In particular, for Fig. , PMMA, N66, PVA, and PVA † are well characterized by four time constants in terms of the multiexponential relaxation of interfacial water whereas all other polymers are sufficiently described by three. Notably, the first three time constants (i = 1, 2, and 3) associated with "fast" relaxation modes are effectively equivalent across all polymers; however, PMMA, N66, PVA, and PVA † exhibit a fourth slower relaxation mode. Similarly for the same set of PMMA, N66, PVA, and PVA † , rotational decorrelation associated with water in L 1 is significantly longer compared to that in other layers whereas there are not striking differences between rotational relaxation times in other polymer-water systems. Between these two groups, the polymers that exhibit longer relaxation times are exclusively those that can participate in hydrogen bonding with water. This suggests that the additional slow mode in Fig. or the generally longer mean-relaxation time in Fig. likely arises due to specific hydrogen-bonding interactions, and the balance of behavior is perhaps more generic water dynamics with minor perturbations based on polymer chemistry.