Theoretical study of the reactions of lanthanide ions (Ce⁺, Pr⁺) with CO₂ in the gas phase

Abstract

ABSTRACT:The mechanisms of the reaction of lanthanide ions (Ce þ and Pr þ ) with the carbon dioxide were investigated at the B3LYP level of theory. The crossing points (CPs) between the different potential energy surfaces (PESs) have been located by means of the intrinsic reaction coordinate approach used by Yoshizawa et al., and corresponding minimum energy crossing points (MECPs) that we obtained by the mathematical algorithm proposed by Harvey et al. has also been used. In addition, possible spin inversion processes are discussed by means of spin-orbit coupling (SOC) calculations. The value of 61.68 cm À1 (for MECP 1 ) and 69.17 cm À1 (for MECP 2 ) for the SOC constants indicates that the spin crossing process in Ln þ þ CO 2 ( 1 P þ g ) reaction can be occurred efficiently because of the large SOC involved. And the O-atom affinities (OA) testified that the argumentation is thermodynamically allowed.

Structural, electronic, and magnetoresponsive properties of triangular lanthanide clusters and their free‐standing nitrides

“…[22][23][24][25][26][27] The reactions of the Ce 1 and Pr 1 ions with CO 2 in two spin states have been studied at the B3LYP/SDD(Ce,Pr)|6-3111G(2df)(C,O) level of theory. 28 DFT/B3LYP and HartreeFock effective core potential calculations have been performed to investigate the reactivity of neutral f-block atoms toward methane CÀ ÀH bond activation. 29 Recently, Zhou and coworkers 30 presented a combined matrix isolation infrared spectroscopic and theoretical study (B3LYP) on the reactions of latter lanthanide metal atoms (Gd-Lu) with water.…”