Measuring and modelling mechanochemical reaction kinetics.

Area of Science:

• Surface science
• Computational chemistry
• Materials science

Background:

• Mechanochemistry involves chemical reactions initiated by mechanical force.
• Understanding the kinetics of mechanochemical reactions is crucial for material design and process optimization.
• Methyl thiolate species on metal surfaces are relevant in catalysis and materials functionalization.

Purpose of the Study:

• To investigate the mechanochemical decomposition of methyl thiolate species on a Cu(100) surface using computational methods.
• To compare theoretical predictions with experimental measurements of reaction rates.
• To develop analytical models for mechanochemical reaction kinetics.

Main Methods:

• Quasi-static density functional theory (DFT) calculations were employed.
• Simulations focused on methyl thiolate species adsorbed on a Cu(100) surface.
• Comparison with experimental data obtained using atomic force microscopy (AFM) in ultrahigh vacuum.

Main Results:

• DFT calculations accurately reproduced the experimentally measured normal-stress dependent rates of mechanochemical decomposition.
• The study validated the predictive power of DFT for mechanochemical processes.
• A strong correlation between theoretical and experimental kinetic data was observed.

Conclusions:

• Quasi-static DFT is a reliable tool for modeling mechanochemical decomposition rates.
• The findings facilitate the development of precise analytical models for mechanochemical reaction kinetics.
• This work provides insights into the fundamental mechanisms of stress-induced chemical transformations on surfaces.