Gas-Phase Reactions of Atomic Lanthanide Cations with CO2 and CS2: Room-Temperature Kinetics and Periodicities in Reactivity

Abstract

Gas-phase reactions of atomic lanthanide cations (excluding Pm+) have been surveyed systematically with CO2 and CS2 using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Observations are reported for reactions with La+, Ce+, Pr+, Nd+, Sm+, Eu+, Gd+, Tb+, Dy+, Ho+, Er+, Tm+, Yb+, and Lu+ at room temperature (295 +/- 2 K) in helium at a total pressure of 0.35 +/- 0.02 Torr. The observed primary reaction channels correspond to X-atom transfer (X = O, S) and CX2 addition. X-atom transfer is the predominant reaction channel with La+, Ce+, Pr+, Nd+, Gd+, Tb+, and Lu+, and CX2 addition occurs with the other lanthanide cations. Competition between these two channels is seen only in the reactions of CS2 with Nd+ and Lu+. Rate coefficient measurements indicate a periodicity in the reaction efficiencies of the early and late lanthanides. With CO2 the observed trends in reactivity across the row and with exothermicity follow trends in the energy required to achieve two unpaired non-f valence electrons by electron promotion within the Ln+ cation that suggest the presence of a kinetic barrier, in a manner much like those observed previously for reactions with isoelectronic N2O. In contrast, no such barrier is evident for S-atom transfer from the valence isolectronic CS2 molecule which proceeds at unit efficiency, and this is attributed to the much higher polarizability of CS2 compared to CO2 and N2O. Up to five CX2 molecules were observed to add sequentially to selected Ln+ and LnX+ cations.