We perform atomistic and mesoscale simulations to explain the origin of experimentally observed stripelike patterns formed by immiscible ligands coadsorbed on the surfaces of gold and silver nanoparticles. We show that when the conformational entropy gained via this morphology is sufficient, microphase-separated stripelike patterns form. When the entropic gain is not sufficient, we instead predict bulk phase-separated Janus particles. We also show corroborating experimental results that confirm our simulational predictions that stripes form on flat surfaces as well as on curved nanoparticle surfaces.

Natural surfaces are often structured with nanometre-scale domains, yet a framework providing a quantitative understanding of how nanostructure affects interfacial energy, gamma(SL), is lacking. Conventional continuum thermodynamics treats gamma(SL) solely as a function of average composition, ignoring structure. Here we show that, when a surface has domains commensurate in size with solvent molecules, gamma(SL) is determined not only by its average composition but also by a structural component that causes gamma(SL) to deviate from the continuum prediction by a substantial amount, as much as 20% in our system. By contrasting surfaces coated with either molecular- (<2 nm) or larger-scale domains (>5 nm), we find that whereas the latter surfaces have the expected linear dependence of gamma(SL) on surface composition, the former show a markedly different non-monotonic trend. Molecular dynamics simulations show how the organization of the solvent molecules at the interface is controlled by the nanostructured surface, which in turn appreciably modifies gamma(SL).

A combination of immiscible molecules in the ligand shell of a gold nanoparticle (NP) has been shown to phase separate into a rippled structure; this phase separation can be used to direct the assembly of the NPs into chains. Here we demonstrate that only NPs within a certain size range can form chains, and we conclude that the rippled morphology of the ligand shell also exists only within that given size range. We corroborate this result with simulations of the ligand arrangement on NPs of various sizes.

We investigate the use of mixed self-assembled monolayers (SAMs) for creating nanoscale striped patterns on nanowires and nanorods. Our simulations predict that SAMs comprised of an equal composition of length-mismatched, thermodynamically incompatible surfactants adsorbed on nanowire surfaces self-organize into equilibrium stripes of alternating composition always perpendicular, rather than parallel, to the nanowire axis. We support the simulation results with preliminary experimental investigations of gold nanorods coated with binary mixtures of ligand molecules, which show stripes roughly perpendicular to the rod axis in all cases.

We describe a simple method based on postadsorption substrate stress induction to modify and control nanoscale phase-separated patterns formed in self-assembled monolayers. We show using mesoscale computer simulations and experiments that this method helps quickly progress a kinetically arrested patchy pattern into the equilibrium striped pattern, which is otherwise difficult to access. This work also establishes the role of curvature in the formation of aligned stripes several molecules wide on spherical nanoparticles and nanocylinders.