Mechanism of Ostwald Ripening in 2D Physisorbed Assemblies at Molecular Time and Length Scale by Molecular Dynamics Simulations.

Ostwald ripening can improve the long-range order of self-assembled monolayers by the growth of large domains and disassembly of smaller ones. Here, coarse-grained molecular dynamics simulations are used to study the dynamics of the stable assembly and the coarsening of defects of physisorbed monolayers of long-chain functionalized alkanes. Our results show that the partial desorption from the surface of one or more adsorbent molecules is the essential process that allows other adsorbent molecules to rearrange on the surface and thereby improve alignment. We also show that the ripening process is faster at higher temperature because the rate of partial desorption is higher.