The structuring and adsorption of solvent at a solid surface is an important factor in the interfacial heat transfer and can have a large effect on thermal interface conductance. For solid spherical nanoparticles, Tascini et al. found that smaller nanoparticles with larger curvature had higher surface adsorption density , which coincided with the increases in G that they observed with the particle curvature. To determine if curvature dependent changes in solvent adsorption could explain the curvature dependence of the AuNP-water G, we examined the structuring and adsorption of water at the surfaces of nanoscale gold (Figure ). For each wetting condition, we first examined the equilibrium density profiles of gold and water at 300 K (i.e., no heating) (Figure ). In the moderate wetting case, the peak in the mass density corresponding to the adsorption layer was 1.7 g mL -1 for the AuNPs and 2.4 g mL -1 at the planar interface (Figure ), whereas in the poor wetting case it was 1.4 g mL -1 for all the gold structures (Figure ). In the absence of heating, the surface adsorption density, ϱ (Equation 8-9), increased linearly with the gold-water interface curvature (Figure ), regardless of the wetting strength. This result is consistent with the trends reported by Tascini et al. who observed an increase in surface adsorption density with interface curvature in simulations of spherical NPs immersed in a monoatomic fluid at various wetting strengths. To better understand the curvature dependence of water adsorption at the gold surfaces, we examined how the relative solvent-accessibility of the gold structures changed with interface curvature. Measures of solvent accessibility were developed in the context of proteins, as a metric to help quantify the role of hydration in protein structure, folding and binding. We computed the solvent accessible surface area, A SASA (see Section 4.3.5), of the initial configuration of each gold structure and normalized it relative to its surface area (A = πd 2 for spherical AuNPs and A = 2L x L y for the planar slab) to quantify the relative accessibility: A SASA /A. The relative accessibility A SASA /A increased linearly with the interface curvature (Figure ). Since A SASA effectively quantifies the maximum amount of water that can adhere at the gold surfaces independent of wetting strength and temperature/heating, the trend in A SASA /A suggests a geometric effect in which there is more space for water to adsorb at the curved gold surfaces. This effect explains why the more highly curved gold surfaces sustain higher ϱ in both the moderate and poor wetting conditions.