A computational investigation of the atmospheric reaction CH3O2+ClO

Theoretical study on the atmospheric reaction of CH3O2with OH

“…The PES scan along the OO bond conforms that the association should take place in a barrierless process. The formation of 1 IM1 is similar to that of CH 3 O 2 with F radical, CH 3 O 2 with ClO radical, CF 3 O 2 with OH radical, and other such radical–radical reactions . Energetically, 1 IM1 is rather stable with a relative energy of −100.61 kJ/mol.…”

“…Thus, the design of possible products should be rational. To get a more complete understanding of this atmospheric chemistry, several related radical–radical reactions have been compared. Based on our calculations, the title reaction could take place through seven possible singlet pathways and seven possible triplet pathways.…”

“…Several experimental data for CH 3 O 2 reactions with molecules or radicals, such as O 3 , NO, NO 2 , ClO, IO, Cl, and Br, have been reported. There are also some theoretical researches on the kinetics or mechanisms of CH 3 O 2 reactions with F, Cl, Br, NO, ClO, IO, and HO 2 . It is worth noting that the reaction of CH 3 O 2 with OH radical is one of the most important degradation processes in the atmosphere.…”

Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase

“…and in general are believed to accelerate ozone loss by recycling halogen atoms and producing (at least in part) alkoxy radicals (6a), that will react with O 2 to form HO 2 radicals 8,9 X + O 3 -XO + O 2 (7) RO + O 2 -R -H O + HO 2 (8) HO 2 + O 3 -OH + 2O 2 (9) Indeed, the reaction of XO with CH 3 O 2 has been studied for ClO, 8,[10][11][12][13][14][15][16][17][18] BrO [19][20][21] and IO [22][23][24] as well as for other XO with RO 2 systems. 25 The reaction between ClO and CH 3 O 2 (10) is believed to be important in the winter polar stratosphere, 8,9 where it recycles Cl and also makes HO 2 and a number of potential product channels have been proposed.…”

Computational study on mechanisms and pathways of the atmospheric C2H5O2 + IO reaction

“…Based on previous and our current theoretical results, for all intermediates formed in the RO 2 + XO (R = H, CH 3 , C 2 H 5 ; X = Cl, Br, I) reactions [12,13,[21][22][23][24][25][26], the order of relative stability among the ROOOX isomers (i.e., HOOOCl, HOOOBr, HOOOI, CH 3 OOOCl, CH 3 OOOBr, CH 3 OOOI, C 2 H 5 OOOCl, C 2 H 5 OOOBr, and C 2 H 5 OOOI) from the most stable to the least stable structure is ROXO 2 > ROOOX > ROOXO > RXO 3 . This implies that the substitution effect of alkyl and halogen makes no significance in RO 3 X surfaces.…”