Model for the Shape of the Relaxation Spectrum in Glass Formers.

Traditionally the broadness of the spectrum of the relaxation times observed in glass-forming materials has been rationalized by local heterogeneity, where a variety of atomistic environments leads to spectrum of single-exponential relaxation responses. However, the assumption of heterogeneity can break down when tested against the shape of the relaxation spectrum. An alternative homogeneous scenario assumes that the relaxation is inherently multiexponential. A recently developed switchback model [Medvedev, G. A. Phys. Rev. E 2023, 107 (3), 034122] naturally results in a multiexponential wedge-like spectrum that is consistent with the dielectric relaxation, light scattering, and the NMR data. As a particular case the switchback model allows for the spectrum to become single-exponential; under the heterogeneous scenario this would require the heterogeneities to completely vanish, which is hard to justify. Using data from photobleaching experiments and molecular dynamic simulations, it is shown that the relaxation spectrum may become single-exponential under large anisotropic deformation. This is interpreted as an argument in favor of the homogeneous scenario and specifically the switchback model for the relaxation of the glass formers.