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

作者：Liu, Hui-Wen; Wang, Yong-Cheng^*; Geng, Zhi-Yuan; Lv, Ling-Ling; Yan, Bing; Wang, Qiang; Cui, Dan-Dan

来源：Journal of Molecular Structure (Theochem), 2010, 944(1-3): 89-96.

DOI：10.1016/j.theochem.2009.12.031

• Density functional theory (DFT)
• Reaction mechanism
• Minimum-energy crossing point (MECP)
• Spin-orbit coupling (SOC)

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+ (F-3, D-1) with N2O (X-1 Sigma) including several reaction pathways and numerous isomers, leads to oxidation, LaO+ ((1)Sigma, (3)Delta) + N-2 (X-1 Sigma(+)(g)) or nitration, LaN+ ((2)Sigma(+), (4)Sigma(+)) + NO (X-1 Pi). 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 (P-1(ISC)) and double (P-2(ISC)) passes are estimated at MECP are approximately 6.682 x 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.

• 出版日期2010-3-30
• 单位西北师范大学; 吉林大学