The complete valence shell photoelectron spectrum of the NO2 molecule
has been studied in the binding energy range between 10 and 50 eV. HeI
and HeII resonance radiation as well as monochromated synchrotron rad
iation have been used for the ionisation. Assignments have been made f
or most of the photoelectron bands by comparison with previous theoret
ical predictions. Photoelectron angular distributions and branching ra
tios for the bands associated with the outer valence shell have been d
etermined for photon energies between 18 and 120 eV. The HeI and HeII
excited spectra have allowed detailed studies to be made of the vibrat
ional fine structure. For the X (1)Sigma(g)(+) ground ionic state, clo
se lying vibrational lines associated with combined excitations of the
symmetric nu(1) and the bending nu(2) modes have been observed for th
e first time. Excitation of the asymmetric stretch nu(3) mode, in one
quantum, is found in the A (1)A(2) photoelectron band, and its presenc
e is explained in terms of vibronic coupling. (C) 1998 Elsevier Scienc
e B.V. All rights reserved.