Is the equilibrium composition of mechanochemical reactions predictable using computational chemistry?

Area of Science:

• Solid-state chemistry
• Computational materials science
• Mechanochemistry

Background:

• Solid-state mechanochemical reactions offer sustainable synthesis pathways.
• Predicting reaction outcomes computationally is crucial for rational design.

Purpose of the Study:

• To assess the capability of computational methods in predicting solid-state mechanochemical reaction equilibria.
• To evaluate crystal structure prediction and lattice energy calculations for aromatic disulfide metathesis.

Main Methods:

• Crystal structure prediction utilizing molecular electronic structure methods.
• Lattice energy calculations incorporating anisotropic atom-atom potentials.
• Analysis of base-catalyzed metathesis reactions in aromatic disulfides.

Main Results:

• Successfully located three out of six target crystal structures as global minima.
• Encountered challenges in predicting relative conformational energies due to density functional theory limitations.
• Overall reaction energy prediction remains difficult for current computational approaches.

Conclusions:

• Computational methods demonstrate potential for predicting solid-state reaction structures.
• Limitations in modeling intramolecular energies and overall reaction energetics require further refinement.
• The study provides a foundation for developing more accurate predictive tools in mechanochemistry.