Effects of pore size on water dynamics in mesoporous silica

Water confined in mesoporous silica plays a central role in its many uses ranging from gas sorption to nanoconfined chemical reactions. Here, the influence of pore diameter (2.5-5.4 nm) on water hydrogen bond (H-bond) dynamics in MCM41 and SBA15 mesoporous silicas is investigated using femtosecond infrared vibrational spectroscopy and molecular dynamics simulations on selenocyanate (SeCN^-) anions dissolved in the pores. As shown recently, SeCN^- spectral diffusion is a reliable probe of surrounding water H-bond structural motions. Additionally, the long CN stretch vibrational lifetime facilitates measurement of the full range of confined dynamics, which are much slower than in bulk water. The simulations shed light on quantitative details that are inaccessible from the spatially averaged observables. The dependence of SeCN^- orientational relaxation and that of spectral diffusion on the distance from the silica interface are quantitatively described with an exponential decay and a smoothed step-function, respectively. The distance-dependence of both quantities is found to be independent of the diameter of the pores, and the spatial distribution of SeCN^- is markedly non-uniform, reaching a maximum between the interface and the pore center. The results indicate that the commonly invoked two-state, or core-shell, model is a more appropriate description of spectral diffusion. Using these insights, we model the full time-dependence of the measured dynamics for all pore sizes and extract the "core" and "shell" dynamical correlation functions and SeCN^- spatial probability distributions. The results are critically compared to those for water confined in reverse micelles.