PHOTOCHEMISTRY OF H2O--F2 COMPLEXES IN SOLID ARGON - INFRARED-SPECTRA OF HF--HOF, HO--HF, AND FO--HF COMPLEXES

Codeposition of H2O and F2 in excess argon on a cold window at 12 +/- 1 K gave new absorptions for the Lewis acid-base H2O--F2 complex. Photolysis of this sample with 220-1000-nm light formed several new products. Ab initio calculations using HONDO 7.0 and the DZP basis set were performed to support the identification of new F2 + H2O product complexes. HF--HOF, FH--FOH, and FH--OHF exhibited nu(s)(HF) modes at 3877.9, 3781.3, and 3638.0 cm-1, respectively. The F atom + H2O reaction product, the FH--OH radical complex, showed further growth upon sample annealing to 31 +/- 2 K and a nu(s)(HF) absorption at 3631.9 cm-1; the matrix plays a unique role in the stabilization of FH--OH, which will be difficult to observe in the gas phase. In addition, complexes of OF and OF2 with HF were formed on photolysis and showed marked growth upon sample annealing. This work reveals product species in the stepwise reaction of water and fluorine.