Theoretical Study of Spectroscopy and Photodynamics of Decatetraene as a Representative Dimethylated Polyene

• DOI: 10.1021/acs.jpca.4c08185
• Publication Date: 2025-02-27T18:02:11Z
• Authors: Anjan Chattopadhyay; Maximilian F. S. ...; Dilawar Singh Sis...; Horst Köppel
• Keywords: Polyene

The photodynamics and UV spectroscopy of decatetraene following excitation to the bright 1Bu state are studied theoretically, based on ab initio computations underlying potential energy (PE) surfaces. Both photophysical photochemical aspects investigated. former involves smaller amplitude displacements, – in addition determining multidimensional PE surfaces also a quantal treatment ensuing nuclear dynamics. inclusion 1Bu–2Ag vibronic interaction allows compute vibrational structure 1Ag–1Bu spectral band femtosecond internal conversion (population transfer). results compared with analogous features octatetraene octatriene. involving larger-amplitude displacements investigated from quantum-chemical point view, focusing stationary points seams conical intersections that involved. A comparison reveals contrasting their 2Ag minima, where latter is more stable dimethylated system. small barrier connecting these two states lies between 0.06 0.11 eV. nonradiative decay channels originating minima characterized by comparatively higher barriers influence outcome radiative processes different manner octatetraene.