complex interplay between spatially dependent friction and nuclear quantum effects even at high temperatures. More specifically, a realistic friction profile can lead to an increase (or decrease) of the quantum (classical) rates with friction within the spatial-diffusion regime, showing that classical and quantum rates display qualitatively different behaviors. Except at very low frictions, we find that RPMD captures most of the quantum effects in the thermal reaction rates.
