Quasi-classical trajectory (QCT) calculations are used in this work to calculate state-specific N(XΣ)+O(P)→2N(S)+O(P) dissociation and N(XΣ)+O(P)→NO(XΠ)+N(S) exchange cross sections and rates based on the 1A″ and 1A' ab initio potential energy surface by Gamallo et al. [J. Chem. Phys. 119, 2545-2556 (2003)]. The calculations consider translational energies up to 23 eV and temperatures between 1000 K and 20 000 K. Vibrational favoring is observed for dissociation reaction at the whole range of collision energies and for exchange reaction around the dissociation limit. For the same collision energy, cross sections for v = 30 are 4 to 6 times larger than those for the ground state. The exchange reaction has an effective activation energy that is dependent on the initial rovibrational level, which is different from dissociation reaction. In addition, the exchange cross sections have a maximum when the total collision energy (TCE) approaches dissociation energy. The calculations are used to generate compact QCT-derived state-specific dissociation (QCT-SSD) and QCT-derived state-specific exchange (QCT-SSE) models, which describe over 1 × 10 cross sections with about 150 model parameters. The models can be used directly within direct simulation Monte Carlo and computational fluid dynamics simulations. Rate constants predicted by the new models are compared to the experimental measurements, direct QCT calculations and predictions by other models that include: TCE model, Bose-Candler QCT-based exchange model, Macheret-Fridman dissociation model, Macheret's exchange model, and Park's two-temperature model. The new models match QCT-calculated and experimental rates within 30% under nonequilibrium conditions while other models under predict by over an order of magnitude under vibrationally-cold conditions.

Quasi-classical trajectory (QCT) calculations are used to study state-specific ro-vibrational energy exchange and dissociation in the O2 + O system. Atom-diatom collisions with energy between 0.1 and 20 eV are calculated with a double many body expansion potential energy surface by Varandas and Pais [Mol. Phys. 65, 843 (1988)]. Inelastic collisions favor mono-quantum vibrational transitions at translational energies above 1.3 eV although multi-quantum transitions are also important. Post-collision vibrational favoring decreases first exponentially and then linearly as Δv increases. Vibrationally elastic collisions (Δv = 0) favor small ΔJ transitions while vibrationally inelastic collisions have equilibrium post-collision rotational distributions. Dissociation exhibits both vibrational and rotational favoring. New vibrational-translational (VT), vibrational-rotational-translational (VRT) energy exchange, and dissociation models are developed based on QCT observations and maximum entropy considerations. Full set of parameters for state-to-state modeling of oxygen is presented. The VT energy exchange model describes 22 000 state-to-state vibrational cross sections using 11 parameters and reproduces vibrational relaxation rates within 30% in the 2500-20 000 K temperature range. The VRT model captures 80 × 10(6) state-to-state ro-vibrational cross sections using 19 parameters and reproduces vibrational relaxation rates within 60% in the 5000-15 000 K temperature range. The developed dissociation model reproduces state-specific and equilibrium dissociation rates within 25% using just 48 parameters. The maximum entropy framework makes it feasible to upscale ab initio simulation to full nonequilibrium flow calculations.

The Chicxulub impact 66.0 Ma ago initiated the second biggest extinction in the Phanerozoic Eon. The cause of the concurrent oceanic nitrogen isotopic anomaly, however, remains elusive. The Chicxulub impactor struck the Yucatán peninsula, ejecting 2 × 1015 kg of molten and vaporized rock that reentered globally as approximately 1023 microscopic spherules. Here we report that modern techniques indicate that this ejecta generates 1.5 × 1014 moles of NOx, which is enough to cause the observed nitrogen enrichment of the basal layer. Additionally, reentry‐based NO production would explain the anomalously heavy isotopic composition of the observed nitrogen. We include N, O, N2, O2, and NO species in simulations of nonequilibrium chemically reacting flow around a reentering spherule. We then determine the net production of NO from all the spherules and use turbulence models to determine how quickly this yield diffuses through the atmosphere. Upon reaching the stratosphere and troposphere, cloud moisture absorbs the NOx and forms nitric acid. We model this process and determine the acidity of the resulting precipitation, which peaks about 1 year after the impact. The precipitation ultimately reaches the upper ocean, where we assume that the well‐mixed surface layer is 100 m deep. We then model the naturally occurring carbonate/bicarbonate buffer and determine the net pH. We find that insufficient NOx reaches the ocean to directly cause the observed end‐Cretaceous oceanic extinction via acidification and buffer removal. However, the resulting nitrates are sufficient to explain the concurrent nitrogen isotopic anomaly and facilitate an end‐Cretaceous algae bloom.

This work quantifies the sensitivity of O2 + O dissociation rates and relaxation to interatomic potential energy surfaces at high-enthalpy, nonequilibrium flow conditions. State-to-state cross sections are obtained by quasi-classical trajectory (QCT) calculations with two potential surfaces. The first is a Morse additive pairwise potential for O3 that is constructed based on O2(3Σg−) spectroscopic measurements and the second is a double many-body expansion potential by Varandas and Pais [Mol. Phys. 65, 843–860 (1988)]. The QCT calculations of cross sections and rates with the two surfaces are compared to each other and shock tube measurements. It is found that, at temperatures between 2500 K and 20 000 K, the equilibrium dissociation rates predicted by the two potentials agree within 12%, and they are bound by experimental dissociation measurements. In contrast, above 10 000 K, ab initio based equilibrium dissociation rates are about a factor of two higher than the widely used Park’s model. The nonequilibrium dissociation rates calculated by the two potentials are within 70% while phenomenological models differ by two orders of magnitude for vibrationally cold conditions of shocks. The analyses provide an approach for improving accuracy of nonequilibrium high-enthalpy flow modeling when ab initio potentials are not available.

This work evaluates high-fidelity vibrational-translational (VT) energy relaxation and dissociation models for pure O2 normal shockwave simulations with the direct simulation Monte Carlo (DSMC) method. The O2–O collisions are described using ab initio state-specific relaxation and dissociation models. The Macheret-Fridman (MF) dissociation model is adapted to the DSMC framework by modifying the standard implementation of the total collision energy (TCE) model. The O2–O2 dissociation is modeled with this TCE+MF approach, which is calibrated with O2–O ab initio data and experimental equilibrium dissociation rates. The O2–O2 vibrational relaxation is modeled via the Larsen-Borgnakke model, calibrated to experimental VT rates. All the present results are compared to experimental data and previous calculations available in the literature. It is found that, in general, the ab initio dissociation model is better than the TCE model at matching the shock experiments. Therefore, when available, efficient ab initio models are preferred over phenomenological models. We also show that the proposed TCE + MF formulation can be used to improve the standard TCE model results when ab initio data are not available or limited.