| Description |
The lanthanide (Ln) series consist of the elements in the f-block of the periodic table and have properties that set them apart from other elements. The thermochemistry and reactivity of Ln+ metals with various small molecules in the gas phase (i.e., O2, CO2, CO, H2, D2, and HD) can provide insight in their application for atmospheric release experiments and as potential catalysts. Additionally, quantum chemical calculations for these heavy metals are complicated by spin-orbit and relativistic effects. The work in this dissertation examines the reactions of the lanthanide cations Ce+, Nd+, and Pr+ with small neutrals in the gas phase using guided ion beam tandem mass spectrometry (GIBMS). The kinetic energy-dependent reaction cross sections are modeled using a modified line-of-centers model, and experimental bond dissociation energies (BDEs) are obtained. Potential energy surfaces (PESs) for the reactions of Ce+, Pr+, and Nd+ with H2 and its isotopologues are examined to obtain insight into the insertion reaction of the Ln+ with H2. Moreover, quantum chemical calculations are performed to provide additional insight into the reaction mechanism and the electronic configuration required for the formation of various product species. Theoretically calculated BDEs are then compared with the experimentally derived BDEs to establish benchmarks for evaluating theoretical methods for these Ln+ metals. These results obtained are then used to establish periodic trends and provide insight into the reactivity, mechanism, and electronic configuration of the Ln+ BDEs. |
