We determined the complete relaxation dynamics of pyrene in ethanol from the second bright state, employing experimental and theoretical broadband heterodyne detected transient grating and two-dimensional photon echo (2DPE) spectroscopy, using pulses with duration of 6 fs and covering a spectral range spanning from 250 to 300 nm. Multiple lifetimes are assigned to conical intersections through a cascade of electronic states, eventually leading to a rapid population of the lowest long-living excited state and subsequent slow vibrational cooling. The lineshapes in the 2DPE spectra indicate that the efficiency of the population transfer depends on the kinetic energy deposited into modes required to reach a sloped conical intersection, which mediates the decay to the lowest electronic state. The presented experimental-theoretical protocol paves the way for studies on deep-ultraviolet-absorbing biochromophores ubiquitous in genomic and proteic systems.

Department of Chemistry University of California Irvine California 92697 2025 United States

Departments of Chemistry and Physics University of Toronto Toronto Ontario M5S 3H6 Canada

Dipartimento di Chimica Industriale Università degli Studi di Bologna Viale del Risorgimento 4 1 40136 Bologna Italy

Institute of Physics ELI Beamlines Academy of Sciences of the Czech Republic Na Slovance 2 CZ 18221 Prague Czech Republic

Instituto de Ciencia Molecular Universitat de València Apartado 22085 ES 46071 Valencia Spain

Max Planck Institute for the Structure and Dynamics of Matter CFEL Luruper Chaussee 149 22761 Hamburg Germany

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