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  • Predicting the α-relaxation...
    Ngai, K. L; Lunkenheimer, P; Loidl, A

    Physical chemistry chemical physics : PCCP, 01/2020, Letnik: 22, Številka: 2
    Journal Article

    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 τ α,conf ( T ) reduced from τ α,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 L corr ( 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 τ α,conf ( T ) and temperature dependence. Since the cooperativity length scales L corr ( 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), τ α,conf ( T ) should be nearly the same as the primitive relaxation time τ 0 ( 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 τ α,conf ( T ) are either the same or slightly longer than the calculated values of τ 0 ( 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. Relaxation times of glycerol confined in 1.16 nm ZIF pores found by Uhl et al. J. Chem. Phys. , 2019, 150 , 024504 are explained quantitatively by the Coupling Model.