Objective molecular dynamics investigation of dissociation and recombination kinetics in high-temperature nitrogen

Abstract

In this study, we propose the use of the novel approach of objective molecular dynamics (OMD) simulating far-from-equilibrium gas dynamics problems with chemical reactions. The OMD method has an exact relation to models in continuum mechanics and can be used to improve those models. We provide a detailed molecular dynamics investigation of chemically reacting nitrogen gas in a space-homogeneous adiabatic reactor. The analysis is based on a first-principles derived reactive ReaxFF potential energy surface, which captures the relevant processes of rovibrational relaxation, dissociation, and exchange as well as recombination in a gas evolving under non-equilibrium conditions. We examine the evolution of the internal mode population distribution of all the molecules as well as the rovibrational probability distribution of the pre-collision dissociating and post-collision recombined N2 molecules to investigate the microscopic selectivity of various reactive processes. Subsequently, we make comparisons with results obtained by means of an alternative modeling approach called direct molecular simulation. The current work illustrates the application of the method of OMD to study the compression and expansion kinetics of dissociation-recombination nitrogen mixture relevant to normal shock wave and nozzle expansion.