Master Equation Study and Nonequilibrium Chemical Reactions for Hydrogen Molecule

摘要

The state-to-state cross sections and rates for collisional transitions of rotational and vibrational states were firstncalculated by using quasi-classical trajectory calculations forH2 u0001 H2 collisions. Accuracy of these calculations wasnverified by comparing themwith the results of quantummechanical and other quasi-classical trajectory calculations.nA system of master equations was constructed for a total of 348 ro-vibrational states with these rate coefficients.nUnlike in existing works, the internal states of the colliding particles were assumed to be distributed under anBoltzmann distribution specified by a nonequilibrium temperature. The nonequilibrium temperature was in turnndetermined from the ro-vibrational energy contents. From the results of the master equation calculation, thenrelaxation rate of vibrational and rotationalmodes, rate of relaxation of number densities, the average ro-vibrationalnenergy transferred during dissociation, the quasi-steady state rate coefficients, and two-temperature rate coefficientsnwere derived. The present results are different from those of Sharma (“Rotational Relaxation of MolecularnHydrogen atModerate Temperatures,” Journal of Thermophysics and Heat Transfer, Vol. 8, No. 1, 1994, pp. 35–39)nand of Furudate et al. (“CoupledRotational-VibrationalRelaxation ofMolecularHydrogen atHighTemperatures,”nJournal of Thermophysics and Heat Transfer, Vol. 20, No. 3, 2006, pp. 457–464), and agree closer with existingnexperimental data.