Time-resolved X-ray and XUV based spectroscopic methods for nonadiabatic processes in photochemistry

Abstract

The photochemistry of numerous molecular systems is influenced by conical intersections (CIs). These omnipresent nonadiabatic phenomena provide ultra-fast radiationless relaxation channels by creating degeneracies between electronic states and decide over the final photoproducts. In their presence, the Born-Oppenheimer approximation breaks down, and the timescales of the electron and nuclear dynamics become comparable. Due to the ultra-fast dynamics and the complex interplay between nuclear and electronic degrees of freedom, the direct experimental observation of nonadiabatic processes close to CIs remains challenging. In this article, we give a theoretical perspective on novel spectroscopic techniques capable of observing clear signatures of CIs. We discuss methods that are based on ultra-short laser pulses in the extreme ultraviolet and X-ray regime, as their spectral and temporal resolution allow for resolving the ultra-fast dynamics near CIs.