Ab initio intermolecular interactions mediate thermochemically real-fluid effects that affect system reactivity: The first application of high-order Virial EoS and first-principles multi-body potentials in trans-/super-critical autoignition modelling

Abstract

The properties of supercritical fluids are dictated by intermolecular interactions that involve two or more molecules. Such intermolecular interactions were described via intermolecular potentials in historical supercritical combustion modeling studies, but have been treated empirically and with no consideration of radical interactions or multi-body interactions involving more than two molecules. This approach has been adopted long ago, assuming sufficient characterization of real-fluid effects during supercritical combustion. Here, with data from ab initio multi-body intermolecular potentials, non-empirical high-order Virial Equation of State (EoS), and real-fluid thermochemical and kinetic simulations, we reveal that empirical intermolecular potentials can lead to significant errors in representing supercritical fluids under common combustion situations, which can be impressively described by ab initio intermolecular potentials. These interactions are also found to greatly influence autoignition delay times, a common measure of global reactivity, with significant contributions from radical interactions and multi-body interactions. It is therefore of necessity to incorporate ab initio intermolecular interactions in studying supercritical combustion and various dynamic systems involving supercritical fluids, which has now been enabled through the new framework developed in the present study.