Rotational Coherence Dominates Early-Time Dynamics and Produces Long-Time Revivals in the S2 State of Azulene

TL;DR

This study reveals that early-time decay in azulene's excited state is due to rotational dephasing, and long-time dynamics include structured rotational revivals, positioning PAHs as models for quantum-coherent wavepacket dynamics.

Contribution

It demonstrates that rotational dephasing explains early decay in azulene and uncovers long-lived rotational coherence revivals, challenging previous IVR-based interpretations.

Findings

Early decay caused by rotational dephasing

Observation of long-time rotational coherence revivals

Azulene exhibits sustained quantum coherence in nanoseconds

Abstract

The ultrafast dynamics of azulene have been debated for decades, with reported picosecond decay constants variously attributed to intramolecular vibrational redistribution (IVR), internal conversion, or rotational dephasing. Using polarization and femtosecond time-resolved Resonance Enhanced Multi-photon Ionization Spectroscopy with a nanosecond delay window, we disentangle this long-standing inconsistency and show that the early 2-5 ps decay component arises entirely from rotational dephasing of an excited-state wavepacket. Identical time constants extracted from the decay of the parallel signal and rise of the perpendicular signal across multiple vibronic origins provide an unambiguous rotational anisotropy signature, eliminating the need for IVR-based interpretations. Extending the measurement window to 1.3 ns reveals well-structured J-type and C-type rotational coherence revivals in S2 azulene on top of the well-documented fluorescence decay, demonstrating that both the short- and long-time dynamics contain information about the coherent rotational dynamics. These results show that azulene, and by extension polycyclic aromatic hydrocarbons (PAH), can sustain structured rotational coherence deep into the nanosecond regime, positioning PAHs as model systems for quantum-coherent wavepacket dynamics and providing a framework for probing coherence, decoherence, and rotational control in electronically rich molecular systems.