Angle-Resolved Auger Spectroscopy as a Sensitive Access to Vibronic Coupling.

In the angle-averaged excitation and decay spectra of molecules, vibronic coupling may induce the usually weak dipole-forbidden transitions by the excitation intensity borrowing mechanism. The present complementary theoretical and experimental study of the resonant Auger decay of core-to-Rydberg excited CH_{4} and Ne demonstrates that vibronic coupling plays a decisive role in the formation of the angle-resolved spectra by additionally involving the decay rate borrowing mechanism. Thereby, we propose that the angle-resolved Auger spectroscopy can in general provide very insightful information on the strength of the vibronic coupling.

Symmetry-forbidden electronic state interference observed in angularly resolved NO+ (A 1Π) deexcitation spectra of the N*O(2σ(-1)2π(2)) resonance.

Quantum mechanical interference between different pathways in inner-shell resonance excitation-deexcitation spectra is a realization of a double-slit experiment on the atomic scale. If the intermediate inner-shell resonances are of different symmetries, this interference is symmetry forbidden in the solid-angle-averaged or magic-angle-recorded deexcitation spectra. It has, however, been suggested that interference may by observable in off-magic-angle-recorded spectra. Here, we prove this interference in angularly resolved deexcitation spectra of the 2σ(-1)2π(2)(2Δ,2Σ±) resonances of N*O by a quantitative comparison between ab initio calculations and experiment.

Raman regime energy dependence of alignment and orientation of KrII states populated by resonant Auger effect.

The energy dependencies of alignment parameters A20 for KrII 4p(4)5p states after the Auger decay of the KrI 3d(9)np resonances were investigated theoretically and experimentally for the first time in the Raman regime with the bandwidth of the exciting radiation (deltaE(FWHM)=20 meV) smaller than the natural width of the resonances (Gamma approximately 80 meV). The observed energy dependence is due to the in-terference between the different resonance channels and the direct photoionization channel. A strong energy dependence for both the orientation parameter O10 and the photoelectron angular distribution parameter beta(el) is also predicted.