Theoretical models for the interpretation of E.S.C.A. spectra

Three features of E.S.C.A. spectra are discussed: the chemical shift, multiplet splitting, and satellite bands. In the chemical shift effect a perturbation theory treatment shows that the electronic relaxation energy in the hole state of the molecules can be attributed to a flow of electrons on to the ionized atom. Thus the relative abilities of surrounding atoms to "feed" electrons to the ionized atom determines the relative importance of the relaxation energy contribution to the chemical shift. This explains why neutral atom charges don't always determine the direction of the chemical shift. In multiplet splitting the same perturbation treatment shows that the sign and magnitude of the relaxation energy contribution to the multiplet splitting is determined by the direction and magnitude of flow of majority electron spin density in going to the relaxed hole state. Unrestricted Hartree-Fock calculations on the series MF ₂, with M first row transition metals, are compared with E.S.C.A. experiments on the corresponding octahedral complexes to show that complex ion formation has only a very small effect on core level multiplet splitting. Relaxed hole state calculations on a series of first row atom (C,N,O,F) containing radicals leads to the conclusion that in these cases correlation energy effects are larger for the high spin multiplets than for the low spin multiplets. The assignments of satellite structure in transition metal complexes is reviewed and multiconfiguration self-consistent field results are presented and discussed for the satellite structure.