| dc.description.abstract | The environmental impact and fate of vinyl butyrate (CH2=CHOC(O)CH2CH2CH3 or VB),
commonly used in the polymer industry and daily-life materials, necessitate a comprehensive
understanding of its chemical transformation in the atmosphere. Herein, we theoretically
investigated the atmospheric OH-initiated oxidation of VB using the stochastic Rice–
Ramsperger–Kassel–Marcus (RRKM)-based master equation kinetic model on the potential
energy surface explored at M06-2X/aug-cc-pVTZ level. Showing an excellent agreement with
limited experimental kinetic data, the model reveals that H-abstraction from C
(-C
H2CH3)
prevails over the OH-addition to the double bond (C=C), even at low temperatures. The
detailed analyses, including those of the time-resolved species profiles, reaction rate, and
reaction flux, reveal the reaction mechanism shift with temperature and the noticeable
pressure dependence of k(T, P) at low temperatures. Additionally, the secondary chemistry
under atmospheric conditions, involving the reaction of the main product with O2 and
subsequent reactions with NO, was characterized, revealing the dominant products of [4-
(ethenyloxy)-4-oxobutan-2-yl]oxidanyl (IM12) + NO2. These findings indicate that VB is not
a persistent organic pollutant but highlight the formation of NO2 as a new environmental
concern. Moreover, through TD-DFT calculations, it is shown that several important species
(1-(ethenyloxy)-1-oxobutan-2-yl (P4), [4-(ethenyloxy)-4-oxobutan-2-yl]dioxidanyl (IM7),
and IM12) can potentially undergo photolysis. | en_US |
