Although glass has been fabricated for thousands of years, the microscopic mechanism governing the glass transition process remains unclear. The main challenge is to understand the non-Arrhenius temperature dependence of the structural relaxation time of the supercooled liquids upon approaching the glass transition temperature. Most researchers ascribe it to cooperative molecular motions. Various experimental results and simulations show that the structural relaxation of a supercooled liquid is spatially heterogeneous. This dynamic heterogeneity is usually attributed to the cooperative molecular motions in local domains. The cooperativity size is estimated from the spatial heterogeneity to be ~1–4 nanometers. However, many important questions are still unsolved, e.g. what is the role of molecular cooperativity in the temperature dependence of the structural relaxation time?
On the other hand, the collective vibration in the GHz-THz frequency range, the so-called boson peak, is also considered to be a manifestation of a cooperative process with a characteristic length scale of a few nanometers. Some researchers even speculate that the length scale associated with the boson peak is related to the cooperativity length scale of the main structural relaxation.
In this dissertation, we estimated the characteristic length scale from the boson peak spectra measured using light scattering for a large number of glass-forming materials. By comparing it to the dynamic heterogeneity length scale of the main structural relaxation acquired via 4-dimensional NMR, we find that the collective vibrations and the structural relaxation involve a similar length scale of molecular cooperativity.
When a supercooled liquid is cooled down to the glass transition temperature, decreases in free volume and thermal energy both contribute to slowing down the structural relaxation. Our analysis demonstrates that only the volume contribution to the variation of the structural relaxation time has a direct correlation with the cooperativity size among different materials, whereas the thermal energy contribution does not. The latter is more dependent on the chemical structure of the studied materials. These results call for a conceptually new approach to the analysis of the mechanism of the glass transition and to the role of molecular cooperativity.