Structure of liquid and glassy methanol confined in cylindrical pores

J Chem Phys. 2004 Jul 15;121(3):1466-73. doi: 10.1063/1.1762872.

Abstract

We present a neutron scattering analysis of the density and the static structure factor of confined methanol at various temperatures. Confinement is performed in the cylindrical pores of MCM-41 silicates with pore diameters D=24 and 35 A. A change of the thermal expansivity of confined methanol at low temperature is the signature of a glass transition, which occurs at higher temperature for the smallest pore. This is evidence of a surface induced slowing down of the dynamics of the fluid. The structure factor presents a systematic evolution with the pore diameter, which has been analyzed in terms of excluded volume effects and fluid-matrix cross correlation. Conversely to the case of Van der Waals fluids, it shows that stronger fluid-matrix correlations must be invoked most probably in relation with the H-bonding character of both methanol and silicate surface.