Nonadiabatic Quantum Dynamics of Molecules Scattering from Metal Surfaces

Area of Science:

• Surface science
• Theoretical chemistry
• Quantum dynamics

Background:

• Nonadiabatic coupling between electrons and molecular motion causes energy loss in chemical surface dynamics.
• Accurately modeling these effects, especially quantum nuclear effects, presents a significant theoretical challenge.

Purpose of the Study:

• To develop and apply a theoretical approach for simulating molecule-surface scattering that includes all nonadiabatic and quantum nuclear effects.
• To provide a rigorous benchmark for evaluating existing mixed quantum-classical methods.

Main Methods:

• Utilized the hierarchical equations of motion (HEOM) approach combined with a matrix product state representation.
• Applied the method to the scattering of nitric oxide (NO) from a gold surface (Au(111)).

Main Results:

• The HEOM approach accurately captures the interplay between nonadiabatic and quantum nuclear effects in molecule-surface interactions.
• The study provides benchmark data for the NO/Au(111) system, validating the theoretical model.

Conclusions:

• The developed HEOM method offers an exact treatment of molecule-surface coupling, crucial for understanding energy dissipation mechanisms.
• Insights were gained into the performance of mixed quantum-classical methods, defining their suitable working regimes for surface dynamics.