Pressure effects on relaxation in a polymer glass: A persistent spectral hole burning study

摘要

The influence of hydrostatic pressure in the range of some kilobars on low-temperature (T < 20 K) relaxation in a polymer (polystyrene) glass after optical excitation of a probe chromophore in it is studied using two different kinds of spectral hole burning experiments-under isothermal-isobaric and in temperature cycling conditions. In the first case, the temperature dependence of the hole width reflects the dynamics of interaction of the electronic transition in a probe molecule with soft localized vibrational modes and with two-level systems, whereas, in the second case, the observed residual hole broadening after the temperature cycle arises from activated (overbarrier) transitions in almost symmetric double-well soft potentials. It is shown that both these processes are essentially suppressed by the applied hydrostatic pressure (the hole width in the first case and its increment in the second case are both reduced about twofold at 5 kbar). An extension of the soft potential model for glasses is proposed explaining in a coherent manner both effects. Its essential points are the presence in the potential of an extra term linear in pressure and the soft coordinate and an assumption about asymmetric distribution of the cubic anharmonicity parameter xi in the potential. (c) 2005 Pleiades Publishing, Inc.