Uncovering reaction sequences on surfaces through graphical methods.

Area of Science:

• Computational Chemistry
• Surface Science
• Chemical Reaction Engineering

Background:

• Predicting reaction mechanisms on surfaces is crucial for catalysis and materials science.
• Existing methods often require prior knowledge of reaction intermediates, limiting exploration.
• Understanding complex surface reactions, like atomic layer deposition, remains challenging.

Purpose of the Study:

• Introduce S-ZStruct, a surface-reaction oriented implementation of the ZStruct graph-based model.
• Enable the generation of reaction pathways for unimolecular and bimolecular surface reactions.
• Explore diverse binding sites and adsorption orientations in surface chemistry.

Main Methods:

• Developed S-ZStruct for surface-reaction pathway generation.
• Applied S-ZStruct to unimolecular dissociation of propanoic acid.
• Utilized S-ZStruct to investigate the atomic layer deposition of TiN on Si(100).

Main Results:

• Discovered multiple unique reaction pathways with varying activation energies for propanoic acid dissociation.
• Identified a novel mechanism for Ti(iv) to Ti(iii) reduction in TiN ALD via β-hydride transfer.
• S-ZStruct successfully sampled different binding sites and adsorption orientations.

Conclusions:

• S-ZStruct is a powerful tool for exploring surface chemistry.
• The model facilitates the discovery of unknown reaction mechanisms.
• This approach enables advancements in understanding and designing surface-based chemical processes.