Probing ultrafast shock-induced chemistry in liquids using broad-band mid-infrared absorption spectroscopy

Abstract

We probe shock-induced chemistry in two organic liquids by measuring broadband, midinfrared absorption in the 800-1400 cm^-1 frequency range. To test this new method and understand the signatures of chemical reactions in time resolved vibrational spectra, we compared liquid benzene shocked to unreactive conditions (shocked to a pressure of 18 GPa for a duration of 300 ps) to nitromethane under reactive conditions (25 GPa). We see clear signatures of shock-induced chemistry that are distinguishable from the pressure- and temperature-induced changes in vibrational mode shapes. While shocked benzene shows primarily a broadening and shifting of the vibrational modes, the nitromethane vibrational modes vanish once the shock wave enters the liquid and simultaneously, a spectrally broad feature appears that we interpret as the infrared spectrum of the complex mixture of product and intermediate species. To further interpret these measurements, we compare them to reactive quantum molecular dynamics simulations, which gives qualitatively consistent results. This work demonstrates a promising method for time resolving shock-induced chemistry, illustrating that chemical reactions produce distinct changes in the vibrational spectra.