title: Ab initio-informed maximum entropy modeling of rovibrational relaxation and state-specific dissociation with application to the O2 + O system.
abstract: 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.
authors.affiliation: Aeronautics and Astronautics, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Marat
authors.initials: M
authors.lastname: Kulakhmetov
authors.affiliation: Engineering Sciences Center, Sandia National Laboratories, Albuquerque, New Mexico 87185, USA.
authors.forename: Michael
authors.initials: M
authors.lastname: Gallis
authors.affiliation: Aeronautics and Astronautics, Purdue University, West Lafayette, Indiana 47907, USA.
authors.forename: Alina
authors.initials: A
authors.lastname: Alexeenko