For example, Mn+2 has a lower binding energy peak in XPS compared to Mn+3. However, Ru+3 has a higher binding energy peak in XPS than Ru+4. So what is the general rule that dictates which (higher or lower) oxidation state will have higher binding energy peak in XPS?
It is based on the effective nuclear charge experienced by the core electrons. A higher oxidation state will have a higher binding energy because core electrons will feel a greater effective nuclear charge due to the electron-electron repulsion and a stronger attraction to the nucleus.
There are some references to understanding the principles of XPS binding energies and oxidation states.
1. Oxidation states and chemical shifts in X-ray Photoelectron spectroscopy: An experimental and theoretical study by M.G. Mason DOI: 10.1103/PhysRevB.26.4199
2. Core-Level Binding energies and Oxidation states of Transition Metals: A new perspective by Wagner DOI: 10.1016/0368-2048(79)80005-3
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