Nitrogen matrix reactions of alkaline earth metal atoms with ozone: Infrared spectra of the alkaline earth metal oxide molecules J. Chem. Phys. 62, 2320 (1975); 10.1063/1.430757Matrix reactions of alkali metal atoms with ozone: Infrared spectra of the alkali metal ozonide moleculesThe matrix reactions of copper atoms with ozone have been studied by infrared spectroscopy. Two products were found in the initial deposit: CuO,. which has a strong absorption at 802.3 cm -I, and CuO, which has its main feature, corresponding to the 6'CU l6 0 isotopic species, at 628.0 cm-I in solid argon. Copper atom reactions with oxygen-18,enriched ozone samples were used to obtain species identifications. The CuO J absorption was very similar in frequency and isotopic splitting behavior to alkali and alkaline earth metal ozonide species previously studied in matrices. The CuO frequency is in good agreement with gas phase measurements which put the ground state CuO vibrational fundamental at 631.3 cm-I • Temperature cycling of the Cu-O J matrices leads to CuO. formation by the secondary reaction of CuO with unreacted ozone.

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Trifluoroacetyl fluoride dimerizes at -108°in the presence of CsF to form CF3CO2C2F0. With (CFsfiCFO--Cs+, COF2, CF3C(0)F, C2FóC(0)F, and C3F7C(0)F react to form the heptafluoroisopropyl esters, FCC>2CF(CF3)2, CF3C02CF(CF3)2, 02 0020 (0 3)2, and C3F7C02CF(CF3)2. Although these compounds are formed only at low temperature, when pure they are stable at 25°and above.

Ultraviolet photolysis of fluoroperoxytrifluoromethane, CF3OOF, in argon matrices at 8 °K produced CF4 and a new species, tentatively identified as the CF3OO radical, with infrared absorptions at 1173.7 and 1094.1 cm−1. This species was also produced, along with CF4, CF3OCF3, and COF2, by photolysis of bistrifluoromethyl trioxide, CF3OOOCF3, at wavelengths below 300 nm. In the latter case, extensive isotopic labeling experiments with CF3 16O16O16OCF3, CF3 16O18O16OCF3, CF3 18O16O18OCF3, and CF3 18O18O18OCF3 led to the observation of four distinct isotopic absorptions for the O–O stretching vibration (1094.1 cm), thus confirming the nonequivalent oxygen atom structure of CF3OO.

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