How are the processes of Mass Spectrometry and Photoelectron Spectrometry different/similar?

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How are the processes of Mass Spectrometry and Photoelectron Spectrometry different/similar?

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UV Vis spec light from a source like a xenon flash lamp or tungsten bulb you break the light down with a prism or monochrometer to its spectrum.
Different chemicals absorb light at differing wavelengths. You can quantify concentration comparing change in absorbance.
Mass spec breaks analytes with an electron beam. Fragments get separated by atomic mass. Usually with a Quadrapole. The fragments are specific and can be compared to a spectral library.