Intersystem Crossing as a Key Component of the Nonadiabatic Relaxation Dynamics of Bithiophene and Terthiophene

Thomas Schnappinger; Marco Marazzi; Sebastian Mai; Antonio Monari; Leticia González; Regina de Vivie-Riedle

doi:10.1021/acs.jctc.8b00492

Titel

Autor*in

Thomas Schnappinger

Ludwig-Maximilians-Universität München

Marco Marazzi

Universidad de La Rioja

Sebastian Mai

Universität Wien

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Abstract

We present a non-adiabatic dynamics study concerning the sub picosecond relaxation of excited states in dimeric and trimeric thiophene chains. The influence of the triplet states in the overall process is, for the first time, taken into account by explicitly including spin-orbit couplings and hence allowing intersystem crossing phenomena. We observe the fundamental role of the triplet state manifold in driving the full relaxation process. In particular we evidence the effect of both, inter-ring rotation and ring-opening, in the process, as compared to the monomer, where the ring-opening process appears as the dominant one. In addition, the evolution of the open structures allows for trans to cis isomerization in the dimer and trimer. The overall relaxation process slows down with chain elongation. The complex decay mechanism characterized by the presence of different competing channels, due to the presence of a quasi degenerate manifold, is explained allowing the rationalization of oligothiophenes photophysics.

Objekt-Typ

journal article

Sprache

Englisch [eng]

Persistent identifier

phaidra.univie.ac.at/o:1049655

DOI

10.1021/acs.jctc.8b00492

Erschienen in

Titel

Journal of Chemical Theory and Computation

Band