Characterization of hydroperoxymethyl formate by microwave spectroscopy: Molecular insight into aerosol formation
Porterfield, Jessie P.
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https://hdl.handle.net/2142/104521
Description
Title
Characterization of hydroperoxymethyl formate by microwave spectroscopy: Molecular insight into aerosol formation
Author(s)
Porterfield, Jessie P.
Contributor(s)
McCarthy, Michael C.
Carroll, Brandon
Dell'Isola, Valentina
Lee, Kelvin
Issue Date
2019-06-21
Keyword(s)
Atmospheric science
Abstract
Hydroperoxide esters are important products in the class of reactions between Criegee intermediates and carboxylic acids. Such reactions are believed to play key roles in the formation of secondary organic aerosols by producing semivolatile and low-volatility organic compounds. We provide the first definitive evidence for the most fundamental reaction in this class, that between carbonyl oxide \chem{CH_2OO} and formic acid HCOOH to form hydroperoxymethyl formate (HPMF), \chem{HOOCH_2OCHO}. Using a modified continuous flow pulsed reactor, HPMF is characterized in the ozonolysis of ethylene by high resolution Fourier transform microwave spectroscopy. Evidence for the most stable conformer - a seven membered, hydrogen bond stabilized ring - is supported with high level calculations and observation of $^{13}$C isotopologues in natural abundance.
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