Molecular Structures and Energetics of the (ZrO2)(n) and (HfO2)(n) (n=1-4) Clusters and Their Anions

作者：Li Shenggang; Dixon David A^*

来源：Journal of Physical Chemistry A, 2010, 114(7): 2665-2683.

DOI：10.1021/jp910310j

The group IVB transition-metal dioxide Clusters and their anions, (MO2)(n) and (MO2)(n)(-) (M = Zr, Hf; n = 1-4), are Studied with Coupled Cluster (CCSD(T)) theory and density functional theory (DFT). Similar to the results for M = Ti, these oxide Clusters have a number of low-lying isomeric structures, which can make it difficult to predict the ground electronic state especially for the anion. Electron affinities for the low-lying structures are calculated and compared with those for M = Ti. Electron affinities of these clusters depend strongly on the Cluster structures. Anion photoelectron spectra are calculated for the monomer and dimer and demonstrate the possibility for structural identification at a spectral line width of <= 0.05 eV. Electron excitation energies from the low-lying states to the singlet and triplet excited states are calculated self-consistently, as well as by the time-dependent DFT and equation-of-motion coupled cluster (EOM-CCSD) methods. The calculated excitation energies are compared to the band energies of bulk oxides, indicating that the excitation energy is not yet converged for n = 4 for these clusters. The excitation energies of the low-lying isomeric clusters are less than the bulk metal oxide band gaps and suggest that these clusters could be useful photocatalysts with a visible light Source.

• 出版日期2010-2-25