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 04:00:00 EDT 2009 · Journal of Physical Chemistry A, 113(42):11273-11288

DOI:https://doi.org/10.1021/jp9082008· OSTI ID:970358

Li, Shenggang; Zhai, Hua Jin; Wang, Lai S; Dixon, David A

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 Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 970358
• Report Number(s): PNNL-SA-68756; 25396; 20691; KP1704020
• Journal Information: Journal of Physical Chemistry A, 113(42):11273-11288, Journal Name: Journal of Physical Chemistry A, 113(42):11273-11288 Journal Issue: 42 Vol. 113
• Country of Publication: United States
• Language: English

Related Subjects

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
ANIONS
BONDING
ELECTRON DETACHMENT
ELECTRONS
EXCITATION
EXCITED STATES
Environmental Molecular Sciences Laboratory
FUNCTIONALS
GROUND STATES
OXIDES
PHOTOELECTRON SPECTROSCOPY
PHOTONS
SPECTRA
SPIN
SYMMETRY
TRANSITION ELEMENTS
http://pubs.acs.org/doi/full/10.1021/jp9082008