November 22, 2007
Journal Article

Benchmark Calculations on the Electron Detachment Energies of MO3? and M2O6?
(M = Cr, Mo, W)

Abstract

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. Neutral and anionic molecules of the monomers and dimers of the group VIB transition metal oxides (MO3 and M2O6) were studied with density functional theory (DFT) and coupled cluster CCSD(T) theory. Franck- Condon simulations of the photoelectron spectra were carried out for the transition from the ground state of the anion to that of the neutral molecule. Molecular structures from the DFT and CCSD(T) methods are compared. Electron detachment energies reported in the literature were evaluated. The calculated adiabatic and vertical electron detachment energies (ADEs and VDEs) were compared with the experimental results. CCSD(T) gives results within 0.12 eV for the ADEs. CCSD(T) predicts VDEs that are in error by as much as 0.3 eV for M = Cr. DFT hybrid functionals were found to give poor results for the ADEs and VDEs for M = Cr due to the substantial amount of multireference character in the wavefunction, whereas the pure DFT functionals give superior results. For M = Mo and W, excellent agreement was found for both CCSD(T) and many DFT fucntionals. The BP86 functional yields the best overall results for the VDEs of all the metal oxide clusters considered. Heats of formation calculated at the CCSD(T) level extrapolated to the complete basis set limit are also in good agreement with available experimental data.

Revised: April 7, 2011 | Published: November 22, 2007

Citation

Li S., and D.A. Dixon. 2007. "Benchmark Calculations on the Electron Detachment Energies of MO3? and M2O6? (M = Cr, Mo, W)." Journal of Physical Chemistry A 111, no. 46:11908-11921. doi:10.1021/jp074768i