A study of the deep structure of the energy landscape of glassy polystyrene: the exponential distribution of the energy-barriers revealed by high-field Electron Spin Resonance spectroscopy

Abstract

The reorientation of one small paramagnetic molecule (spin probe) in glassy polystyrene (PS) is studied by high-field Electron Spin Resonance spectroscopy at two different Larmor frequencies (190 and 285 GHz). The exponential distribution of the energy-barriers for the rotational motion of the spin probe is unambigously evidenced at both 240K and 270K. The same shape for the distribution of the energy-barriers of PS was evidenced by the master curves provided by previous mechanical and light scattering studies. The breadth of the energy-barriers distribution of the spin probe is in the range of the estimates of the breadth of the PS energy-barriers distribution. The evidence that the deep structure of the energy landscape of PS exhibits the exponential shape of the energy-barriers distribution agrees with results from extreme-value statistics and the trap model by Bouchaud and coworkers.