Predicting the α-relaxation time of glycerol confined in 1.16 nm pores of zeolitic imidazolate frameworks.

Abstract

Uhl et al. [J. Chem. Phys., 2019, 150, 024504] studied the molecular dynamics of glycerol confined in a microporous zeolitic imidazolate framework (ZIF-8) with well-defined pore diameters of 1.16 nm by broadband dielectric spectroscopy. Of interest is a fast process in the central part of the pores identified as the α-relaxation of the confined supercooled glycerol with relaxation times τα,conf(T) reduced from τα,bulk(T) of bulk glycerol and having a temperature dependence different from the super-Arrhenius temperature of the latter. The focus of Uhl et al. was relating the confined molecular dynamics to the cooperativity length scales Lcorr(T) of molecular motion above the glass transition, and deducing the limiting high-temperature value of the correlation length of about 1.22 nm. Not yet considered by anyone are the observed values of τα,conf(T) and temperature dependence. Since the cooperativity length scales Lcorr(T) were found to be larger than the pore size of ZIF-8 over the temperature range studied and the density of the glycerol in the pore is possibly lower than the bulk, the cooperativity of the α-relaxation of glycerol confined in ZIF-8 is drastically reduced. Thus, within the framework of the Coupling Model (CM), τα,conf(T) should be nearly the same as the primitive relaxation time τ0(T) for glycerol when devoid of intermolecular coupling and cooperativity. Consistent with the absence of cooperativity of the glycerol confined in ZIF-8, we find the calculated τα,conf(T) are either the same or slightly longer than the calculated values of τ0(T). The quantitative prediction of the CM is verified. At this time we know of no other theory that can make such a quantitative prediction.