Showing papers by "Mary K. Gilles published in 1998"
TL;DR: In this paper, the quantum yields for O(¹D) production in O3 photolysis between 203 and 320 K, and 289 to 329 nm were measured, and a portion of the observed quantum yields at wavelengths greater than 310 nm was attributed to a spin-forbidden channel and the variation of quantum yield with temperature is ascribed to photodissociation of vibrationally (or rotationally excited ozone.
Abstract: The quantum yields for O(¹D) production in O3 photolysis between 203 and 320 K, and 289 to 329 nm were measured. A portion of the observed O(¹D) quantum yields at wavelengths greater than 310 nm is attributed to a spin-forbidden channel and the variation of quantum yield with temperature is ascribed to photodissociation of vibrationally (or rotationally) excited ozone. Our results yield atmospheric O(¹D) production rates larger than those obtained from current recommendations, especially at high solar zenith angles, low temperatures, and large overhead ozone columns.
95 citations
TL;DR: In this article, the role of closed-ring intermediates in chemistry, in general, and focuses on recent experimental and theoretical works that provide compelling evidence for a five-membered ring intermediate in the gas phase.
Abstract: This review considers the role of closed-ring intermediates in chemistry, in general, and focuses on recent experimental and theoretical works that provide compelling evidence for a fivemembered ring intermediate in the gas phase. The reactions of oxygen atoms with ethyl iodide and larger alkyl iodides produce HOI and a corresponding ethylenic compound via attack of the oxygen atom at the iodine and closure of the five-membered ring between the oxygen and a hydrogen on the beta-carbon. Detailed results are gathered from infrared chemiluminescence and molecular beam scattering, as well as new kinetics and product yield experiments. The theoretical calculations fully support and characterize the novel reaction mechanism.
10 citations