Detection of valences of a element using XRF and LIBS?

[xhtp2000]

Dear all, I have two questions for you:
1: As in known, in the case for transition and rare Earth elements, different valences lead to totally different properties. It is said that XRF can only detect the concentration of a certain element, but can not distinguish the valences of this element. Is there anyone who can tell me why? Because the wavelength of the fluorescence emission depends on the difference between the core and outer energy state and in different combined state i.e. different valences of the element, this difference between the core and outer energy state should also be different. Is that because the resolution of detector can not tell this slim difference?
2: In the case of laser-induced breakdown spectroscopy, the electrons are excited to quasi-free electrons due to the ionization during that breakdown process, can this state of electrons be described as sth. similar to Bosse-Einstein state as for photons? The excited electrons will come back to the valence state afterwards, this valence state should be different in different combined state? If yes, then the wavelength of emission should also be different, and if this difference detectable using high resolution spectrograph?

Thanks so much!

 

[BigJDubs]

1: XRF can distinguish the concentration of an element, but it cannot tell the difference between the different valences of that element. This is because the wavelength of the fluorescence emission is determined by the difference between the core and outer energy state of the atom, and the resolution of the detector is not high enough to distinguish the differences between the different valences.2: Laser-induced breakdown spectroscopy (LIBS) excites electrons to quasi-free electrons due to the ionization process during the breakdown. This excited state is not the same as the Bose-Einstein condensate of photons, but it is still a quantum mechanical state where the electrons are in a superposition of several different energy levels. When the electrons come back to the valence state afterwards, they will have different wavelengths of emission depending on the valence state. However, the resolution of the spectrograph may not be high enough to detect these slight differences.