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 04:00:00 EDT 2008 · Journal of the American Chemical Society, 130(15):5167-5177

DOI:https://doi.org/10.1021/ja077984d· OSTI ID:934641

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

Photoelectron spectroscopy has been conducted for a series of (CrO3)n- (n = 1-5) clusters and compared with density functional calculations. Well-resolved photoelectron spectra were obtained for (CrO3)n- (n = 1-5) at 193 nm (6.424 eV) and 157 nm (7.866 eV) photon energies, allowing for accurate measurements of the electron binding energies, low-lying electronic excitations for n = 1 and 2, and the energy gaps. Density functional and molecular orbital theory (CCSD(T)) calculations were performed to locate the ground and low-lying excited states for the neutral clusters and to calculate the electron binding energies of the anionic species. The experimental and computational studies firmly establish the unique low-spin, non-planar, cyclic ring structures for (CrO3)n and (CrO3)n- for n ≥ 3. The structural parameters of (CrO3)n are shown to converge rapidly to those of the bulk CrO3 crystal. The extra electron in (CrO3)n- (n ≥ 2) is shown to be largely delocalized over all Cr centers, in accord with the relatively sharp ground state photoelectron bands. The measured energy gaps of (CrO3)n exhibit a sharp increase from n = 1 to n = 3 and approach to the bulk value of 2.25 eV at n = 4 and 5, consistent with the convergence of the structural parameters.

• 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: 934641
• Report Number(s): PNNL-SA-59300; 20691; 19795; KC0301020
• Journal Information: Journal of the American Chemical Society, 130(15):5167-5177, Journal Name: Journal of the American Chemical Society, 130(15):5167-5177 Journal Issue: 15 Vol. 130; ISSN JACSAT; ISSN 0002-7863
• Country of Publication: United States
• Language: English

Related Subjects

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS
CHROMIUM OXIDES
CONVERGENCE
ELECTRONS
ENERGY GAP
EXCITED STATES
Environmental Molecular Sciences Laboratory
FUNCTIONALS
GROUND STATES
PHOTOELECTRON SPECTROSCOPY
PHOTONS
SPECTRA