Atmospheric chemistry of CF2ClO2: a theoretical study on mechanisms and kinetics of the CF2ClO2 + HO2 reaction.

Abstract

The singlet and triplet potential energy surfaces of the HO2 with CF2ClO2 reaction have been probed at the BMC-CCSD/cc-pVTZ level according to the B3LYP/6-311++G(d,p) level obtained geometrical structure. On the singlet PES, the association/dissociation, direct H- abstraction, and SN2 displacement mechanisms have been taken into account. On the triplet PES, SN2 displacement and indirect H- abstraction reaction mechanisms have been investigated and the H- abstraction channel makes more contribution to the CF2ClO2 with HO2 reaction. The rate constants have been computed at 10-10 to 1010 atm and 200-3000 K by RRKM-TST theory. The results show that at T ≤ 600 K, the generation of IM1 (CF2ClO4H) by collisional deactivation is dominant pathway; at high temperatures, the production of P8 (CF2ClOOH + O2(3Σ)) becomes predominate. The predicted data for CF2ClO2 + HO2 agrees closely with available experimental value. Moreover, OH radicals act as inhibitors in the CF2ClOOH→CF2O + HOCl and CF2ClOOH→CFClO + HOF reactions. The dominant products for the reaction of CF2ClOOH + OH are CF2ClO2 + H2O.