Electron Spectroscopy of Open-Shell Systems: Spectra of Ni(C5H5)2, Fe(C5H5)2, Mn(C5H5)2, and Cr(C5H5)2

Abstract

The high resolution HeI electron spectra of Ni(C5H5)2, Fe(C5H5)2, Mn(C5H5)2, and Cr(C5H5)2 have been recorded and analyzed in terms of a molecular orbital description of the electronic structure. The ground state electronic configurations have been assigned by considering the feasible ground state configurations, determining the number and type of ionic states obtained from ionization of these configurations, and then comparing the predicted transitions with those observed experimentally. The ground state configuration and adiabatic first ionization potential of these molecules are: Cr(C5H5)2, ··· (e2g)3(a1g)1, 3E2g, I.P.=5.50 eV; Mn(C5H5)2, ··· (e2g)4 (a1g)1, 2A1g, I.P.=6.55 eV; Fe(C5H5)2, ··· (a1g)2 (e2g)4, 1A1g, I.P.=6.72; Ni(C5H5)2, ··· (a1g)2 (e2g)4 (e1g)2, 3A2g, I.P.=6.2 eV. Vibrational structure has been observed in the spectrum of ferrocene and is assigned to progressions in ν4, the symmetric ring-metal stretching mode.