Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 3, Issue 22, Pages 3399-3403Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz301585c
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- Division of Chemical Sciences, Geosciences, and Biosciences, the Office of Basic Energy Sciences, the U.S. Department of Energy
- National Nuclear Security Administration [DE-AC04-94-AL85000]
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The formation of I atom and Criegee intermediate (CH2OO) in the reaction of CH2I with O-2 has potential relevance for aerosol and organic acid production in the marine boundary layer. We report measurements of the absolute yield of I atom as a function of pressure for N-2, He, and O-2 buffer at 298 K. Although the overall rate coefficient is pressure-independent, the I-atom yield, correlated with CH2OO, decreases with total pressure, presumably because of increased stabilization of CH2IOO. The extrapolated yield of the I + Criegee channel under tropospheric conditions is small but nonzero, similar to 0.04. The zero-pressure limiting 1-atom yield is unity, within experimental error, implying negligible branching to IO + CH2O. The apparent collision efficiency of O-2 in stabilizing CH2IOO is a remarkable factor of 13 larger than that of N-2, which suggests unusually strong interaction or possible reaction between the chemically activated CH2IOO# and O-2.
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