Elucidating cerium + H2O reactivity through electronic structure: A combined PES and DFT study

摘要: Abstract The anion photoelectron (PE) spectra of CexOyHz− products formed in sequential reactions between cerium oxide and hydroxide with water are presented interpreted supporting density functional theory calculations. PE (x = 2, 3) complexes the sequence initiated CexOx− + H2O, exhibit a prominent photodetachment transition indicating that highest occupied molecular orbital these species can be described as combinations Ce 6s atomic orbitals. electrons diffuse orbitals reliably have low binding energies range 0.6–1 eV. combination poor overlap energy is amenable to ionic OH bond formation water, rather than O formation, which observed more reduced clusters 5d-based Spectral simulations based on computational results, predict numerous close-lying spin states arising from singly 4f each center, support specific structural assignments for Ce2OyHz− cluster series. A Ce3OyHz− also characteristic 6s-based MO transition. Based comparison calculations stable hydride structures, we infer Ce3OyHz− + H2O proceeds along path metastable structures.