title: Competition between H2O and (H2O)2 reactions with CH2OO/CH3CHOO.
abstract: In this study, we performed ab initio calculations and obtained the bimolecular rate coefficients for the CH2OO/CH3CHOO reactions with H2O/(H2O)2. The energies were calculated with QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) and the partition functions were estimated with anharmonic vibrational corrections by using the second order perturbation theory. Furthermore, we directly measured the rate of the CH2OO reaction with water vapor at high temperatures (348 and 358 K) to reveal the contribution of the water monomer in the CH2OO decay kinetics. We found that the theoretical rate coefficients reproduce the experimental results of CH2OO for a wide range of temperatures. For anti- (syn-) CH3CHOO, we obtained theoretical rate coefficients of 1.60 × 10(-11) (2.56 × 10(-14)) and 3.40 × 10(-14) (1.98 × 10(-19)) cm(3) s(-1) for water dimer and monomer reactions at room temperature. From the detailed analysis of the quantum chemistry and approximations for the thermochemistry calculations, we conclude that our calculated values would be within a factor of 3 of the correct values. Furthermore, at [H2O] = 1 × 10(17) to 5 × 10(17) cm(-3), we estimate that the effective first-order rate coefficients for CH2OO, anti- and syn-CH3CHOO reactions with water vapor will be ∼10(3), ∼10(4), and ∼10(1) s(-1), respectively. Thereby, for Criegee intermediates with a hydrogen atom on the same side as the terminal oxygen atom, the reaction with water vapor will likely dominate the removal processes of these CIs in the atmosphere.
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw and Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Liang-Chun
authors.initials: LC
authors.lastname: Lin
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw.
authors.forename: Hung-Tzu
authors.initials: HT
authors.lastname: Chang
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw.
authors.forename: Chien-Hsun
authors.initials: CH
authors.lastname: Chang
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw and Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Wen
authors.initials: W
authors.lastname: Chao
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw and Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720, USA.
authors.forename: Mica C
authors.initials: MC
authors.lastname: Smith
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw.
authors.forename: Chun-Hung
authors.initials: CH
authors.lastname: Chang
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw and Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
authors.forename: Jim
authors.initials: J
authors.lastname: Min Lin
authors.affiliation: Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan. kt@gate.sinica.edu.tw jimlin@gate.sinica.edu.tw.
authors.forename: Kaito
authors.initials: K
authors.lastname: Takahashi