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

Phys Rev Lett. 2016 May 13;116(19):193002. doi: 10.1103/PhysRevLett.116.193002. Epub 2016 May 12.

Abstract

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.