A theoretical study of the reaction of La+ with N2O in the gas phase

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 (X1∑) including several reaction pathways and numerous isomers, leads to oxidation, LaO+ (1∑, 3Δ) + N2 (X1∑g+) or nitration, LaN+ (2∑+, 4∑+) + NO (X1∏). 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 (P1ISC) and double (P2ISC) 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.