Supramolecular structure vs. rheological properties: 1,4–Butanediol at room and elevated temperatures

High-Pressure and Temperature Effects on the Clustering Ability of Monohydroxy Alcohols

“…At 413 K both 2E1H and 2M3H show no preference for the number of molecules in clusters and are composed of a considerably large percent of free molecules. One of the very few studies conducted under high temperature or at high pressure up to around 1 GPa on alcohols 23 is consistent with our results. Increasing the temperature was reported to decrease the sizes of H-bonded aggregates in diols, while the prepeak position remained stable in the temperature-dependent diffraction patterns.…”

“…Namely, lowering temperature causes clear sharpening and an increase in amplitude of both peaks, whereas under high temperature they are seriously broadened and damped. The effect of the increasing background with growing temperature at the low scattering vector range, giving an impression of an apparent increase in the prepeak's intensity, has already been observed 23 and explained by changes in the compressibility. 24 With increasing pressure, the diffraction peaks gradually decrease and become wider.…”

“…Although, based on this, one may intuitively hypothesize that high pressure induces a destructive effect on the intermolecular structure, such a straightforward interpretation may be incorrect. Recent molecular dynamics simulations have shown that a simplified analysis of only the total diffraction intensities obtained in experiments may lead to wrong conclusions. ,, In fact, the total structure factor consists of partial atomic functions, which describe the correlations between specific atom types and can be easily derived from a theoretical molecular model. Therefore, given the very good compliance between the experimental and simulation results presented in Figure , we further analyze the partial functions derived from optimized theoretical models.…”