Knowledge Bank

The thermal decomposition of solid $O2\mathrm{<mrow\; data-mjx-texclass="ORD">+</mrow>}AsF6\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ produces a gas phase species which contains an extremely labile fluorine atom. Studies of the decomposition of similar salts have led to the suggestion that this species may be the $O2F$ radical, a molecule in which the fluorine atom is bound by only $\sim 15$ kcal/mole. Our measurements of the ultra-violet absorption of the decomposition products of $O2\mathrm{<mrow\; data-mjx-texclass="ORD">+</mrow>}AsF6\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ strongly support this hypotheses. Gaseous $O2F$ radicals produced in this fashion can undergo a number of extremely energetic reactions to produce electronically excited fluorides. The reaction of $O2F$ with nitrogen atoms produces electronically excited NF and (by a subsequent reaction) $N2$. Reactions of the radical with halogen atoms produce excited halogen monofluorides which, in the presence of singlet molecular oxygen, emit $B(3\Pi O\mathrm{<mrow\; data-mjx-texclass="ORD">+</mrow>})\to X(1\Sigma +)$ radiation. Using this technique, we have been able to record the $B\to X$ emission spectrum of G1F for the first time. Similar results are obtained for the reaction with bromine atoms. It seems plausible that the study of this and similar reactions can yield a wealth of information regarding the lower excited electronic states of the halogen monofluorides.