Theoretical modeling study of the reaction H + CF 4 → HF + CF 3

The high-temperature hydrogenation of CF4 in mixtures and H2 is assumed to involve the reaction H + → HF CF3. hydrogen atoms here are either formed by F CF3 (i.e., products thermal dissociation CF4) with H2, or H2. In former case, a complicated chain process started, while proceeds more direct way latter. This article determines rate constant CF3, characterizing its transition state quantum-chemical methods. Over temperature range 1000–3000 K, most accurate results for can be represented form 1.64 × 1014 (T/1000 K)1.95 exp(−178.8 kJ mol–1/RT) cm3 mol–1 s–1, based on coupled cluster theory extrapolated complete basis set limit, incorporating vibrational anharmonicity, electron correlation through CCSDT(Q), relativistic non-Born–Oppenheimer effects.