Importance of orientational rearrangement during vitrification of hydrocarbons: dependence on molecular shape

Abstract

On the basis of Monte Carlo calculations of 2,2-dimethylpropane (neopentane), n-pentane, and 2,2-dimethylbutane (neohexane) at several temperatures, thermodynamic properties and radial distribution functions as well as dimerization and bonding energy distribution functions are reported for both liquid and glassy states. Changes in the radial distribution functions on cooling depend on whether the groups are accessible (peripheral) or inaccessible. Peaks in the radial distribution functions corresponding to peripheral groups do not shift to lower distances on cooling and at times display a large increase in the intensity of the first peak. The peaks due to inaccessible groups, on the other hand, shift to lower distances on cooling. The magnitude of the reorientational contribution in determining the resulting structure of the glass is estimated for the different hydrocarbon molecules investigated. The reorientational contribution is highest for neopentane (26%) followed by isopentane (24%), neohexane (22%), and n-pentane (0%). It appears that molecular geometry has an important role in determining the magnitude of the reorientational contribution to the structure of the glass.