Microscopic understanding of the Johari-Goldstein β relaxation gained from nuclear γ-resonance time-domain-interferometry experiments.

Traditionally the study of dynamics of glass-forming materials has been focused on the structural α relaxation. However, in recent years experimental evidence has revealed that a secondary β relaxation belonging to a special class, called the Johari-Goldstein (JG) β relaxation, has properties strongly linked to the primary α relaxation. By invoking the principle of causality, the relation implies the JG β relaxation is fundamental and indispensable for generating the α relaxation, and the properties of the latter are inherited from the former. The JG β relaxation is observed together with the α relaxation mostly by dielectric spectroscopy. The macroscopic nature of the data allows the use of arbitrary or unproven procedures to analyze the data. Thus the results characterizing the JG β relaxation and the relation of its relaxation time τ_{β} to the α-relaxation time τ_{α} obtained can be equivocal and controversial. Coming to the rescue is the nuclear resonance time-domain-interferometry (TDI) technique covering a wide time range (10^{-9}-10^{-5}s) and a scattering vector q range (9.6-40nm^{-1}). TDI experiments have been carried out on four glass formers, ortho-terphenyl [M. Saito et al., Phys. Rev. Lett. 109, 115705 (2012)10.1103/PhysRevLett.109.115705], polybutadiene [T. Kanaya et al., J. Chem. Phys. 140, 144906 (2014)10.1063/1.4869541], 5-methyl-2-hexanol [F. Caporaletti et al., Sci. Rep. 9, 14319 (2019)10.1038/s41598-019-50824-7], and 1-propanol [F. Caporaletti et al., Nat. Commun. 12, 1867 (2021)10.1038/s41467-021-22154-8]. In this paper the TDI data are reexamined in conjunction with dielectric and neutron scattering data. The results show the JG β relaxation observed by dielectric spectroscopy is heterogeneous and comprises processes with different length scales. A process with a longer length scale has a longer relaxation time. TDI data also prove the primitive relaxation time τ_{0} of the coupling model falls within the distribution of the TDI q-dependent JG β-relaxation times. This important finding explains why the experimental dielectric JG β-relaxation times τ_{β}(T,P) is approximately equal to τ_{0}(T,P) as found in many glass formers at various temperature T and pressure P. The result, τ_{β}(T,P)≈τ_{0}(T,P), in turn explains why the ratio τ_{α}(T,P)/τ_{β}(T,P) is invariant to changes of T and pressure P at constant τ_{α}(T,P), the α-relaxation time.