We develop the elastically collective nonlinear Langevin equation theory of bulk relaxation of glass-forming liquids to investigate molecular mobility under compression conditions. The applied pressure restricts more molecular motion and therefore significantly slows down the molecular dynamics when increasing the pressure. We quantitatively determine the temperature and pressure dependence of the structural relaxation time. To validate our model, dielectric spectroscopy experiments for three rigid and nonpolymeric supramolecules are carried out at ambient and elevated pressures. The numerical results quantitatively agree with experimental data.

In this work we report synthesis, unexpected glass-forming properties, molecular dynamics and conformational analysis of two glass-forming thiacrown ethers: 6-methyl-2,3-dihydro-1,4-benzodithiine (1) of a six-membered heterocyclic ring and macrocyclic 2,3-(4’-methylbenzo)-1,4-dithia-7-oxacyclononane (2)....

When we cool down a liquid below the melting temperature, it can either crystallize or become supercooled, and then form a disordered solid called glass. Understanding what makes a liquid to crystallize readily in one case and form a stable glass in another is a fundamental problem in science and technology. Here we show that the crystallization/glass-forming tendencies of the molecular liquids might be correlated with the strength of the intermolecular attractions, as determined from the combined experimental and computer simulation studies. We use van der Waals bonded propylene carbonate and its less polar structural analog 3-methyl-cyclopentanone to show that the enhancement of the dipole-dipole forces brings about the better glass-forming ability of the sample when cooling from the melt. Our finding was rationalized by the mismatch between the optimal temperature range for the nucleation and crystal growth, as obtained for a modeled Lennard-Jones system with explicitly enhanced or weakened attractive part of the intermolecular 6–12 potential.