Structural and Electronic Properties of Reduced Transistion Metal Oxide Clusters, M3O8 and M3O8- (M=Cr, W), from photoelectron spectroscopy and quantum chemical calculations
We report a comparative study of reduced transition metal oxide clusters, M3O8- (M = Cr, W) anions and their neutrals, via anion photoelectron spectroscopy (PES) and density functional theory (DFT) and molecular orbital theory (CCSD(T)) calculations. Well-resolved PES spectra are obtained for M3O8- (M = Cr, W) at 193 and 157 nm photon energies. Different PES spectra are observed for M = Cr versus M = W. Extensive DFT and CCSD(T) calculations are performed to locate the ground and low-lying excited states for the neutrals and anions. The ground states of Cr3O8 and Cr3O8- are predicted to be the 3B2 and 4B2 states of a C2v structure, respectively, revealing ferromagnetic spin coupling for Cr 3d electrons. In contrast, the ground states of W3O8 and W3O8- are predicted to be the 1A- state (Cs symmetry) and the 2A1 state (C2v symmetry), respectively, showing strong metal-metal d-d bonding in the anion. The current cluster geometries are in qualitative agreement with prior DFT studies at the PBE level for M = Cr and the B3LYP level for M = W. The BP86 and PW91 functionals significantly outperform the B3LYP functional for the Cr species, in terms of relative energies, electron detachment energies, and electronic excitation energies; whereas the B3LYP functional is better for the W species. In addition, accurate heats of formation for the ground states of M3O8 are calculated from the clustering energies and the heats of formation of MO2 and MO3.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 970358
- Report Number(s):
- PNNL-SA-68756; 25396; 20691; KP1704020; TRN: US1001019
- Journal Information:
- Journal of Physical Chemistry A, 113(42):11273-11288, Vol. 113, Issue 42
- Country of Publication:
- United States
- Language:
- English
Similar Records
Benchmark Calculations of Energetic Properties of Groups 4 and 6 Transition Metal Oxide Nanoclusters Including Comparison to Density Functional Theory
Benchmark Calculations on the Electron Detachment Energies of MO₃⁻ and M₂O₆⁻ (M = Cr, Mo, W)
Related Subjects
ANIONS
BONDING
ELECTRON DETACHMENT
ELECTRONS
EXCITATION
EXCITED STATES
FUNCTIONALS
GROUND STATES
OXIDES
PHOTOELECTRON SPECTROSCOPY
PHOTONS
SPECTRA
SPIN
SYMMETRY
TRANSITION ELEMENTS
http://pubs.acs.org/doi/full/10.1021/jp9082008
Environmental Molecular Sciences Laboratory