Chemically Accurate Simulation of a Polyatomic Molecule-Metal Surface Reaction

Area of Science:

• Computational Chemistry
• Surface Science
• Heterogeneous Catalysis

Background:

• Accurate modeling of polyatomic molecule reactions on metal surfaces is crucial for heterogeneous catalysis but lags behind gas-phase dynamics.
• Existing methods struggle with quantitative accuracy for complex molecules on metal surfaces.

Purpose of the Study:

• To extend the quantitative accuracy of computational modeling for reactions between polyatomic molecules and metal surfaces.
• To develop a computationally tractable method for simulating dissociation on transition metals.

Main Methods:

• Utilized the specific reaction parameter (SRP) approach within density functional theory (DFT).
• Integrated SRP-DFT with ab initio molecular dynamics (AIMD) for reaction simulations.
• Applied the method to CHD3 (deuterated methane) reactions on a Ni(111) surface.

Main Results:

• The SRP-AIMD method was fitted to supersonic beam experimental data for CHD3 + Ni(111).
• The developed functional accurately reproduced initial-state selected sticking measurements with chemical accuracy (within 4.2 kJ/mol).
• The computational scheme requires only semilocal exchange, enhancing tractability for transition metal systems.

Conclusions:

• The SRP-AIMD approach significantly advances the ability to model complex molecule-surface reactions.
• This method provides quantitative accuracy, extending capabilities beyond light molecules like H2.
• The computational efficiency makes it suitable for studying dissociation processes on transition metals.