We begin by considering the impact of polymer chemistry on contact angle at the polymerwater-air interface (Fig. ) in our MD simulations. Fig. shows that the simulated contact angle θ sim readily distinguishes most simulated polymer surfaces. Generally θ sim increases with the number of water molecules N w in the system; this is expected by consideration of the modified Young equation 115 (i.e., cos(θ) = cos(θ 0 ) -τ /(γa) where θ is a measured contact angle, θ 0 is the macroscopic contact angle, τ is the line tension, γ is the water-vapor surface tension, and a is the base radius of the droplet) since the radius will increase with increasing N w . The relative ordering of polymers based on θ sim is relatively robust, although PMMA and N66 are nearly equal at low N w as are PTFE and PE; PE and PVC are quite comparable over intermediate N w . The data possess overall small statistical errors, suggesting that the indepently generated surfaces exhibit similar geometries and compositions on lengthscales commensurate with droplet size. Given that measurements at the largest N w = 2000 provide clear distinction amongst the various surfaces, these are compared to aggregated experimental measurements in Fig. . The agreement between θ sim and θexp is good, particularly preserving the relative ordering of the various polymer surfaces. Prior work featuring similarly sized simulated water droplets found that the difference between simulated and macroscopic contact angles was less than four degrees, which is considerably smaller than both the statistical uncertainties associated with our simulations and the standard deviation across experiments. It should be noted that the experimental values are averages across potentially different preparation and measurement protocols, which can obfuscate specific comparisons. This may partly explain the disparity in results for PVA. We find that our amorphous PVA surface is particularly soft and vulnerable to water uptake, resulting in small or immeasurable contact angles. However, PVA is known to exhibit crystallinity and was prepared by powder-casting, 105 such that the simulated morphology may not be commensurate with that examined experimentally. Nevertheless, the MD simulations, which feature only a nanoscopic droplet, roughly recapitulate the same wetting behavior as represented by experimental contact angles. We next examine two less conventional metrics for nanoscale hydrophobicity: a dehydration energy β∆f σ and the volume-adjusted excess chemical potential of water β μex w (N w ). The motivation underlying these metrics is that water affinity or repulsion with respect to the environment generated by a polymer interface should be fundamentally captured by aspects of the system free energy. The metric β∆f σ essentially captures the minimum work required to displace a certain number of water molecules from the vicinity of a given polymer surface (per water molecule displaced); the expectation is that water on strongly hydrophobic surfaces would be quite easily displaced, resulting in lesser work compared to a surface that leads to strongly bound water. The metric β μex w (N w ) relates to the free energy (beyond ideal contributions) of adding one additional water molecule to a polymer-water system with N w water molecules already present; the expectation is that hydrophilic surfaces would generate favorable environments that would result in more negative chemical potentials. While contact angle can be readily measured via experiment, neither of these metrics would seem routinely accessible for direct comparison. to polymer chemistry and can distinguish the various surfaces (Fig. ). Using β μex w (N w )