Ring Polymer Molecular Dynamics in Gas-Surface Reactions: Inclusion of Quantum Effects Made Simple

Accurately modeling gas-surface collision dynamics presents a great challenge for theory, especially in the low-energy (or temperature) regime where quantum effects are important. Here, a path integral-based nonequilibrium ring polymer molecular dynamics (NE-RPMD) approach is adapted to calculate dissociative initial sticking probabilities (S₀) of H₂ on Cu(111) and D₂O on Ni(111), revealing the distinct quantum nature in the two benchmark surface reactions. NE-RPMD successfully captures quantum tunneling in H₂ dissociation at very low energies, where the quasi-classical trajectory (QCT) method suddenly fails. Additionally, QCT substantially overestimates S₀ of D₂O because of severe zero point energy (ZPE) leakage, even at collision energies greater than the ZPE-corrected barrier. Instead, NE-RPMD predicts S₀ values of D₂O in much improved agreement with reference results obtained by the quantum wavepacket method with reasonable corrections of the thermal contribution. Our results suggest NE-RPMD as a promising approach to model quantum effects in gas-surface reactions.