HOSO+X(X=F,Cl,Br)的反应机理及电子密度拓扑分析

Abstract

The reaction mechanisms of the reactions between HOSO and X(X=F, Cl, and Br) were investigated at the CCSD(T)/6-311++G(d, p)//MP2/6-311++G (d, p) level. The geometries of the reactants, transition states and the products were optimized at the MP2/ 6-311++G (d, p) level. The intrinsic reaction coordinates were traced according to Fukuis theory and the relationships between the transition states, the reactants and the products confirmed. The single point energies of the species were corrected at the CCSD(T)/ 6-311++G(d, p) level. Reaction rate constants were calculated over a temperature range of 200-3000 K using classical transition state theory and canonical variational transition state theory combined with a small-curvature tunneling correction. The results show that the HOSO+X(X= F, Cl and Br) reaction could occur in the singlet and the triplet reaction channels. The singlet reaction channels are dominant and HX + SO₂ are the main products. The formation and breaking of the chemical bond in the main reaction channel was analyzed by topological analysis of the electron density.