Metadynamics simulations of calcite crystallization on self-assembled monolayers

Area of Science:

• Materials Science
• Computational Chemistry
• Surface Science

Background:

• Predicting crystal orientation on surfaces is crucial for materials design.
• Traditional methods require computationally expensive calculations or prior structural knowledge.

Purpose of the Study:

• To present a novel metadynamics simulation approach for predicting crystal orientation on self-assembled monolayers.
• To dynamically treat organic components and include explicit surface water without intensive calculations.

Main Methods:

• Application of advanced metadynamics simulations to direct crystallization simulations.
• Dynamic modeling of organic monolayers and explicit surface water.
• Simulation of calcite crystallization on alkanethiol-coated Au(111) surfaces.

Main Results:

• Successfully predicted crystal orientation without epitaxial constraints.
• Observed an odd-even effect in selectivity based on organic chain length.
• Identified a mutual control mechanism between organic and mineral components driving ordering.

Conclusions:

• Metadynamics simulations offer a powerful, computationally efficient method for predicting surface crystallization.
• The dynamic simulation approach accurately reproduces experimental observations, including odd-even effects.
• Understanding interfacial ordering dynamics is key to controlling crystal growth on surfaces.