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

Abstract

The mechanisms of the reaction of lanthanide ions (Ce+ and Pr+) 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−1 (for MECP1) and 69.17 cm−1 (for MECP2) for the SOC constants indicates that the spin crossing process in Ln+ + CO2 (1∑) reaction can be occurred efficiently because of the large SOC involved. And the O-atom affinities (OA) testified that the argumentation is thermodynamically allowed. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011