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Inner-shell excitation spectra of GeCl 4 , SnCl 4 , PCl 3 and AsCl 3 were obtained in gas phase at room temperature with a total ion-yield technique at the LURE Super ACO and DCI storage rings in Orsay. The inner-shell excitation spectra include Ge 2p, Sn 2p, P 1s, As 2p, and Cl 1s in GeCl 4 , SnCl 4 , PCl 3 and AsCl 3 , respectively, and are interpreted in the framework of the potential barrier concept, according to electric dipole selection rules. The well-resolved below-edge features in the metal 2p excitation spectra of GeCl 4 and SnCl 4 show a similar shape. Moreover, complementary experimental results of ETS with the support of MS-X α calculations are reported and correlated with the C 1s, Si 2p, Ge 2p and Sn 2p term values of the lowest vacant orbitals for CCl 4 , SiCl 4 , GeCl 4 and SnCl 4 , respectively, in order to study the trend of the stabilization energy of the various empty orbitals in the neutral and in the core ionized molecules. The P 1s spectrum of PCl 3 has been assigned and the As 2p spectrum of AsCl 3 compared with the published P 2p spectrum of PCl 3 . The 1s excitation spectra of the chlorine ligand in the tetrachloride (GeCl 4 , SnCl 4 and trichloride (PCl 3 , AsCl 3 ) series are very sensitive to the change of symmetry and bonding. A linear correlation between (MCl) bond lenght (with M Ge, Sn, P, As) and the energy of the Cl 1 s → σ ∗ (MCl) shape resonance observed above the Cl is ionization threshold has been obtained. |
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