Sub-picosecond to Sub-nanosecond Vibrational Energy Transfer Dynamics in Pentaerythritol Tetranitrate

Abstract

The time scale associated with shock-induced detonation is a key property of energetic materials that remains poorly understood. Herein, we test aspects of one potential mechanism, the phonon up-pumping mechanism, where shock compression excites lattice phonon modes, transferring energy to intramolecular vibrations leading to chemical bond cleavage and reaction. Using ultrafast infrared pump-probe spectroscopy on pentaerythritol tetranitrate (PETN), we reveal sub-picosecond vibrational energy transfer (VET) from the photoexcited band at 1660 cm^-1 into every other infrared-active mode in the probed frequency range 800-1800 cm^-1. Energy transfer processes remain incomplete at 150 ps. Computational predictions from density functional theory are used in tandem to elucidate VET pathways in PETN.