Abstract

Relative partial photoionization cross sections as a function of photon energy, over the range 20–110 eV, have been measured for the valence bands of Cr(CO) 6, Mo(CO) 6 and W(CO) 6. All three t 2g −1 bands show a very pronounced increase in intensity at photon energies ( hv) corresponding to np resonant absorption (Cr(CO) 6, hv = 52.5 eV, n = 3; Mo(CO) 6, hv = 48 eV, n = 4; W(CO) 6, hv = 44 and 53 eV, n = 5). The other valence bands show a small intensity increase at similar energies. Observation of such resonant photoemission provides an unambiguous method for assignment of nd bands in the photoelectron spectra of gas-phase molecules.

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