Quantum-chemical and kinetic study of the reactions of the ClSO2 radical with H, O, Cl, S, SCl and ClSO2 in the atmosphere of Venus

ADELA E. CROCE; CARLOS J. COBOS

Computational and Theoretical Chemistry

Elsevier

Lugar: Amsterdam; Año: 2018 vol. 1140 p. 14 - 23

2210-271X

Rate constants for the reactions between the ClSO2 radical and H, O, Cl, S, SCl and ClSO2 were studied over the 150?700 K temperature range employing the statistical adiabatic channel model/classical trajectory approach and the canonical transition state theory on potential energy surfaces based on G4//B3LYP/6-311++G(3df,3pd) calculations. For these processes the following rate constants (in cm3 molecule−1 s−1) are predicted:2.71 x 10-11 (T/250)0.47 (ClSO2+H→HCl+SO2); 7.69 x 10-11(T/250)0.093 (ClSO2+O→Cl+SO3); 1.44 x 10-11 (T/250)0.47 (ClSO2+Cl→Cl2SO2); 6.73 x 10-11(T/250)0.18 (ClSO2+S→SCl+SO2); 9.38 x 10-13(T/250)0.75 (ClSO2+SCl→ClS(O2)SCl); 2.64 x 10-14(T/250)0.61 (2 ClSO2→(O2)ClSSCl(O2)). These data are in marked contrast with those normally used for the modeling of the lower and middle atmosphere of Venus. Therefore, in the absence of experimental and theoretical investigations, the above rate constants are proposed for these studies.