Interplay of high-precision shock wave experiments with first-principles theory to explore molecular systems at extreme conditions: A perspective

Conventional methods for probing molecular changes in condensed matter systems, such as electronic and vibrational spectroscopy, are difficult to implement at the extreme conditions associated with dynamic compression experiments. This is particularly true for experiments in the multimegabar regime; to achieve the requisite energy density to produce such pressures, sample sizes are necessarily quite small and experimental timescales are, therefore, extremely short. Furthermore, these extreme pressure conditions also result in high temperatures and, therefore, significant thermal emission even in the visible to infrared regime and in some cases render the sample opaque or reflective, thereby precluding bulk spectroscopy techniques, such as Raman scattering. These experimental challenges require a different approach to evaluating shock-induced changes at the molecular or atomic level in the multimegabar or the so-called warm dense matter regime. The past few decades have seen significant advances in the use of first-principles methods to investigate materials under extreme conditions, enabling these methods to become a powerful tool for exploring molecular systems at extreme conditions. Here, we discuss the construct of combining high-precision shock wave experiments with first-principles theory to explore molecular systems at extreme conditions. The results from high-fidelity dynamic compression experiments are used to evaluate first-principles theoretical frameworks and identify the framework that best reproduces experimental results in the regime of interest. That validated framework is then used to perform detailed simulations of the system of interest, providing unique insight into the response of the system at the molecular level.