Facetted patchy particles through entropy-driven patterning of mixed ligand SAMS

TL;DR

This paper develops a microscopic theory and uses simulations to show how entropy-driven effects cause larger ligands to preferentially align along edges and vertices of faceted nanoparticles, revealing a new patterning mechanism.

Contribution

The study introduces a novel entropy-driven patterning mechanism for mixed ligand SAMs on faceted nanoparticles, supported by theoretical predictions and Monte Carlo simulations.

Findings

Larger ligands align along edges and vertices due to entropy effects.

The intrinsic conformational entropy stabilizes the edge-aligned phase.

Monte Carlo simulations confirm the theoretical predictions.

Abstract

We present a microscopic theory that describes the ordering of two distinct ligands on the surface of a faceted nanoparticle. The theory predicts that when one type of ligand is significantly bulkier than all others, the larger ligands preferentially align themselves along the edges and vertices of the nanoparticle. Monte Carlo simulations confirm these predictions. We show that the intrinsic conformational entropy of the ligands stabilizes this novel edge-aligned phase.