Terahertz normal mode relaxation in pentaerythritol tetranitrate

Normal vibrational modes for a three-dimensional defect-free crystal of the high explosive pentaerythritol tetranitrate were obtained in the framework of classical mechanics using a previously published unreactive potential-energy surface [J. Phys. Chem. B 112, 734 (2008)]. Using these results the vibrational density of states was obtained for the entire vibrational frequency range. Relaxation of selectively excited terahertz-active modes was studied using isochoric-isoergic (NVE) molecular dynamics simulations for energy and density conditions corresponding to room temperature and atmospheric pressure. Dependence of the relaxation time on the initial modal excitation was considered for five excitation energies between 10 and 500 kT and shown to be relatively weak. The terahertz absorption spectrum was constructed directly using linewidths obtained from the relaxation times of the excited modes for the case of 10 kT excitation. The spectrum shows reasonably good agreement with experimental results. Dynamics of redistribution of the excited mode energy among the other normal modes was also studied. The results indicate that, for the four terahertz-active initially excited modes considered, there is a small subset of zero wave vector (k = 0) modes that preferentially absorb the energy on a few-picosecond time scale. The majority of the excitation energy, however, is transferred nonspecifically to the bath modes of the system.