Theoretical analysis on reactions between syn‐methyl Criegee intermediate and amino alcohols

Abstract

AbstractDue to their strong zwitterionic character, Criegee intermediates can interact strongly with hydrogen bonding molecules in the atmosphere, such as water vapor, alcohols, acids, amines, and thiols. To gain a physical understanding of the reactivity of Criegee intermediates toward these molecules, we theoretically studied the reaction of syn‐CH3CHOO with linear n‐amino alcohol and branched amino alcohols that contain three carbon atoms. We found that the interaction contribution is the determining factor for the increase in reactivity when we elongate the alkyl chain length and when we place a methyl group in the amino group. This finding was rationalized by evaluating the electron‐donating ability of the amino alcohol. Consistent with the increase in reactivity for NH(CH3)C2H4OH and NH2C4H8OH compared to NH2C2H4OH, we found that these two amino alcohols have vertical ionization energies ~0.5 eV smaller than NH2C2H4OH.