Unravelling time-resolved Interparticle Coulombic Decay: From spectral formation to decay lifetimes

Abstract:Electronic decay processes provide a fascinating window into correlated electronic rearrangements occurring on ultrafast timescales. Following these dynamics in real time has become increasingly accessible experimentally, but extracting the underlying electronic dynamics from measured spectra requires understanding how nuclear motion shapes the observable signal. Here, we extend an analytical description of time-resolved electronic decay spectra to include dissociative nuclear dynamics and apply it to Interparticle Coulombic Decay (ICD) in the neon dimer. The resulting spectra reproduce the experimentally observed spectral shape and reveal an unexpectedly important role of interference between pathways involving different vibronic resonance states. We further establish a clear connection between the temporal build-up of the spectral structure and the nuclear wavepacket dynamics in the decaying electronic state. Most strikingly, our analytical expressions reveal that the time-dependent integrated ICD signal contains contributions proportional to both $\exp(-t/\tau)$ and $\exp[-t/(2\tau)]$. Nevertheless, a conventional mono-exponential fit can describe the temporal signal remarkably well while yielding a decay lifetime that differs substantially from the underlying value. Applying the theoretically derived fitting model to experimental data for the neon dimer yields an ICD lifetime $\tau$ of 73 fs, rather than the previously extracted 150(50) fs, placing the experimental value within the range of previous theoretical predictions. Since the underlying temporal structure is common to electronic decay processes, our findings have implications for extracting lifetimes from time-resolved decay spectra well beyond ICD.

arXiv:2607.24597 [quant-ph]

(or arXiv:2607.24597v1 [quant-ph] for this version)

https://doi.org/10.48550/arXiv.2607.24597 Focus to learn more arXiv-issued DOI via DataCite (pending registration)

arXivLabs is a framework that allows collaborators to develop and share new arXiv features directly on our website.

Both individuals and organizations that work with arXivLabs have embraced and accepted our values of openness, community, excellence, and user data privacy. arXiv is committed to these values and only works with partners that adhere to them.

Have an idea for a project that will add value for arXiv's community? Learn more about arXivLabs.