A quantum theory investigation on atmospheric oxidation mechanisms of acrylic acid by OH radical and its implication for atmospheric chemistry.

Abstract

The hydroxyl radical, as the most important oxidant, controls the removal of some volatile organic compounds (VOCs) in the atmosphere. In this work, the atmospheric oxidation processes of acrylic acid by OH radical have been investigated by density functional theory (DFT). The energetic routes of the reaction of CH2CHCOOH with OH radical have been calculated accurately at the CCSD(T)/cc-pVTZ//M06-2X/6-311++G(d,p) level. It is implicated that the oxidation has five elementary reaction pathways mostly hinging on how hydroxyl radical approaches to the carbon skeleton of acrylic acid. The atmospheric degradation mechanisms of the CH2CHCOOH by OH radical are the formation of reactive intermediates IM1 and IM2. Meanwhile, the further oxidation mechanisms of IM1 and IM2 by O3 and NO are also investigated. The rate coefficients have been computed using tight transition state theory of the variflex code. The calculated rate coefficient is 2.3×10-11cm3molecule-1s-1 at standard pressure and 298K, which is very close to the laboratory data (1.75 ± 0.47×10-11cm3molecule-1s-1). Moreover, the atmospheric lifetime of acrylic acid is about 6h at 298K and 1atm, implying that the fast sinks of acrylic acid by hydroxyl radical.