Structures, Vibrational Spectra, and Relative Energetics of CH3COIO3 Isomers

Abstract

Abstract The structures, vibrational spectra, relative energetics, and enthalpies of formation of CH3COIO3 isomers have been investigated with B3LYP, B3P86 and B3PW91 methods in conjugation with the 6‐31+G(d), 6‐311+G(d,p) and 6‐311++G(3df,3pd) basis sets. The CH3COOIO2 structure was found to be the most stable form among the isomers with an estimated enthalpy of formation of −314.6 kJ·mol−1. The enthalpies of formation for CH3COOOOI, CH3COOOIO and CH3COIO3 are −180.7, −184.9 and −50.6 kJ·mol−1, respectively. The implication of the formation of CH3COIO3 isomers from the atmospheric cross‐reactions of the acetylperoxy (CH3COO2) and iodine monoxide (IO) radicals was examined and the possible dissociation products of the most likely CH3COIO3 isomers were determined.