Master equation modeling of wide range temperature and pressure dependence of CO + OH → products

摘要: The rate coefficient of CO + OH products is analyzed with RRKM/master equation analyses and Monte Carlo simulations. are based on the recent CCSD(T)/cc-pvTZ potential energy surface Yu et al. Chem Phys Lett 2001, 349, 547–554). It shown that experimental data over temperature range 80–2500 K pressure from 1 Torr to 800 bar can be satisfactorily reproduced by lowering barrier for CO2 + H exit channel kcal/mol more importantly, considering an equilibrium factor in thermal constant formulation. This accounts populations rovibrationally excited trans- cis-HOCO, which then allowed dissociate only through specific paths open them. By modeling isothermal but pressure-dependent Fulle (J 1996, 105, 983–1000) 98 819 K, we obtained 〈Edown〉 value equal 150 cm−1 M = He. values M = N2, Ar, CF4, SF6 were also fitting OD at 298 K. Based theoretical analyses, recommended following expression used CO + OH  CO2 + H 120 2500 lower than P(bar) = 9 × 10−17T5.9 exp(520/T): k1b,0(cm3 molecule−1s−1) =1.17 × 10−19T2.053exp(139/T) 9.56 10−12T−0.664 exp(−167/T). Fall-off parameterization proposed under extremely high pressures CO + OH  HOCO © 2005 Wiley Periodicals, Inc. Int J Kinet 38:57–73, 2006