Low-Lying Electronic States of M₃O₉- and M₃O₉²- (M = Mo, W).

Journal Article · Thu Nov 01 04:00:00 EDT 2007 · Journal of Physical Chemistry, 111(38):11093-11099

DOI:https://doi.org/10.1021/jp074187t· OSTI ID:921825

Li, Shenggang; Dixon, David A

The research described in this product was performed in part in the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory. Multiple low-lying electronic states of M₃O₉- and M₃O₉²- (M = Mo, W) arise from the occupation of the near-degenerate low-lying virtual orbitals in the neutral clusters. We used density functional theory (DFT) and coupled cluster theory (CCSD(T)) with correlation consistent basis sets to study the structures and energetics of the electronic states of these anions. The adiabatic and vertical electron detachment energies (ADEs and VDEs) of the anionic clusters were calculated with 27 exchange-correlation functionals including one local spin density approximation functional, 13 generalized gradient approximation (GGA) functionals, and 13 hybrid GGA functionals, as well as the CCSD(T) method. For Mo₃O₉-, CCSD(T) and nearly all of the DFT exchange-correlation functionals studied predict the 2A1 state arising from the Jahn-Teller distortion due to singly occupying the degenerate e' orbital to be lower in energy than the ²A₁' state arising from singly occupying the nondegenerate a₁' orbital. For W₃O₉-, the ²A₁' state was predicted to have essentially the same energy as the ²A₁' state at the CCSD(T) level with core-valence correlation corrections included and to be higher in energy or essentially isoenergetic with most DFT methods. The calculated VDEs from the CCSD(T) method are in reasonable agreement with the experimental values for both electronic states if estimates for the corrections due to basis set incompleteness are included. For M₃O₉²-, the singlet state arising from doubly occupying the nondegenerate a₁' orbital was predicted to be the most stable state for both M ) Mo and W. However, whereas Mo₃O₉²- was predicted to be less stable than Mo₃O₉-, W₃O₉²- was predicted to be more stable than W₃O₉-.

• 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: 921825
• Journal Information: Journal of Physical Chemistry, 111(38):11093-11099, Journal Name: Journal of Physical Chemistry, 111(38):11093-11099 Journal Issue: 38 Vol. 111
• Country of Publication: United States
• Language: English

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36 MATERIALS SCIENCE
CALCULATION METHODS
ELECTRONIC STRUCTURE
Environmental Molecular Sciences Laboratory
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