Role of the Recombination Channel in the Reaction between the HO and HO2 Radicals

详细信息    查看全文

• 作者：María P. BadenesMaría E. Tucceri ; Carlos J. Cobos
• 刊名：Journal of Physical Chemistry A
• 出版年：2017
• 出版时间：January 19, 2017
• 年：2017
• 卷：121
• 期：2
• 页码：440-447
• 全文大小：435K
• ISSN：1520-5215

文摘

The kinetics of the gas phase recombination reaction HO + HO₂ + He → HOOOH + He has been studied between 200 and 600 K by using the SACM/CT model and the unimolecular rate theory. The molecular properties of HOOOH were derived at the CCSD(T)/aug-cc-pVTZ ab initio level of theory, while relevant potential energy features of the reaction were calculated at the CCSD(T)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVDZ level. The resulting high and low pressure limit rate coefficients are k_∞ = 3.55 × 10^–12 (T/300)^0.20 cm³ molecule^–1 s^–1 and k₀ = [He] 1.55 × 10^–31 (T/300)^−3.2 cm³ molecule^–1 s^–1. The rate coefficients calculated over the 6 × 10^–4 – 400 bar range are smaller at least in a factor of about 60 than the consensus value determined for the main reaction channel HO + HO₂ → H₂O + O₂, indicating that the recombination pathway is irrelevant.