L. Cooper et al., A study of the threshold photoelectron spectra and the photoionisation yield curves of the silicon tetrahalides, CHEM PHYS, 270(2), 2001, pp. 363-381
The threshold photoelectron spectra and the photoionisation yield curves of
SiF4, SiCl4 and SiBr4 have been recorded in the photon energy range 10-240
eV using synchrotron radiation. The outer valence shell photoelectron band
s exhibit effects due to spin-orbit splitting and to Jahn-Teller interactio
ns, and vibrational progressions associated with the Jahn-Teller active mod
es have been observed. The continuous nature of the inner valence shell pho
toelectron bands and the absence of main-lines demonstrates the importance
of electron correlation in redistributing the intensity amongst satellite s
tates. New Rydberg series have been observed in the photoionisation yield c
urves associated with excitation from the valence shell, and the improved r
esolution has allowed some earlier assignment discrepancies to be clarified
. The threshold photoelectron spectra and ion yield curves recorded at high
er energies display features attributable to the Si 2p,2s, Cl 2p and Br 3p
shells. The photoelectron spectra have enabled the following splittings to
be measured: Si 2p-2s, Si 2p(1/2)-2p(3/2), Cl2p(1/2)-2p(3/2) and Br 3p(1/2)
-3P(3/2), and the corresponding values are 51.21, 0.52, 1.62 and 4.6 eV, re
spectively. The interpretation of the features observed in the SiBr4 spectr
a has been based upon previously reported assignments of similar structure
in SiF4. (C) 2001 Elsevier Science B.V. All rights reserved.