Structural Evolution in a Glass-Forming Liquid Alcohol by X-Ray Scattering: Contrasting Behaviors of Main Peak and Prepeak Structures

X-ray scattering of liquid 2-ethyl-1-hexanol (2E1H) has been measured from its liquid state to its glassy state with focus on the main scattering peak and the prepeak. The main peak, associated with the packing of the alkyl chains, shifts to higher angle and sharpens in a manner consistent with closely packed spheres, until kinetic arrest at the glass transition temperature <i>T</i>_g (146 K). In contrast, the prepeak, associated with the correlation of the hydroxyl groups separated by the hydrocarbon chains, shows a transition near 220 K, below which its width is nearly frozen and insensitive to the passage of <i>T</i>_g. This transition coincides with a similar transition in the Kirkwood factor <i>g</i>_K which reports the orientational correlation of the OH dipoles, and with the transition reported previously as the "250 K anomaly" based on other observables. This transition arises from the increased hydrogen bonding between the hydroxyl groups and the resulting improvement of the regularity of the alcohol bilayers.