Attosecond Intramolecular-Scattering and Vibronic Delay

TL;DR

This paper investigates the complex interplay of nuclear and electronic motions during CO molecule photoionization, revealing how photoelectron delays and vibrational states are affected by intramolecular scattering and broadband pulses.

Contribution

It introduces an analytical model to analyze the temporal signatures of entangled nuclear-electronic dynamics in molecular photoionization, highlighting non-adiabatic effects beyond the Franck-Condon approximation.

Findings

Photoelectron emission delay decomposed into localization and resonance components

Broadband soft-x-ray pulses create tunable vibrational ionic states

Photoionization does not follow the Franck-Condon approximation

Abstract

The photoionization of the CO molecule from the C$-1s$ orbital does not obey the Franck-Condon approximation, as a consequence of the nuclear recoil that accompanies the direct emission and intra-molecular scattering of the photoelectron. We use an analytical model to investigate the temporal signature of the entangled nuclear and electronic motion in this process. We show that the photoelectron emission delay can be decomposed into its localization and resonant-confinement components. Finally, photoionization by a broadband soft-x-ray pulse results in a coherent vibrational ionic state with a tunable delay with respect to the classical sudden-photoemission limit.