Infrared Spectroscopic Observation of the Stabilized Intermediate Complex FO₃ Formed by Reaction of Mobile Fluorine Atoms with Ozone Molecules Trapped in an Argon Matrix

Abstract

Chemical reaction of F atoms with O 3 molecules in a solid argon matrix was studied with FTIR spectroscopy. Fluorine atoms were generated by UV photolysis of F 2 molecules in dilute solutions of F 2 and O 3 in solid argon. The FO-O 2 complex is observed for the first time as an intermediate product by reaction of mobile F atoms with isolated ozone molecules. The observed complex is characterized by two intense absorption bands at 1522 and 968 cm -1 . Use of isotopic mixtures 16 O/ 18 O provides strong evidence for assignment of these bands to the O-O stretch and F-O stretch fundamentals of the complex, which are red-shifted by 34 and 61 cm -1 , respectively, from the corresponding values for O 2 and FO. Photolysis at 532 nm leads to decay of the FO-O 2 complexes and to the appearance of isolated free FO radicals.

Das Trifluormethyltrioxyradikal, CF3OOO

“…Das Wasserstofftrioxyradikal (HOOO) konnte in der Gasphase6 und anschließend auch in Edelgasmatrix7 identifiziert werden. Berichtet wurde außerdem über die Bildung von FOOO durch Reaktion von Fluoratomen mit Ozon in einer Argonmatrix 8. Ein experimenteller Nachweis von Trioxyradikalen mit organischen Substituenten wie CH 3 oder fluorhaltigen Substituenten wie CF 3 steht allerdings noch aus.…”

Photochemistry in the charge transfer and neutral excited states of HCl in Xe and Kr matrices

“…The broad linewidth of the Xe n H emission band in Fig. [43][44][45] The fragments in our case were generated by HCl dissociation, and the lightinduced migration can lead with a high probability to geminate recombination. 35 The nonradiative relaxation from the excitation energy to the energy of the emitting center deposits, in addition, a significant amount of energy locally.…”

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“…The change of the UV spectrum is displayed in Figure 11. These findings can be interpreted as follows: On photolysis of ClO 3 in Ne matrix, a complex of the composition ClO ⋅ O 2 in analogy to the FO ⋅ O 2 complex215 is formed, which is characterized by two UV bands (see Figure 11) and an IR band at 839.5 cm −1 . Additionally, a second ClOO 2 species is formed, which is assigned to a ClO radical situated next to an oxygen molecule in the same Ne matrix cage showing a weaker interaction.…”