Electronic and Structural Evolution and Chemical Bonding in Ditungsten Oxide Clusters: W₂On⁻ and W₂On (n = 1-6)
Journal Article
·
· Journal of Physical Chemistry A, 109(27):6019-6030
We report a systematic and comprehensive investigation of the electronic structures and chemical bonding in a series of ditungsten oxide clusters, WOn⁻ and WOn (n = 1-6), using anion photoelectron spectroscopy and density functional theory (DFT) calculations. Well-resolved photoelectron spectra were obtained at several photon energies (2.331, 3.496, 4.661, 6.424, and 7.866 eV) and W 5d-based spectral features were clearly observed and distinguished from O 2p-based features. More complicated spectral features were observed for the oxygen-deficient clusters due to the W 5d electrons. With increasing oxygen content in WOn⁻, the photoelectron spectra were observed to shift gradually to higher binding energies, accompanied by a decreasing number of W 5d-derived features. A behavior of sequential oxidation as a result of charge transfers from W to O was clearly observed. A large energy gap (2.8 eV) was observed in the spectrum of WO₆⁻, indicating the high electronic stability of the stoichiometric WO₆ molecule. Extensive DFT calculations were carried out to search for the most stable structures of both the anion and neutral clusters. Time-dependent DFT method was used to compute the vertical detachment energies and compare to the experimental data. Molecular orbitals were used to analyze the chemical bonding in the ditungsten oxide clusters and elucidate their electronic and structural evolution.
- 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:
- 15020667
- Report Number(s):
- PNNL-SA-45650; 3227a; 3568; KP1303000
- Journal Information:
- Journal of Physical Chemistry A, 109(27):6019-6030, Journal Name: Journal of Physical Chemistry A, 109(27):6019-6030 Journal Issue: 27 Vol. 109
- Country of Publication:
- United States
- Language:
- English
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