Frontier molecular orbital correlations for predicting rate constants between alkenes and the tropospheric oxidants NO3, OH and O3

Abstract

Two types of correlation relating the value of the energy of the highest occupied molecular orbital (HOMO) of an alkene to the logarithm of its rate constant for reaction with NO₃, OH or O₃ have been formulated. Both correlations have been shown to be consistent with frontier molecular orbital theory. The correlation can be used to predict the rate constants for the reaction of an alkene with NO₃, OH or O₃ by calculating the value of the HOMO energy of the alkene. The accuracy of these predictions is quoted as a 48, 40 and 97% minimum probability that the predicted rate constant for reaction of an alkene with NO₃, O₃ and OH, respectively, will be within a factor of two of the measured rate constant. This probability is increased to a minimum of 73, 80 and approaches 100% for the reactions of NO₃, O₃ and OH, respectively, with conjugated dienes.