ENERGY-DEPENDENCE OF THE OUTER CORE-LEVEL MULTIPLET STRUCTURES IN ATOMIC MN AND MN-CONTAINING COMPOUNDS

We consider the energy dependence of the Mn 3s and 3p multiplets from gas-phase atomic Mn and crystalline MnF2 and KMnF3 over the range from x-ray photoelectron spectroscopy (XPS) energies down to energies near threshold. First comparing atomic and solid-state spectra for these m ultiplets permits concluding that the splittings in the compounds MnF2 , MnO, and Cd0.3Mn0.7Te are highly atomic in character, with no signif icant effects due to extra-atomic screening. Measuring the energy depe ndence for atomic Mn, MnF2, and KMnF3 then shows for both the 3s and 3 p multiplets that there is a decrease in the intensities of the higher -binding-energy quintet states relative to those of the corresponding septet states as the excitation energy is lowered. This effect on the quintet:septet branching ratios is also found to extend to rather high energies, with the ratios at the XPS limit of almost-equal-to 1400 eV above threshold being approximately 25-30 % greater than those at alm ost-equal-to 200 eV above threshold. We show that this energy-dependen t final-state branching ratio is not due simply to spin-dependent dipo le matrix elements as derived from single-configuration Hartree-Fock c alculations. We suggest that this effect is caused by the sudden-to-ad iabatic transition, which at lower energies favors the exchange-stabil ized septet states that are the ground states of the ions formed. Howe ver, two prior theoretical models for such sudden-to-adiabatic intensi ty changes [Stohr, Jaeger, and Rehr, Phys. Rev. Lett. 51, 821 (1983) a nd Thomas, Phys. Rev. Lett. 54, 182 (1985)] were not found to describe our results well, particularly in the extension of the effect to high er energies. We consider qualitatively a configuration-interaction mod el with quintet-septet interchannel coupling that may better describe these effects and form the basis for more quantitative calculations.