Dynamics of hydrogen-bonded liquids confined to mesopores: A dielectric and neutron spectroscopy study

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Abstract
In this paper we present and discuss experimental results on molecular mobility in propylene glycol and its three oligomers confined to the ∼100 Å pores of a controlled porous glass. The objective is to elucidate the finite size effects on the dynamics of hydrogen‐bonded liquids of different molecular weights but identical chemical composition. The methods of dielectric and neutron spectroscopy have been employed to investigate both the low‐ and high‐frequency features as a function of temperature. We find that all fluids in pores separate into two distinct liquid phases. (i) molecules physisorbed at the surface which exhibit a dramatic frustration of their mobility related to a substantial positive shift of the glass transition temperature Tg by up to ΔTg≊+47 K; and (ii) relatively ‘‘free’’ molecules in the inner pore space subject to only moderate retardation of the α and normal mode relaxation and substantial broadening of the distribution of relaxation times. The shift in Tg for the α process with ΔTg≊+5 K is maximal for the monomer liquid and gradually diminishes with increasing molecular weight or decreasing intermolecular hydrogen bonding. The inelastic neutron spectrum of confined propylene glycol shows the boson peak as expected in bulk strong and intermediate glass formers in the vicinity of Tg. This effect can be attributed to the finite‐size induced crossover from long wave vibrations characteristic of a continuous medium to localized vibrations in a confined geometry.

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