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The compounds RMn2Si2 (R = Sm, Tb) with tetragonal ThCr2Si2 − type structure was studied. XRD analysis showed the presence of the intermetallic phase other than tetragonal crystal lattice, with a fraction of less than 3%. Experiments on resonant photoemission were performed, and the partial densities of Sm 4f, Tb 4f, and Mn 3d states, which form a valence band in the layered intermetallic RMn2Si2 (R = Sm, Tb), were found. When the energy of the exciting photons coincides with the binding energy of the internal level of the atom, the yield of photoemission from the valence state of this atom is resonantly enhanced by tens times. The main mechanisms of the decay of photoexcited states of rare- earth and transition elements are determined. [ABSTRACT FROM AUTHOR]