ANALYTICAL SCIENCES APRIL 1993, VOL. 9 Manabu FUJIWARAT, Takayuki MATSUSHITA and Shigero IKEDA X-Ray Photoelectron Spectroscopy of Copper(II) Complexes with Donor Sets of O 4, N 2 O 4, N 2 O 2, N 4, N 2 S 2, and S 4

The X-ray photoelectron spectra on the first row transition metal (2p)'s in oxides or complexes with paramagnetism have frequently been found to have some satellite peaks in the higher energy regions above each main peak. These satellite peaks were assigned to the shake up transitions from 3d to 4s of metal orbitals and/or the charge transfer transitions from metal 3d orbitals to anti-bonding orbitals of ligand.

X-ray Photoelectron Spectra of Copper(II) Complexes For the more common oxidation states of copper it is generally agreed that copper(II) will demonstrate satellite structure in the 2p spectral region (except possibly with certain sulfur donor ligand), while copper(I) will show no satellite structure. Earlier papers attributed the presence or absence of satellite structure in transition-metal XPS directly to the presence or absence of unpaired electrons in the complex. Theoretical attempts to explain the satellite structure in transition- metal systems, especially copper(II), have invoked a charge- transfer mechanism which leads to satellite states. In this case the criterion for the possibility of observing satellite structure is the presence of a partially filled (or empty) d shell, although this does not apparently necessitate the presence of a satellite of observable intensity. Inorganic Chemistry, Vol. 15, No. 2, 1976

Quantitative Chemical State XPS Analysis of First Row Transition Metals, Oxides and Hydroxides M C Biesinger et al 2008 J. Phys.: Conf. Ser Shake up lines are common with paramagnetic states. Multiplet splitting arises when an atom has unpaired electrons (eg.Cr(III) – 3p 6 3d 3 ). When a core electron vacancy is made by photoionization, there can be coupling between the unpaired electron in the core with the unpaired electrons in the outer shell. This can create a number of final states which will be seen in the photoelectron spectrum.

交通大學 - 材料科學與工程學系 潘扶民 化學分析電子儀概論

Cu - ligand complex shake-up transition σ→σ*