HIGH-RESOLUTION GE 3D AND SN 4D CORE-LEVEL PHOTOELECTRON-SPECTRA - LIGAND-FIELD AND VIBRATIONAL EFFECTS

High-resolution (almost-equal-to 0.1 eV) Ge 3d and Sn 4d photoelectron spectra of eleven Ge and Sn gas-phase molecules (GeH4, GeF4, (CH3)xGe Cl4-x (x=0, 2, 3, 4), (CH3)xSnCl4-x (x=0, 1, 3, 4) and (CH3)6 Sn2) hav e been recorded using monochromatized synchrotron radiation. The Ge 3d spectrum of GeH4 yields total 3d3/2 and 3d5/2 linewidths of 0.26 eV, and very little evidence of vibrational structure. However, all other molecules show splitting and/or broadening of the d levels which is du e to three different effects: the direct interaction of inner-valence F 2s and Cl 3s levels with the core d orbitals (e.g. in GeF4 and SnCl4 ); vibrational broadening of the d levels (e.g. in the tetrahedral spe cies GeF4, SnCl4, GeCl4, (CH3)4Sn and (CH3)4Ge); and broadening of the d levels due to ligand field splitting in the non-tetrahedral molecul es (e.g. (CH3)xMCl4-x) (x=1, 2, 3,), M=Ge, Sn).