Effect of Water and Ammonia on the HO + NH3 → NH2 + H2O Reaction in Troposphere: Competition between Single and Double Hydrogen Atom Transfer Pathways

Publication date: Available online 11 February 2020Source: Computational and Theoretical ChemistryAuthor(s): Tianlei Zhang, Kaiyue Zhai, Yongqi Zhang, Lin Geng, Zerong Geng, Mi Zhou, Yousong Lu, Xianzhao Shao, Makroni LilyAbstractA comprehensive investigation of the roles of H2O and NH3 on the HO + NH3 → NH2 + H2O reaction in the troposphere has been carried out by CCSD(T)-F12a/cc-pVDZ-F12//M06-2X/6-311+G(2d,2p) method, and the canonical variational transition state theory with small curvature tunneling correction. The results show that both H2O and NH3 catalyzed reactions prefer the single hydrogen atom transfers (HAT) pathways than the double HAT routes. Meanwhile, the catalytic effect of H2O is more obvious as compared with NH3 with its effective rate constant (k'(WM)) larger by 2-5 orders of magnitude. However, within the temperature range of 213-320 K, the calculated value of k'(WM) is smaller by 5-9 orders of magnitude than the corresponding rate constant of the naked reaction. This result is in agreement with H2O catalyzed OH + CH2CH2, OH + CH2O and OH + CH2NH reactions, where water-assisted reaction cannot accelerate the reaction.Graphical abstract

Source: Computational and Theoretical Chemistry - February 12, 2020 Category: Chemistry Source Type: research