MATRIX PHOTOIONIZATION OF BROMOFORM AND CHLORINE SUBSTITUTED HALOFORMS

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1977

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Ohio State University

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Dilute samples of bromoform in argon were deposited onto a $15^\circ K$ cesium iodide sample window while exposed to the radiation from a microwave discharge of argon. Several product bands observed in the infrared spectrum were susceptible to subsequent photolysis by the filtered light of a high pressure mercury are lamp. Bands at 734 1205 and 2733 $cm^{-1}$, which disappeared after exposure to 300--1000 nm light, were assigned to $CHBr_{2}{^{-}}$ which is consistent with the spectrum of $CHCl_{2}{^{-}}$ reported by Jacox and Milligan. Other bands at 898 and 1227 $cm^{-1}$, which decreased in intensity following exposure to 220--1000 nm light were assigned to $CHBr_{2}$ which was also consistent with the earlier work. In addition, bands attributable to $CBr_{3}$ and $CBr_{3}{^{+}}$ grew substantially with photolysis in these systems. The chlorine substituted reagents $CHClBr_{2}$ and $CHCl_{2}Br$ gave products which were analogous to the pure bromo and chloro products and deuterium substitution produced the expected shifts for all of the products observed.""

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Author Institution: Department of Chemistry, University of Virginia

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