Semiempirical structure analysis for long-wave X-ray emission satellites. 2. Period II and III transition-element hydrides

Conclusions

Comparison with OCM calculations shows that the Rydberg states and states in the continuum are very important in configuration interaction for the hydrides, which is due to the very small numbers of vacant MO included in the CI basis (only one each for HF and HCl). Therefore, the hydrides are the most inconvenient substances for LWS structure calculations for x-ray spectra by this method. Nevertheless, here again the role of the vacant MO in the CI is important. One naturally expects that the role of those MO will increase considerably as their number increases (see in particular [17]).

The conclusions are that for lines corresponding to transitions from the upper filled MO, the long-wave satellites have little effect on the spectrum shape but alter the intensities by 3–7%. As one proceeds to the deeper MO, the role of the LWS increases rapidly, and leads in fact to the diagram lines vanishing. For the hydrides, that range begins with the MO for which the ionization potentials are 15–20 eV. Here one gets the L spectra of the corresponding elements with complicated LWS. One can say that at these ionization potentials, one gets a multielectron limit, beyond which the one-electron approach to interpreting the spectra becomes inadequate. The K_{α, β} spectra for these compounds are almost undistorted by long-wave satellites, and one can use the changes in intensity ratio in the K spectra for the interacting compounds to draw conclusions on the participation of the orbitals in the bonding.