Molecular Structures and Energetics of the (ZrO₂)n and (HfO₂)n (n = 1-4) Clusters and Their Anions
Journal Article
·
· Journal of Physical Chemistry A, 114(7):2665-2683
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.
- Research Organization:
- Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 1001485
- Journal Information:
- Journal of Physical Chemistry A, 114(7):2665-2683, Journal Name: Journal of Physical Chemistry A, 114(7):2665-2683 Journal Issue: 7 Vol. 114; ISSN 1089-5639; ISSN 1520-5215; ISSN JPCAFH
- Country of Publication:
- United States
- Language:
- English
Similar Records
Structural and Electronic Properties of Reduced Transition Metal Oxide Clusters, M 3 O 8 and M 3 O 8 - (M = Cr, W), from Photoelectron Spectroscopy and Quantum Chemical Calculations
Probing the Electronic and Structural Properties of Chromium Oxide Clusters (CrO3)n- and (CrO3)n (n=1-5): Photoelectron Spectroscopy and Density Functional Calculations
Structural and Electronic Properties of Reduced Transistion Metal Oxide Clusters, M3O8 and M3O8- (M=Cr, W), from photoelectron spectroscopy and quantum chemical calculations
Journal Article
·
Mon Sep 28 00:00:00 EDT 2009
· Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
·
OSTI ID:1001530
Probing the Electronic and Structural Properties of Chromium Oxide Clusters (CrO3)n- and (CrO3)n (n=1-5): Photoelectron Spectroscopy and Density Functional Calculations
Journal Article
·
Wed Apr 16 00:00:00 EDT 2008
· Journal of the American Chemical Society, 130(15):5167-5177
·
OSTI ID:934641
Structural and Electronic Properties of Reduced Transistion Metal Oxide Clusters, M3O8 and M3O8- (M=Cr, W), from photoelectron spectroscopy and quantum chemical calculations
Journal Article
·
Thu Oct 22 00:00:00 EDT 2009
· Journal of Physical Chemistry A, 113(42):11273-11288
·
OSTI ID:970358