Substantial breakdown of the hydrogen-bonding network, local density inhomogeneities and fluid-liquid structural transitions in supercritical octanol-1: A molecular dynamics investigation.

Abstract

Molecular dynamics simulations have been employed to explore the hydrogen-bonding structure and dynamics in supercritical octanol-1 at a near-critical temperature and up to high densities and pressures. A substantial breakdown of the hydrogen-bonding network when going from ambient-liquid to supercritical conditions is revealed. The fraction of the non-hydrogen bonded molecules significantly increases in supercritical octanol-1, and a substantial decrease in the intermittent hydrogen-bond lifetime is observed. This behavior is also reflected on the maximum local density augmentation, which is comparable to the values obtained for non-polar and non-hydrogen bonded fluids. The existence of a structural transition from an inhomogeneous fluid phase to a soft-liquid one at densities higher than 2.0 ρc is also revealed. At higher densities, a significant change in the reorientational relaxation process is observed, reflected on the significant increase in the ratio of the Legendre reorientational times τ1R/τ2R. The latter becomes much higher than the value predicted by the Debye model of diffusive reorientation and the corresponding ratio for ambient liquid octanol-1. The non-polar tail of octanol-1 under supercritical conditions reorients more slowly in comparison with the polar tail. Interestingly, the opposite behavior is observed for the ambient liquid, further verifying the strong effect of the breakdown of the hydrogen bonding network on the properties of supercritical octanol-1. In accordance with the above-mentioned findings, the static dielectric constant of supercritical octanol-1 is very low even at high densities and pressures, comparable to the values obtained for non-polar and non-hydrogen bonded fluids.