Time-Resolved Photoelectron Spectroscopy of Conical Intersections with Attosecond Pulse Trains.

Conical Intersections (CIs), which are believed to be ubiquitous in molecular and biological systems, open up ultrafast nonradiative decay channels. A superposition of electronic states is created when a molecule passes through a CI and the nuclear wave packet branches. The resulting electronic coherence can be considered a unique signature of the CI. The involved electronic states can be resolved in the energy domain with photoelectron spectroscopy using a femtosecond pulse as a probe. However, the observation of the created electronic coherence in the time domain requires probe pulses with several electron volts of bandwidth. Attosecond pulses can probe the electronic coherence but are unable to resolve the involved electronic states. In this Letter, we propose to address this restriction by using time-resolved photoelectron spectroscopy with an attosecond pulse train as a probe. We theoretically demonstrate that the resulting photoelectron spectrum may yield energy resolution as well as the information on the created coherences in the time domain.