PNNL

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. 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-.