Elimination of HF from CH3F by As+ and Bi+: A comparative theoretical study

Kinetics Studies of the Reactions of Main Fourth-Period Monocations (Ga+, Ge+, As+, and Se+) with Methyl Fluoride

“…The previous studies reported for this reaction 18,19 (at the B3LYP level followed by CCSD(T) single-points calculations on the stationary points on the triplet energy PES 19 and CASSCF-MRMP2 level for the triplet and singlet PESs 18 ) present a similar description for the As + + CH 3 F reaction. However, in both cases, the energy barriers are higher than in our predictions.…”

“…However, in both cases, the energy barriers are higher than in our predictions. As we have already commented for the case of the Ge + + CH 3 F reaction, the barriers found for TS5 in these works (28.5 and 8.4 kcal/mol) are not compatible with the experimental rate constant …”

“…However, in both cases, the energy barriers are higher than in our predictions. As we have already commented for the case of the Ge + + CH 3 F reaction, the barriers found for TS5 in these works (28.5 19 + ( 2 B 2 ) + HF] is also the most stable one on the doublet PES, but in this case, it is clearly exothermic (−42.5 kcal/mol at the CCSD(T)/QZVPP//mPW1K/QZVPP level).…”

“…In a recent work, the PESs for the channels evolving from the low-lying electronic states of the reactants in the M + + CH 3 F (M = Ge, As, Se, Sb) reactions have been studied at the CASSCF-MRMP2 level. The formation of AsCH 2 + from the reaction of As + + CH 3 F in the ground state has also been studied employing the B3LYP functional followed by CCSD­(T) single-point calculations on the resulting stationary points. However, it should be stressed that there are no kinetics studies available for these reactions, and consequently, a direct comparison with Zhao et al’s experimental data is not possible.…”