Molecular dynamics simulations vs field-cycling NMR relaxometry: Structural relaxation mechanisms in the glass-former glycerol revisited

• Published in: The Journal of chemical physics Vol. 154; no. 12; pp. 124503 - 124518
• Main Authors: Becher, M., Wohlfromm, T., Rössler, E. A., Vogel, M.
• Format: Journal Article
• Language: English
• Published: United States 28.03.2021
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0048131

We combine field-cycling (FC) relaxometry and molecular dynamics (MD) simulations to study the rotational and translational dynamics associated with the glassy slowdown of glycerol. The 1H NMR spin-lattice relaxation rates R1(ω) probed in the FC measurements for different isotope-labelled compounds are computed from the MD trajectories for broad frequency and temperature ranges. We find high correspondence between experiment and simulation. Concerning the rotational motion, we observe that the aliphatic and hydroxyl groups show similar correlation times but different stretching parameters, while the overall reorientation associated with the structural relaxation remains largely isotropic. Additional analysis of the simulation results reveals that transitions between different molecular configurations are slow on the time scale of the structural relaxation at least at sufficiently high temperatures, indicating that glycerol rotates at a rigid entity, but the reorientation is slower for elongated than for compact conformers. The translational contribution to R1(ω) is well described by the force-free hard sphere model. At sufficiently low frequencies, universal square-root laws provide access to the molecular diffusion coefficients. In both experiment and simulation, the time scales of the rotational and translational motions show an unusually large separation, which is at variance with the Stokes–Einstein–Debye relation. To further explore this effect, we investigate the structure and dynamics on various length scales in the simulations. We observe that a prepeak in the static structure factor S(q), which is related to a local segregation of aliphatic and hydroxyl groups, is accompanied by a peak in the correlation times τ(q) from coherent scattering functions.