Having established the hydrophobic ordering of the polymer surfaces, we now seek to understand the molecular physics that give rise to these otherwise coarse characterizations. A ). The relaxation dynamics in PTFE, PE, PE * , PVC, PVC * , and N66 * are characterized by three time constants, while the remaining polymers (highlighted by gray boxes) are described by four. 'NC' denotes 'not calculated.' (b) Characteristic relaxation times τk,rot for rotational diffusion of water molecules relative to the water-polymer interface; see Eqs. ( ) and (9). Analysis is spatially resolved based on the initial position of a water molecule in one of four layers of increasing distance from the water-polymer interface. For a given polymer, data is arranged left-to-right in order of increasing distance from the interface. (c) Correlation between characteristic relaxation times and the dehydration free energy β∆f σ . In all panels, error bars reflect statistical uncertainties reported as the standard error of the mean. guiding hypothesis is that the strength of polymer-water interactions, which relates to the surface hydrophobicity, will manifest in measurably discernible dynamics of water in proximity to the polymer-water interface; prior work has established that disparate translational and rotational dynamics of water can arise in the vicinity of solutes and interfaces, depending on whether they are viewed as hydrophilic or hydrophobic. Figs. demonstrate that interfacial water dynamics indeed vary dramatically based on polymer surface chemistry. Fig. specifically examines the residence time of water nearby the polymer-water interface, while Fig. instead examines the timescale for rotational decorrelation of water as a function of distance from the polymer-water interface. Both analyses suggest that the studied polymers can be qualitatively separated into two groups.