In energy dispersive spectroscopy how every element is directly related it's corresponding k l m n series irrespective of their unique atomic structure. It is directly given eds spectra no doubt but it will be interesting to know the element and series relationship irrespective of x rays are given out from shell with ejection of electrons at different levels. Is their any relationship between outer electronic configuration and different series
So, just to recapitulate: your question is why the EDS/EDX peaks are as characteristic and well-localized as they are and why they don't shift due to the outer binding situation?
If that is the question, you have to be aware that you are working with keV-sized incident electron and outgoing photon energies. In XPS (i.e. the reverse effect) the outer shells lead to binding energy shifts in the single eV magnitude (=3 orders of magnitude smaller). The resolution of EDS is much lower than that, see
http://www.globalsino.com/EM/page4652.html
So, there is an influence, but it's so small you can't resolve it. If your sample allows it, XPS is a good option for that.
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