A variable energy photoelectron study of the valence and Hg 5d levels of Hg(CH3)2

Abstract

A variable energy photoelectron study of the valence levels and I 4d core levels of CF3I J. Chem. Phys. 85, 3840 (1986); 10.1063/1.450904 Photoelectron study of the valence level cross sections of XeF2 from 21 to 50 eV photon energy J. Chem. Phys. 84, 3603 (1986); 10.1063/1.450196 304 Å photoelectron spectra of atomic Hg, Tl, and Pb 5d levels; interaction of open shellsUsing monochromatized synchrotron radiation, the gas phase photoelectron spectra of the Hg 5d and valence levels ofHg(CH 3 h have been obtained between 21 and 100 eV photon energies. Experimental valence band branching ratios have been compared with theoretical branching ratios from MS-Xa calculations. Our results strongly suggest that the ordering of valence levels is 20; < 3a; < 2e' < 2e", rather than 20; < 3a; < 2e" < 2e' from previous theoretical calculations. For the 3a; orbital, two shape resonances are predicted at 30 and 50 eV kinetic energy. Only the one at 30 eV is observed. Interchannel coupling with Hg 5d photoemission is important for the outermost 20; and 3a; orbitals. Shape resonances and interchannel coupling strongly suggest that He II:He I cross section ratios cannot generally be used to infer orbital character. TheHg 5d intensity ratio in Hg(CH 3 )2 differs from that of atomic Hg in the low photon energy region. This effect is probably due to the differences in the outgoing/wave potential between Hg and Hg(CH 3 h