Vibrational dynamics of a glass forming liquid in nanoscopic confinement as probed by inelastic neutron scattering

Abstract

In this article we present incoherent inelastic neutron scattering results, as a function of temperature, on the vibrational dynamics of a glass-forming liquid, namely propylene glycol, confined to the ∼26 Å pores of a controlled porous glass. The aim is to elucidate the effects induced by surface interactions ( chemical traps) and geometrical restrictions ( physical traps) on the fast microscopic dynamics of hydrogen-bonded liquids. The most prominent effect is the appearance of the ‘boson peak’ in the vibrational spectra. It is ascribed to an excess density of vibrational states due to quasilocalized collective atomic vibrations induced by confinement. A destructuring effect on the transient aggregates with the highest degree of connectivity, promoted by PG in the bulk phase, is hypothesized under confinement as a consequence of interactions, via hydrogen bond, between the hydroxyl groups (OH) of the PG molecule and the active silanol groups (Si–OH) on the surface of the porous glass. Interfacial and/or finite-size effects are also found to give rise to a destructuring effect, under confinement, of the disordered Longitudinal Acoustic Mode, together with a broadening of the highest frequency torsional vibration and a stabilization, vs. T, of the internal CCO bending vibration.