Dmp. Holland et al., An experimental and theoretical study of the valence shell photoelectron spectrum of bromobenzene, CHEM PHYS, 252(1-2), 2000, pp. 257-278
The valence shell photoelectron spectrum of bromobenzene has been studied,
both experimentally and theoretically, in order to characterise the main ba
nds due to single-hole states and to assess the importance of electron corr
elation in the formation of satellite states. Synchrotron radiation has bee
n employed to measure photoelectron angular distributions and branching rat
ios in the photon energy range 16-120 eV, and high-resolution spectra have
been recorded using HeI excitation. The results indicate that the 2b(1) and
the 6b(2) lone-pair orbitals retain their atomic properties to a substanti
al degree, and that the photoionisation dynamics associated with these two
orbitals exhibit effects due to the presence of a Cooper minimum. The resul
ts for bromobenzene are compared with corresponding data for benzene and it
appears that several of the orbitals remain essentially unperturbed by the
introduction of the halogen atom. The high-resolution spectra have enabled
detailed assignments to be made of the vibrational structure displayed in
the (X) over tilde(2)B(1), (A) over tilde(2)A(2), (B) over tilde B-2(2), (C
) over tilde(2)B(1) and (K) over tilde(2)A(1) photoelectron bands. Two vari
ations of the many-body Green's function method have been employed to evalu
ate the ionisation energies and pole strengths (relative intensities) of al
l valence states. These predictions have helped assign and interpret the fe
atures caused by configuration interaction. (C) 2000 Elsevier Science B.V.
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