A theoretical study of the reaction of La + with N 2O in the gas phase

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 N 2O ( X 1∑) including several reaction pathways and numerous isomers, leads to oxidation, LaO + ( 1∑, 3Δ) + N 2 ( X 1 ∑ g + ) or nitration, LaN + ( 2∑ +, 4∑ +) + NO ( X 1∏). The attack of the La + on the O-end of N 2O 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 ( P 1 ISC ) and double ( P 2 ISC ) 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.