Imaging electron dynamics with time- and angle-resolved photoelectron spectroscopy

TL;DR

This paper presents a theoretical framework for using time- and angle-resolved photoelectron spectroscopy to image and analyze coherent electron dynamics in molecules, emphasizing the importance of rigorous analysis for accurate interpretation.

Contribution

It introduces a comprehensive theoretical approach that accounts for transition indistinguishability and electron correlation effects in photoelectron spectra analysis.

Findings

Fourier analysis can track electron dynamics in molecules.

Rigorous theoretical analysis is essential for interpreting spectra.

Application demonstrated on indole molecular cation.

Abstract

We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet (XUV) probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into account the indistinguishability of transitions induced by the ultrashort, broadband probe pulse and electron hole correlation effects, is necessary for the interpretation of time- and angle-resolved photoelectron spectra. We show how a Fourier analysis of time- and angle-resolved photoelectron spectra from a molecule can be applied to follow its electron dynamics by considering photoelectron distributions from an indole molecular cation with coherent electron dynamics.