Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO

Abstract

The kinetics and mechanisms for the reaction of the Criegee intermediate CH2OO with HNO3 and the unimolecular decomposition of its reaction product CH2(O)NO3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO3CH2OOH* with internal energy similar to 44 kcal mol(-1). A fragmentation of this excited intermediate produces CH2(O)NO3 + OH with its transition state located 5.0 kcal mor(-1) below that of the reactants. Further decomposition of CH2(O)NO3 produces HCO + HNO3, forming a catalytic cycle for destruction of CH2OO by HNO3. The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N-2) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH2OO + HNO3 at 295 K, 5.1 x 10(-10) cm(3) molecule(-1) s(-1), agrees satisfactorily with the experimental value, (5.4 +/- 1.0) X 10(-10) cm(3) molecule(-1) s(-1). The predicted branching ratios at 295 K are 0.21 for the formation of NO3CH2OOH and 0.79 for CH2(O)NO3 + OH at a pressure of 40 Torr (N-2), and 0.79 for the formation of NO3CH2OOH and 0.21 for CH2(O)NO3 + OH at 760 Torr (N-2). This new catalytic conversion of CH2OO to HCO + OH by HNO3 might have significant impact on atmospheric chemistry.