Dynamics of a wetting liquid in nanopores: An optical Kerr effect study of the dynamics of acetonitrile confined in sol-gel glasses

The orientational dynamics of acetonitrile and acetonitrile-d3 confined in nanoporous glasses have been studied using optical Kerr effect spectroscopy. The decays can be fit to the sum of three exponentials, the fastest of which corresponds to relaxation of bulk-like liquid. We present evidence that the intermediate exponential arises from the exchange of molecules bound to the pore surfaces into the bulk liquid, whereas the slowest exponential corresponds to surface relaxation. A comparison to nuclear magnetic resonance data demonstrates that the liquid at the pore surfaces is more highly ordered than that in the bulk. Surface-modification studies demonstrate that hydrogen bonding is responsible for the extreme inhibition of dynamics at the pore surfaces.