Probing coherent electronic superpositions of singly- and doubly-excited states of krypton with attosecond four-wave mixing spectroscopy

TL;DR

This paper demonstrates how attosecond four-wave mixing spectroscopy can probe and analyze the coherent superpositions of excited electronic states in krypton, revealing interactions between singly and doubly excited states.

Contribution

It introduces a combined experimental and theoretical approach to study complex electronic states, including a minimal model that accurately reproduces observed dynamics.

Findings

Observation of quantum beats in krypton autoionizing states

Identification of interactions between singly and doubly excited states

Development of a multichannel quantum defect theory model

Abstract

Radiative nonlinear four-wave mixing can monitor the evolution of electronic wave packets, providing access to lifetimes and quantifies the light induced couplings between excited states. We report the observation of quantum beats in an autoionizing electronic wavepacket in krypton, probed using this technique. Analysis of the signal reveals that these beats originate from the contribution of previously unassigned, doubly excited states interacting with singly excited ones. We introduce a minimal theoretical model, based on multichannel quantum defect theory, that quantitatively reproduces both the wavepacket dynamics and the static spectrum. This work combines a versatile, background-free experimental scheme with a tractable model, establishing a powerful approach for the metrology and control of complex, correlated electronic states.