Energetic Properties, Spectroscopy, and Reactivity of NF₃O

The heats of formation of NF₃O and similar C, S, and Si systems are predicted using the accurate composite computational chemistry Feller-Peterson-Dixon (FPD) method. The harmonic vibrational frequencies at the CCSD(T)/aug-cc-pVTZ level are reported and compared to the experimental values for NF₃O, its isoelectronic species CF₃O^- and NF₄⁺, and NF₃. The infrared intensities were calculated at the MP2/aug-cc-pVTZ level and show that the infrared absorption is predicted to be like those of CF₂Cl₂ and SF₆ within a factor of ∼2. The calculated heats of formation are in good agreement with the available experimental values. These heats of formation are used to calculate a range of bond dissociation energies (BDEs). It is predicted that NF₃O is unlikely to decompose either thermally or photolytically in the troposphere. The potential energy curves for the decomposition of NF₃O to NF₂O + F are all repulsive, as are the channels to form NF₃ and either O³P or O¹D. The predicted persistence of NF₃O in the troposphere is attributed to the high barrier of its reaction with the OH radical and that light with the wavelength needed for its photodissociation will not reach the troposphere. Reliable experimental measurements of the global warming potential of NF₃O are needed to confirm our predictions that NF₃O is like NF₃ in this respect.