The CeO(2)(+) Cation: Gas-Phase Reactivity and Electronic Structure

"Bare" CeO(2)(+) ions can be prepared in the gas phase by consecutive oxidation of Ce(+) with O(2) and NO(2). The ability to activate saturated and unsaturated hydrocarbons is investigated by use of Fourier-transform ion cyclotron resonance mass spectrometry. In the reactions of CeO(2)(+) with linear and branched alkanes C-H bond activation is observed almost exclusively. In contrast, both oxygen-atom transfer and C-H bond activation processes occur when thermalized CeO(2)(+) cations react with simple alkenes and aromatic compounds. C-C bond activation is not observed at all. Insight into the structural and electronic properties of neutral CeO(2) and cationic CeO(2)(+) is provided by means of quasirelativistic density-functional and ab initio pseudopotential calculations. They reveal a (2)Sigma(u)(+) ground state for CeO(2)(+) which is best described as a linear cerium dioxide with a resonating pi bond. Finally, we discuss the influence of oxo ligands on the chemistry of the cationic CeO(n)()(+) (n = 0-2) species toward hydrocarbons.     

Wave operators and similarity of certain non-normal one-parameter groups

This paper starts from a self-adjoint Schrödinger operator H(0) for three particles. If the interaction is dilation-analytic, H(0) has an analytic continuation H() (>0). G(t,) (–(±,a,) defined as strong limits, when t±, of t-dependent operators. The wave operators establish transformations under which the subgroups are similar to unitary groups. The scattering matrix determined by G(t,) is diagonal with respect to a.This work was supported in part by the National Science Foundation under grant DMS-8301096.