Temperature effects in x-ray photoelectron spectra of paramagnetic cupric and iron complexes with anomalous magnetic properties

The temperature dependence of the XPS spectra of paramagnetic cupric and iron complexes with anomalous magnetic properties is studied. It was found that the XPS spectra of polynuclear complexes with antiferromagnetic interaction, such as cupric acetate, do not change with temperature, although their magnetic moments diminish essentially. The Fe 2p spectra of mononuclear iron (III) complexes with the spin multiplicity transitions S = $\text{1}\text{2}$ ? S = $\text{5}\text{2}$ exhibit temperature-dependent reversible alterations of shake-up satellite intensity which correlate with the spin state of the paramagnetic Fe(III) ion. The results obtained prove the mechanism of appearance of intensive shake-up satellites in XPS spectra of paramagnetic 3d element complexes, which relates shake-up excitations with the interaction of the photoelectron with unpaired valence 3d electrons during photoionization.