Why the Brillouin Light Scattering Relaxation Times of Molten Zinc Chloride Are Shorter and Weaker in Temperature Dependence than the Structural Relaxation Times from Depolarized Light and Neutron Spin Echo Spectroscopy

Abstract

A longstanding problem in the Brillouin light scattering (BLS) study of polymers is the relaxation times τBLS(T) being more than an order of magnitude shorter than the α-relaxation times τα(T) determined by dielectric, depolarized light scattering (DLS), and molecular dynamics simulations. In tackling the problem, τBLS(T) was identified with the relaxation time τ0(T) of the primitive relaxation in the coupling model, which can be calculated from τα(T) and the stretch exponent βK of the Kohlrausch correlation function for the α-relaxation.. The problem was solved by finding that indeed τ0(T) is in good agreement with τBLS(T). A recent work performed the neutron spin echo study of the structural α-relaxation of the network ionic liquid ZnCl2 and found the same anomaly as polymers. The α-relaxation time τNSE(T) from neutron spin echo (NSE) as well as the α-relaxation time τDLS(T) from DLS of ZnCl2 are much longer than τBLS(T) from BLS obtained before by several research groups. The finding of the same anomaly in ZnCl2 and polymers with very different chemical and physical structures offers an opportunity to critically test the explanation given before. The test was carried out by calculating the primitive relaxation times τ0,DLS(T) and τ0,NSE(T) from τDLS(T) and τNSE(T), respectively, in zinc chloride. Good agreements of τBLS(T) from BLS with τ0,DLS(T) and τ0,NSE(T) were found and thus the explanation given for polymers remains valid for ZnCl2. The test was extended to glycerol by comparing τBLS(T) with τ0,ICNS(T) and τ0,CNS(T) calculated from the α-relaxation time τICNS(T) and τCNS(T) from incoherent and coherent neutron scattering, respectively. There is good agreement between τBLS(T) and τ0,ICNS(T) in glycerol. There is also semiquantitative agreement of τBLS(T) with τ0,DS(T) from dielectric spectroscopy as well as τ0,CNS(T). Thus, the explanation for polymers is verified in the two very different glass formers, ZnCl2 and glycerol, and it is an advancement in the application of BLS to study the dynamics of glass formers.