Vibronic coupling in the superoxide anion: the vibrational dependence of the photoelectron angular distribution.

We present a comprehensive photoelectron imaging study of the O(2)(X  (3)Σ(g)(-),v(')=0-6)←O(2)(-)(X  (2)Π(g),v(")=0) and O(2)(a (1)Δ(g),v(')=0-4)←O(2)(-)(X  (2)Π(g),v(")=0) photodetachment bands at wavelengths between 900 and 455 nm, examining the effect of vibronic coupling on the photoelectron angular distribution (PAD). This work extends the v(')=1-4 data for detachment into the ground electronic state, presented in a recent communication [R. Mabbs, F. Mbaiwa, J. Wei, M. Van Duzor, S. T. Gibson, S. J. Cavanagh, and B. R. Lewis, Phys. Rev. A 82, 011401(R) (2010)]. Measured vibronic intensities are compared to Franck-Condon predictions and used as supporting evidence of vibronic coupling. The results are analyzed within the context of the one-electron, zero core contribution (ZCC) model [R. M. Stehman and S. B. Woo, Phys. Rev. A 23, 2866 (1981)]. For both bands, the photoelectron anisotropy parameter variation with electron kinetic energy, β(E), displays the characteristics of photodetachment from a d-like orbital, consistent with the π(g)(∗) 2p highest occupied molecular orbital of O(2)(-). However, differences exist between the β(E) trends for detachment into different vibrational levels of the X  (3)Σ(g)(-) and a (1)Δ(g) electronic states of O(2). The ZCC model invokes vibrational channel specific "detachment orbitals" and attributes this behavior to coupling of the electronic and nuclear motion in the parent anion. The spatial extent of the model detachment orbital is dependent on the final state of O(2): the higher the neutral vibrational excitation, the larger the electron binding energy. Although vibronic coupling is ignored in most theoretical treatments of PADs in the direct photodetachment of molecular anions, the present findings clearly show that it can be important. These results represent a benchmark data set for a relatively simple system, upon which to base rigorous tests of more sophisticated models.