Direct simulation of rovibrational excitation and dissociation in molecular nitrogen using an ab initio potential energy surface

We present an atomic-level study of vibrational excitation and chemical dissociation in molecular nitrogen at high temperature. The computational techniques, quasiclassical trajectory calculations (QCT) and classical trajectory calculation direct simulation Monte Carlo (CTC DSMC), solely rely on the specification of a highly accurate ab initio surface for N₂-N₂ interactions. We show that the simulations accurately reproduce the vibrational relaxation times obtained from the Millikan-White correlation and further support existing high-temperature corrections. Using both QCT and CTC DSMC methods with the same PES, we show that dissociation proceeds 4 to 5 times faster under equilibrium conditions compared to quasi-steady-state nonequilibrium conditions. At high translational energies (20,000 K and 30,000 K), the overall vibrational energy ladder is depleted, and dissociation proceeds at a rate approximately corresponding to a lower vibrational temperature. Conversely, at lower energies (10,000 K), almost no dissociation occurs from low-lying vibrational energy states. In this case, even a slight depletion of the upper-level vibrational energy states, which preferentially dissociate and are not rapidly re-populated due to slow bound-bound energy transfer mechanisms, causes a remarkable reduction of the dissociation rate. The ab initio CTC DSMC method is able to directly simulate rovibrational excitation and dissociation processes without computing the large number of cross-sections required by a state-resolved approach, and can be used directly to form new CFD models.