Journal of Chemical Physics, Vol.117, No.18, 8368-8384, 2002
Vector correlations in dissociative photoionization of O-2 in the 20-28 eV range. II. Polar and azimuthal dependence of the molecular frame photoelectron angular distribution
A combined experimental and theoretical study of the polar and azimuthal dependence of the molecular frame photoelectron angular distributions (MFPADs) for inner-valence-shell photoionization of the O-2 molecule into the O-2(+) (B(2)Sigma(g)(-),3 (2)Pi(u), c (4)Sigma(u)(-)) states is reported. The measured MFPADs, for each orientation of the molecular axis with respect to the linear polarization of the synchrotron radiation, are derived from the spatial analysis of the (Vo+, V-e, P) vector correlation, where the nascent ion and electron velocity vectors Vo+ and V-e are determined for each dissociative photoionization (DPI) event using imaging and time of flight resolved coincidence technique as described in the companion paper of this series [J. Chem. Phys. 114, 6605 (2001)]. Expressed in the general form of four F-LN (theta(e)) functions which contain all the dynamical information about the photoionization processes, they are compared with the MFPADs computed using the multichannel Schwinger configuration interaction method. A very satisfactory agreement is found. When the lifetime of the O-2(+) ionic states is a significant fraction of the rotational period, the rotational motion of the molecule is included in the quantal derivation of the MFPADs. Measured MFPADs are also reported for the additional DPI process identified in Paper I, and for DPI involving the excitation of the neutral (3 (2)Pi(u),4s sigma(g)) Rydberg state.