Photodetachment anisotropy for mixed s-p states: 8/3 and other fractions.

An approximate model for analytical prediction of photoelectron angular distributions in anion photodetachment from mixed s-p states is presented. Considering the dipole-allowed s, p, and d free-electron partial waves, the model describes photodetachment anisotropy in terms of the fractional p character of the initial orbital and the A and B coefficients describing the relative intensities of the p → d to p → s and s → p to p → s channels, respectively. The model represents an extension of the central-potential model to an intermediate regime encompassing varying degrees of s and p contributions to the initial bound orbital.

Photoelectron angular distributions in negative-ion photodetachment from mixed sp states.

We describe an approach for constructing analytical models for the energy-dependence of photoelectron angular distributions in the one-electron, non-relativistic approximation. We construct such a model for electron emission from an orbital described as a superposition of s- and p-type functions, using linearly polarized light. In the limits of pure s or pure p electron photodetachment or photoionization, the model correctly reproduces the familiar Cooper-Zare formula.

Solvation effects on angular distributions in H- (NH3)n and NH2(-) (NH3)n photodetachment: role of solute electronic structure.

We report 355 and 532 nm photoelectron imaging results for H(-)(NH(3))(n) and NH(2)(-)(NH(3))(n), n = 0-5. The photoelectron spectra are consistent with the electrostatic picture of a charged solute (H(-) or NH(2)(-)) solvated by n ammonia molecules. For a given number of solvent molecules, the NH(2)(-) core anion is stabilized more strongly than H(-), yet the photoelectron angular distributions for solvated H(-) deviate more strongly from the unsolvated limit than those for solvated NH(2)(-).

Further evidence for resonant photoelectron-solvent scattering in nitrous oxide cluster anions.

The effects of anion solvation by N(2)O on photoelectron angular distributions are revisited in light of new photoelectron imaging results for the NO(-)(N(2)O)(n), n = 0-4 cluster anions at 266 nm. The new observations are examined in the context of the previous studies of O(-) and NO(-) anions solvated in the gas phase by nitrous oxide [Pichugin; et al. J.

Photoelectron imaging: an experimental window into electronic structure.

Photoelectron imaging is finding increasingly widespread use in probing electronic structure and chemical dynamics. In this tutorial review, two benchmark systems, H(-) and I(-), are used to introduce essential concepts linking photoelectron images of negative ions with parent electronic structure. For pedagogical reasons, a qualitative approach based upon spectroscopic selection rules is emphasized in interpreting the images.

Solvent resonance effect on the anisotropy of NO(-)(N(2)O)(n) cluster anion photodetachment.

Photodetachment from NO(-)(N(2)O)(n) cluster anions (n< or =7) is investigated using photoelectron imaging at 786, 532, and 355 nm. Compared to unsolvated NO(-), the photoelectron anisotropy with respect to the laser polarization direction diminishes drastically in the presence of the N(2)O solvent, especially in the 355 nm data. In contrast, a less significant anisotropy loss is observed for NO(-)(H(2)O)(n).