E. Appelman, A. J. Downs, C. Gardner
Jan 26, 1989
Citations
0
Influential Citations
6
Citations
Journal
The Journal of Physical Chemistry
Abstract
The infrared spectrum of the hypofluorous acid molecule, HOF, trapped in different solid matrices at low temperatures shows that the vibrational fundamentals {nu}{sub 1} and {nu}{sub 2} are perturbed to extents that vary with the basicity of the adjacent molecule, D, and the appearance of absorptions attributable to librational motions of the D{hor ellipsis}H-OF unit implies the formation of specific hydrogen-bonded complexes in some cases. As the matrix concentration of HOF increases, aggregation occurs to give (HOF){sub 2} and higher multimers. Exposure of HOF isolated in an Ar matrix to broad-band ultraviolet radiation results in photodissociation with the formation of two products thought to be O{hor ellipsis}(HF){sub 2} and O{sub 2}{hor ellipsis}(HF){sub 2} in proportions dependent on the concentration of HOF. Photolysis of HOF trapped in a reactive matrix results in oxygenation of the matrix molecules, X, and complexation of the product XO by HF; e.g. X = N{sub 2}, CO, O{sub 2}, or CH{sub 4}. The CO, O{sub 2}, or CH{sub 4} matrices also yield on photolysis small but significant amounts of FCO{sup {sm bullet}}, O{sub 2}F{sup {sm bullet}}, or CH{sub 3}{hor ellipsis}HF, respectively, products that signal the intervention of fluorine atoms. Photolysis of an Ar matrix including HOFmore » together with a potential substrate, Y, at concentrations > 1% results exclusively in oxygenation, and not fluorination, to give YO (Y = PF{sub 3}, AsF{sub 3}, or H{sub 2}O). The results are discussed in relation to the mechanisms likely to govern the matrix photochemistry of HOF.« less