Theoretical calculation of atmospheric reactions. The case of CH 3–CH xOH(CH 3) 1−x–CH y(CH 3) 3−y, ( x = 1,0; y = 2,1) + Cl

Abstract

In this work, the reactions of Cl with a series of secondary alcohols: 2-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, and 2,3-dimethyl-2-butanol have been studied through ab initio Möller–Plesset second order perturbation treatment (MP2) calculations with 6-311G ∗∗ basis sets. Optimized geometries and vibrational frequencies have been obtained for transition states and molecular complexes appearing along the different reaction pathways. Furthermore, molecular energies have been calculated at Quadratic Configuration Interaction with Single, Double, and Triple Excitations (QCISD(T)) level in order to get an estimation of activation barriers. The theoretical rate constant was also calculated for the main reaction pathways using the Transition State Theory. The main aim of this work is to extend, from a theoretical point of view, the knowledge of this kind of reactions that play a significant role in atmospheric chemistry.