Non-Adiabatic Electronic and Vibrational Ring-Opening Dynamics resolved with Attosecond Core-Level Spectroscopy

TL;DR

This paper demonstrates that attosecond core-level spectroscopy can effectively resolve the real-time non-adiabatic electronic and vibrational dynamics during ring-opening reactions in molecules like furan, revealing pathway details and transient states.

Contribution

The study introduces a novel application of attosecond core-level spectroscopy to directly observe electronic-nuclear correlations during non-adiabatic molecular dynamics.

Findings

Revealed the pathway dynamics of furan across conical intersections.

Detected electronic coherence dephasing due to nuclear motion.

Identified ring-opened isomer as the main product.

Abstract

Non-adiabatic dynamics and conical intersections play a central role in the chemistry of most polyatomic molecules, ranging from isomerization to heterocyclic ring opening and avoided photo-damage of DNA. Studying the underpinning correlated dynamics of electronic and nuclear wave packets is a major challenge in real-time and, many times involves optically dark transient states. We show that attosecond core-level spectroscopy reveals the pathway dynamics of neutral furan across its conical intersections and dark states. Our method measures electronic-nuclear correlations to detect the dephasing of electronic coherence due to nuclear motion and identifies the ring-opened isomer as the dominant product. These results demonstrate the efficacy of attosecond core level spectroscopy as a potent method to investigate the real-time dynamics of photochemical reaction pathways in complex molecular systems.