Polarization of the gold surface appears to slightly decrease the fraction of bound citrate as well as the gold surface coverage. In order to bind to the gold surface, a citrate molecule must compete with water molecules near the surface. The SPC/E oxygen is more negatively charged than the citrate carboxylate oxygens and the citrate hydroxyl oxygen. When using a polarizable metal, the gold surface will respond to higher oxygen charges with a larger positive surface charge, yielding a stronger binding with SPC/E water. This likely explains the decrease in citrate binding when the gold surface is polarizable. Citrate binding preferences are shown in Figure . When the gold surface is polarized, there is very little difference in binding across nanostructure geometries. For the slab systems, the 0-arm configuration is most heavily favored. For the nanoparticle systems, the percentage of 0-arm and 1-arm configurations are nearly identical. Therefore, we can conclude that a significant number of bound citrates position themselves with the binding central groups perpendicular to the plane of the gold surface and the terminal carboxylates. Since the citrate molecules are likely parallel to the plane of the gold surface, the increased curvature of the nanoparticle would result in a comparatively greater percentage of citrates bound in the 1-arm configuration. This behavior also reduces the 2-arm and bridge binding, in which both terminal carboxylate groups bend toward the surface. As modeled here, the citrate molecules are too rigid for this degree of bending to occur to a significant degree. Since the 0-arm, 1-arm, and 2-arm configurations can be bound by one or both of the central groups, the distributions of these sub-configurations were also determined and can be found in Figure in the SI. When the citrates were simulated using interaction parameters from Wright et al., we did not observe any binding to the gold surface. This is almost certainly due to the larger Lennard-Jones radii of the citrate oxygen atoms in that model. Citrate binding is in direct competition with water binding to the surface, and small changes in σ Au-O can dramatically alter the relative binding energies of the two models.