Reactions with Criegee intermediates are the dominant gas-phase sink for formyl fluoride in the atmosphere

Experimental and theoretical study of Criegee intermediate (CH2OO) reactions with n-butyraldehyde and isobutyraldehyde: kinetics, implications and atmospheric fate

“…The mixing ratio values considered in this calculation were [OH] = 1.0 × 10 6 molecule cm −3 , 83 [Cl] (in marine boundary) = 1.3 × 10 5 molecule cm −3 , 84 and [CH 2 OO] = 10 4 molecule cm −3 . 12,22,85 The T CUM value for the studied aldehydes ranges from 3–7 hours, which suggests that these aldehydes have very localized effects near the source and undergo removal in a few hours from the atmosphere.…”

Quantitative kinetics of the atmospheric reaction between isocyanic acid and hydroxyl radicals: post-CCSD(T) contribution, anharmonicity, recrossing effects, torsional anharmonicity, and tunneling

“…We calculated rate constants by utilizing a dual-level strategy. 60–62 The direct kinetics calculations at the M05-2X/aug-cc-pVTZ level were performed by using canonical variational transition state theory (CVT), in which the tunneling transmission coefficient is computed by using small-curvature tunneling (SCT) approximation. 63–66 The rate constant was calculated using the following eqn (3).Here, k ( T ) TST HL is the conventional transition state theory (TST) rate constant calculated with the electronic structure parameters obtained by the GMM(P).L//CCSD(T)-F12a/cc-pVTZ-F12 level, Γ ( T ) LL is the recrossing transmission coefficient calculated by M05-2X/aug-cc-pVTZ, which equals , k SCT LL is the tunneling transmission coefficient calculated by using small-curvature tunneling (SCT) approximation at the M05-2X/aug-cc-pVTZ level from the pre-reactive complex to the corresponding product, and F MS-T act is the multi-structural torsional anharmonicity factor calculated by using the multi-structural method with torsional anharmonicity based on a coupled torsional potential.…”

“…We calculated rate constants by utilizing a dual-level strategy. [60][61][62] The direct kinetics calculations at the M05-2X/ aug-cc-pVTZ level were performed by using canonical variational transition state theory (CVT), in which the tunneling transmission coefficient is computed by using small-curvature tunneling (SCT) approximation. [63][64][65][66] The rate constant was calculated using the following eqn (3).…”

Rapid Atmospheric Reactions between Criegee Intermediates and Hypochlorous Acid

“…The rate constants of CH 2 OO/ syn- CH 3 CHOO + HOCl were calculated by using a dual-level (DL) strategy. ,− The rate constant is provided by the following formula in eq k = k SS − TST HL κ SCT LL Γ CVT LL where k SS–TST HL was calculated by using the high-level W3X-L//CCSD(T)-F12a/cc-pVTZ-F12 and W3X-L//DF-CCSD(T)-F12b/cc-pVDZ-F12 for conventional transition state theory without tunneling with the specific reaction parameter scale factor in the CH 2 OO/ syn- CH 3 CHOO + HOCl reaction, respectively. κ SCT LL and Γ CVT LL denote the tunneling and recrossing transmission coefficients calculated by using canonical vibrational transition theory (CVT) , with small-curvature tunneling (SCT) at the validated MN15-L/MG3S level with the standard scale factor.…”