As a consequence of these interactions, the molecular motion of H 2 O molecules are strongly correlated in ways that depend on the size and surface chemistry of the surrounding pores. Although Ti-BEA, Ti-MFI, and Si-CDO zeolites all stabilize H 2 O molecules as oligomeric chains, the translational motion of H 2 O within the pores differs significantly among these frameworks and with the presence of (SiOH) x . Analysis of time-averaged spatial distributions from MD simulations (Section S4.2) show that H 2 O molecules can radially translate up to ~2.2 Å from the centerline of the Ti-BEA-F pores but only ~ 1 and 0.6 Å from the center of pores within Ti-MFI-F and Si-CDO-OH, respectively. Moreover, the space accessed by H 2 O molecules increases significantly with the addition of (SiOH) 4 . These changes in spatial and structural confinement of the chains of H 2 O molecules within these zeolites significantly affects the thermodynamic properties of these solvent structures (vide infra). The thermodynamic stability of hydrogen bonds between H 2 O molecules entrained within zeolites depend strongly on the shape and size of the solvent cluster. We measured IR spectra of H 2 O molecules in the bulk-fluid phase and within pores of hydrophilic and hydrophobic zeolite frameworks (FAU, BEA, MFI, CDO) as functions of temperature to interrogate the changes in enthalpy and entropy that result from the disruption of HBs within H 2 O structures in these distinct environments. Figure shows IR spectra of bulk H 2 O as a function of temperature (303 -343 K) possess ν(O-H) that systematically shift to higher wavenumbers with increasing temperature and shows a clear isosbestic point at 3345 cm -1 , which agrees with previously reported Raman and infrared spectra of H 2 O. The blue shift in ν(O-H) with temperature reflects a change in the populations of H 2 O that exist in one of the five hydrogen bonding configurations (vide supra). The change in enthalpy associated with disrupting a single hydrogen bond among H 2 O molecules (ΔH <HB> ) within the different pore environments was quantified via van't Hoff analysis of the changes in 〈𝑁〉 . In this analysis, the molar extinction coefficients for ν(O-H) of H 2 O within the various HB arrangements are assumed to be the same. The enthalpy change associated with disrupting a H 2 O molecule (ΔH HB ) is then determined by multiplying ΔH <HB> by 〈𝑁〉 , which describes the change in enthalpy associated with perturbing the average H 2 O molecule within a given environment (Section S2.3.1). The corresponding change in entropy due to breaking a hydrogen bond (ΔS HB ) was determined using statistical mechanics (i.e., comparing the populations of H 2 O in the varying bonding configurations; Section S2.3.1). 54 ). These values agree with literature values for the changes in enthalpy (~10 kJ mol -1 ) and entropy (~25 J (mol H 2 O) -1 K -1 ) associated with the disruption of hydrogen bonding interactions within bulk H 2 O. H 2 O within Ti-FAU form nearly three-dimensional structures that result in H 2 O molecules with <N HB > values only slightly less than that for bulk water (<N HB > = 3.3). As a result, values of ΔH HB for H 2 O entrained within Ti-FAU (~9 ± 2 kJ (mol H 2 O) -1 ) resemble that for bulk H 2 O. Within Ti-BEA and Ti-MFI, H 2 O appears to exist as oligomers (vide supra) that merge and gain additional HB at intersections within these three-dimensional pore networks, such that H 2 O molecules possess two to three hydrogen bonds, on average. Consequently, values of ΔH HB within Ti-BEA and Ti-MFI (~5 kJ (mol H 2 O) -1 ) are approximately half the value of those found in Ti-FAU and bulk H 2 O. Interestingly, the value of <N HB > for Si-CDO-OH is the lowest among all structures (<N HB > = 2.0) and ΔH HB approaches zero, because the vibrational spectra of H 2 O show negligible changes with increasing temperature. This behavior suggests that H 2 O oligomers within Si-CDO-OH access multiple configurations with similar energies (Section S2.4). We postulate that the disruption of individual HB between pairs of H 2 O molecules results in concomitant restructuring of the H 2 O oligomers to form HB with nearby (SiOH) x functions, which maintains a constant average of two HB and gives nearly equivalent interaction energies. This interpretation seems consistent with values of ΔH HB that do not depend on the density of (SiOH) x within a given framework despite the significant fraction of HB observed between H 2 O and (SiOH) 4 in simulations (Tables and). Comparisons among these measurements show that the intrinsic enthalpic stabilization afforded by a single hydrogen bond (i.e., values of ΔH <HB> ) does not depend on the topology or defect density of a zeolite, however, the entropy gained when a hydrogen bond cleaves depends strongly on the remaining number of hydrogen bonds to the H 2 O molecule.