Electronic Structure of the 3d Metal Monoxide Anions

Abstract

The electronic and geometrical structure of the ground and excited states of the 3d metal monoxide anions ScO-, TiO-, VO-, CrO-, MnO-, FeO-, CoO-, NiO-, CuO-, and ZnO- were calculated using density functional theory and different formulations of generalized-gradient approximations for the exchange-correlation potential. It was found that the anion states with low- and high-spin multiplicities with respect to the ground-state spin multiplicities of the corresponding neutral parents are stable toward autodetachment of the extra electron. All the low-spin multiplicity anion states are more stable than the high-spin ones, except for that of CrO-, whose ground state appears to be a high-spin multiplicity state. Computed electron affinities of the neutral monoxides are in good agreement with the experimental values obtained by laser photoelectron spectroscopy. It is shown that pure density functional methods are generally superior to a hybrid Hartree−Fock density-functional-theory approach, except for reproducing bond rupture energies.

Photoelectron Spectroscopy of Nickel, Palladium, and Platinum Oxide Anions

“…The Pt-O bond length in the anion was found to be 1.778Å while that of the neutral was shorter at 1.707Å. This bond contraction of 0.071Å is in excellent agreement both with the analysis above and with the contraction calculated for ONiO (40). Table 8 shows calculated frequency values that agree very well with the experimental values, when scaled by an empirical 0.93 factor.…”

“…Assuming a symmetric linear molecule, the Pt-O bond length changes by 0.07 ± 0.01Å upon electron detachment. If OPtO behaves as calculated (40) for ONiO, then this change would correspond to shortening of the Pt-O bond upon electron detachment. For further details, see Ref.…”

“…Experimental data exist for ONiO and OPtO (14,15,39), and a few theoretical studies have calculated molecular structures and electronic properties (26,29,40). Several photoelectron spectroscopic studies have been carried out on similar metal molecules, including CuO − (41,42), (45).…”

Ground and low‐lying excited C2v states of FeO2—A challenge to computational methods

“…MRCI energies for the septet states are not available. The vertical excitation energies for septet states obtained with the DFT, CC, and TD-DFT methods range from 3.9 to 4.7 eV for 1 7 given in Table IV Tables III and IV, many higher states have been obtained in the MRCI calculations that were performed for six roots of each irrep.…”

Density Functional Theory Study of trans‐Dioxo Complexes of Iron, Ruthenium, and Osmium with Saturated Amine Ligands, trans‐[M(O)2(NH3)2(NMeH2)2]2+ (M=Fe, Ru, Os), and Detection of [Fe(qpy)(O)2]n+ (n=1, 2) by High‐Resolution ESI Mass Spectrometry

“…[48] In the B3LYP optimized quintet state, the O-Fe-O asymmetric and symmetric stretching frequencies drop to 656 and 533 cm À1 , respectively, owing to lengthening of the Fe À O bond.…”