Journal article

A Theoretical Study of the Photoisomerization of Glycolaldehyde and Subsequent OH Radical-Initiated Oxidation of 1,2-Ethenediol

Sui So, Uta Wille, Gabriel da Silva

The Journal of Physical Chemistry A | AMER CHEMICAL SOC | Published : 2015


It has recently been discovered that carbonyl compounds can undergo UV-induced isomerization to their enol counterparts under atmospheric conditions. This study investigates the photoisomerization of glycolaldehyde (HOCH2CHO) to 1,2-ethenediol (HOCH═CHOH) and the subsequent (•)OH-initiated oxidation chemistry of the latter using quantum chemical calculations and stochastic master equation simulations. The keto-enol tautomerization of glycolaldehyde to 1,2-ethenediol is associated with a barrier of 66 kcal mol(-1) and involves a double-hydrogen shift mechanism to give the lower-energy Z isomer. This barrier lies below the energy of the UV/vis absorption band of glycolaldehyde and is also cons..

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