Photoelectron Spectroscopy of Nickel, Palladium, and Platinum Oxide Anions |
| |
Authors: | Tanya M RamondGustavo E Davico,Fredrik HellbergFredrik Svedberg,Peter Salé nPatrick Sö derqvist,W.Carl Lineberger |
| |
Affiliation: | JILA, University of Colorado and National Institute of Standards and Technology, and Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado, 80309-0440 |
| |
Abstract: | The 364-nm negative ion photoelectron spectra of XO and OXO molecules (X=Ni, Pd, and Pt) are reported. The spectra yield the electron affinities (EAs): EA(NiO)=1.455±0.005 eV; EA(PdO)=1.672±0.005 eV; EA(PtO)=2.172±0.005 eV; EA(ONiO)=3.043±0.005 eV; EA(OPdO)=3.086±0.005 eV; EA(OPtO)=2.677±0.005 eV. In addition, for the diatomics, transitions from the anion X?2Π3/2 and X?′2Π1/2 states into neutral X?3Σ−, 3Π, and for NiO and PdO, 1Π, are assigned. Several states have been reassigned from those in the existing literature. Anion 2Π3/2-2Π1/2 spin-orbit splittings are measured, as are neutral 3Π2-3Π1 spin-orbit splittings: the XO 3Π 2-3Π1 splittings increase from 405±30 cm−1 (NiO) to 805±30 cm−1 (PdO) to 3580±40 cm−1 (PtO). A bond length shortening of 0.03±0.01 Å is measured upon electron detachment from NiO−, resulting in an anion bond length of 1.66±0.01 Å. The bond length does not change upon electron detachment from PdO− using 3.4-eV photons. The Pt-O bond length decreases by 0.035±0.010 Å in the 3Π1←2Π3/2 transition. The spectrum of OPtO displays a significantly more extended vibrational progression than those of ONiO or OPdO, and the O-Pt bond length is found to decrease by 0.07±0.01 Å upon electron detachment. The spectra support the view that the Ni-O bond is largely ionic, the Pd-O bond is somewhat less so, and the Pt-O bond displays a substantial covalent character. |
| |
Keywords: | transition-metal oxides |
本文献已被 ScienceDirect 等数据库收录! |
|