Title
Intersystem Crossing as a Key Component of the Nonadiabatic Relaxation Dynamics of Bithiophene and Terthiophene
Author
Thomas Schnappinger
Ludwig-Maximilians-Universität München
Author
Marco Marazzi
Universidad de La Rioja
Author
Sebastian Mai
... show all
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.
Object type
Language
English [eng]
Persistent identifier
https://phaidra.univie.ac.at/o:1049655
Appeared in
Title
Journal of Chemical Theory and Computation
Volume
14
Issue
9
From page
4530
To page
4540
Publisher
American Chemical Society (ACS)
Version type
Date accepted
2018-08-09
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