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Abstract: The spin-forbidden reaction mechanism of Ir+ with CH3F to yield H2 or HF has been investigated using density functional theory (DFT) calculations. The overall H2 elimination reaction is calculated to be exothermic, by 36.3 kcal/mol. One pathway is found on three potential energy surfaces (PESs), whereas the HF-elimination reaction is exothermic by 32.8 kcal/mol, two reaction pathways are identified on the quintet and triplet surfaces, only one reaction pathway is identified on the singlet surface. The reaction mechanism can be explained by the simple donor–acceptor model. According to the revealed mechanism and the calculated potential energy surfaces, H2-elimination is energetically much more favorable than HF-elimination. These conclusions are consistent with the experimental observations. [Copyright &y& Elsevier]

Abstract: Activation of the N–N and N–O bonds by La+ in nitrous oxide has been examined systematically using both DFT and CCSD(T) methods. The calculated results indicate that the reaction of La+ (3F, 1D) with N2O (X 1∑) including several reaction pathways and numerous isomers, leads to oxidation, LaO+ (1∑, 3Δ)+N2 () or nitration, LaN+ (2∑+, 4∑+)+NO (X 1∏). The attack of the La+ on the O-end of N2O involves intersystem crossing (ISC) between singlet and triplet state potential-energy surfaces (PESs). Thus, possible spin-inversion process is discussed by means of spin–orbit coupling (SOC) calculations. The probability values of the single () and double () passes are estimated at MECP are approximately 6.682×10−2 and 0.125, respectively. The calculated results also revealed that the O-transfer reaction is energetically more favorable than the N-transfer reaction on the both spin state PESs. These results are in good agreement with experimental observations. [Copyright &y& Elsevier]