The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time τ(T, P) constant (i.e., isochronal superpositioning) has been well established in molecular and polymeric glass-formers. Not known is whether the frequency dispersion or time dependence of the faster processes including the caged molecule dynamics and the Johari-Goldstein (JG) β relaxation possesses the same property. Experimental investigation of this issue is hindered by the lack of an instrument that can cover all three processes. Herein, we report the results from the study of the problem utilizing molecular dynamics simulations of two different glass-forming metallic alloys. The mean square displacement 〈Δrt〉, the non-Gaussian parameter αt, and the self-intermediate scattering function Fq,t at various combinations of T and P were obtained over broad time range covering the three processes. Isochronal superpositioning of 〈Δrt〉, αt, and Fq,t was observed over the entire time range, verifying that the property holds not only for the α relaxation but also for the caged dynamics and the JG β relaxation. Moreover, we successfully performed density ρ scaling of the time τT,P at the peak of αt and the diffusion coefficient D(T, P) to show both are functions of ρ/T with the same γ. It follows that the JG β relaxation time τ(T, P) is also a function of ρ/T since τT,P corresponds to τ(T, P).
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http://dx.doi.org/10.1063/5.0072527 | DOI Listing |
Phys Chem Chem Phys
November 2024
"Glass and Time", IMFUFA, Department of Science and Environment, Roskilde University, Postbox 260, DK-4000 Roskilde, Denmark.
This paper presents dielectric and neutron spectroscopy data on two different glycerol-water mixtures at elevated pressures. Glycerol-water liquid mixtures have a high concentration of hydrogen bonds which usually is expected to lead to complex dynamics. However, with regard to the pressure dependence of the dynamics we reveal a surprisingly simple picture.
View Article and Find Full Text PDFSci Rep
June 2023
Department of Pharmacognosy and Phytochemistry, Faculty of Pharmaceutical Sciences in Sosnowiec, Medical University of Silesia in Katowice, Jagiellonska 4, 41-200, Sosnowiec, Poland.
In this paper, the molecular dynamics at different thermodynamic conditions of hydrogen-bonded (H-bonded) active pharmaceutical ingredient-ticagrelor (TICA) have been investigated. Extensive high-pressure (HP) dielectric studies revealed surprising high sensitivity of the structural (α)-relaxation to compression. They also showed that unexpectedly the shape of the α-peak remains invariable at various temperature (T) and pressure (p) conditions at constant α-relaxation time.
View Article and Find Full Text PDFJ Chem Phys
December 2021
CNR-IPCF, Largo B. Pontecorvo 3, I-56127 Pisa, Italy.
The superposition of the frequency dispersions of the structural α relaxation determined at different combinations of temperature T and pressure P while maintaining its relaxation time τ(T, P) constant (i.e., isochronal superpositioning) has been well established in molecular and polymeric glass-formers.
View Article and Find Full Text PDFEur J Pharm Sci
September 2021
Department of Pharmacognosy and Phytochemistry, Faculty of Pharmaceutical Sciences in Sosnowiec, Medical University of Silesia in Katowice, ul. Jagiellonska 4, 41-200 Sosnowiec, Poland. Electronic address:
In this paper, the molecular dynamics as well as inter- and intramolecular interactions in the homogenous solid dispersions (SDs) of active pharmaceutical ingredient - probucol (PRO) with acetylated glucose (acGLU), acetylated sucrose (acSUC), and sucrose acetoisobutyrate (aibSUC), prepared in 5:1 molar ratio, have been investigated using broadband dielectric (BD) and Fourier transform infrared (FTIR) spectroscopy. Importantly, high pressure dielectric measurements revealed that as for neat PRO, a breakdown of the isochronal structural (α) and JG-β exact superpositioning, due to increasing separation between both processes under compression, can also be detected in its mixtures with acetylated saccharides (acSACCHs). Furthermore, the analysis of temperature dependences of JG-β-relaxation times for PRO and PRO-acSACCH SDs at selected isobaric conditions indicated the increase in the cooperativity of the secondary process (reflected in the value of the activation entropy, ΔS) at elevated pressure in all systems.
View Article and Find Full Text PDFJ Phys Chem B
July 2020
State Key Lab of Metastable Materials Science and Technology and College of Materials Science and Engineering, Yanshan University, Qinhuangdao, Hebei 066004, China.
The dielectric spectra of methyl -toluate (MMT) in supercooled liquid and glassy states were measured over wide ranges of temperature at ambient and elevated pressures . We found that the frequency dispersion of the loss peak contributed by the structural α-relaxation is invariant to changes of and , while keeping the loss peak frequency (,) constant. This isochronal superposition property of the α-relaxation holds for different choices of (,).
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