It seems X-ray absorption spectroscopy is usually ascribed to the interation between photons and inner electrons. Does it mean inner electrons are much preferred by X-ray photons to outer electrons? If so, why? Thank you very much!
From the wikipedia article on x-ray absorption spectroscopy:
If you read further you will see that this is a photoelectric effect , where the X-ray scatters and kicks off a bound electron, i.e. a transition from n=1 or 2 or 3 to infinity.
The reason Xrays scatter off inner orbit electrons is because when the frequency of the X-ray is the same as the energy level of the electron it can transition to infinity ( the quantum mechanical probability of transitioning is high) and the result is seen as the absorption of the X-ray at that frequency/energy. X-rays ( as TMS also observed) are too energetic to be absorbed totally by outer electrons. The transition is a quantum effect, i.e the probability of scattering as a compton scattering is very low, and it will not show in the absorption spectrum as a distinct transition.
As you maybe already know, in hydrogen atom energetic levels are proportional to $1/n^2$ where $n$ is main quantum number (orbit number), so the bigger $n$ (the further our orbit) makes $\Delta E$ smaller, thus we need less energy to excite the electron, but as you know X-Ray has relatively high energy, so to be sure that our high energy photon will be absorbed by some electron, we need this electron to have next nearest energetic level relatively far to jump to (remember Bohr's postulates, when election jumps from one orbit to another he will absorb/emit photon with energy equal to the difference of energetic levels that he jumped between)
Now what related to far orbits, electrons there can be excited too, anyway that not because we have "some" photons in our X-Ray with smaller energies, but because electrons can not only jump to nearest orbits but can "skip" couple orbits and jump further if they have excited by high energy photon, anyway, quantum mechanics says that probability of such jump (with skips) is quit small comparing to usual jumping.