After an initial 20 ps structural relaxation (NVT), the systems were equilibrated in an isobaricisothermal (NPT) ensemble for 400 ps to find a suitable box volume, and then thermally equilibrated to a temperature of 300 K in a canonical (NVT) ensemble for 200 ps. This was followed by a 200 ps equilibration in the microcanonical (NVE) ensemble. The spherical nanoparticles were built with a radius of 20 Å and a lattice constant of 4.08 Å using nanoparticleBuilder, another OpenMD utility. Atoms were given velocities sampled from a Maxwell-Boltzmann distribution at 5 K, and the nanospheres underwent incremental structural relaxation at 5 K, 100 K, 200 K, and 300 K using normal thermostatting methods. Metallic structures were subsequently combined with the solvent (which was built using Packmol and another OpenMD utility ). The central gold atom at the center of each nanoparticle were given a large mass to anchor the particle to the origin and prevent drifting. Prior to sampling, the systems were simulated with a Langevin Hull integrator for 1 ns. After these equilibration steps, the distributions of citrate configurations were sampled every 20 ps over a 2 ns period (in the microcanonical ensemble for slab systems and using a Langevin Hull integrator for nanoparticle systems). Further details regarding the systems simulated in this work are shown in Table . All systems have similar citrate concentrations and water densities. We have adopted the categorization of citrate binding motifs from Chong et al. In the tall configuration, the citrate is bound to the gold surface solely through one terminal carboxylate. In the bridge configuration, the citrate is bound through both terminal carboxylates. The 0-arm, 1arm, and 2-arm configurations describe a citrate bound via either the central hydroxyl or central carboxylate (or both) along with zero, one, or two terminal carboxylates, respectively. A citrate is considered bound to the surface if an oxygen is within 3.5 Å of the gold surface. A visual representation of these configurations is shown in Figure .