Computationally enabling surface-hopping dynamics on the Anderson-Holstein Hamiltonian.

Area of Science:

• Computational Chemistry
• Surface Science
• Quantum Dynamics

Background:

• Electron-electron repulsion in molecules on metals is often simplified using mean-field approaches or ignored.
• These simplifications arise because accurately modeling electron interactions with a metal continuum is computationally intensive.

Purpose of the Study:

• To develop a novel algorithm for simulating the dynamics of molecules interacting with metal surfaces.
• To accurately account for electron-electron repulsion and quantum effects in these systems.

Main Methods:

• Propose an algorithm to selectively incorporate discretized metallic states into the Hamiltonian.
• Construct a constrained Hamiltonian enabling surface hopping dynamics.
• Benchmark the active space surface hopping algorithm against Marcus theory for the Anderson-Holstein Hamiltonian.

Main Results:

• The active space surface hopping algorithm demonstrates utility in simulating systems with significant electron correlation.
• The method effectively captures coherent quantum effects, which are missed by rate theory-based approaches.
• Benchmarking against Marcus theory validates the algorithm's accuracy for the Anderson-Holstein Hamiltonian.

Conclusions:

• The active space surface hopping algorithm provides a computationally tractable yet accurate method for studying molecule-metal surface dynamics.
• This approach enables the simulation of complex quantum phenomena in surface chemistry.
• The algorithm advances the study of electron correlation effects in molecular systems interacting with metals.