Molecular dynamics simulation of nanoconfined glycerol

Rémi Busselez (1) , Ronan Lefort (1) , Qing Ji (1) , Frederic Affouard (2) , Denis Morineau (1)

1 IPR - Institut de Physique de Rennes
2 LDSMM - Laboratoire de dynamique et structure des matériaux moléculaires

We present results from molecular dynamics simulations of liquid glycerol confined in a realistic model of a cylindrical silica nanopore. The influence of the hydrophilic surface and the geometrical confinement on the structure, hydrogen-bond lifetime, rotational and translational molecular dynamics are analysed. Layering and dynamical heterogeneities are induced by confinement. These features share some similarities with previous observations in simpler van der Waals glass-forming liquids. In addition, the specificity of glycerol as an associated liquid shows up in confinement by the formation of interfacial hydrogen bonds and some modifications of the in-pore hydrogen-bonding network. Confinement is also seen to influence the relaxation dynamics and the glassy behaviour in the supercooled state. These phenomena revealed by molecular simulation are important inputs for a better understanding of the many recent experimental results on confined glycerol and more generally for the possible manipulation of associated liquids in porous or fluidic devices.

Rémi Busselez, Ronan Lefort, Qing Ji, Frederic Affouard, Denis Morineau. Molecular dynamics simulation of nanoconfined glycerol. Physical Chemistry Chemical Physics, 2009, 11 (47), pp.11127-33. ⟨10.1039/b911859d⟩. ⟨hal-00665708⟩