Pressure Dependence of the Boson Peak of Glassy Glycerol

The pressure dependence of the boson peak (BP) of glycerol, including its behavior across the liquid-glass transition, has been studied using Raman scattering. A significant increase of the BP frequency was observed with pressure up to 11 GPa at room temperature. The pressure dependence of BP frequency ν_BP is proportional to (1+P/P₀)^1/3, where P and P₀ are the pressure and a constant, respectively, consistent with a soft potential model. The characteristic length of medium range order is close in size to a cyclic trimer of glycerol molecules, as predicted by the medium range order of a BP excitation using molecular dynamics simulations, and the pressure dependence of a characteristic medium range order is nearly constant. The pressure induced structural changes in glycerol can be understood in terms of the shrinkage of voids with cyclic trimers persisting to at least 11 GPa. Pressure dependence of the intermolecular O-H stretching mode indicates that the intermolecular hydrogen bond distances gradually decrease up to the glass transition pressure of ∼5 GPa and become nearly constant in the glassy state, indicating the disappearance of free volume in the dense glass.