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Schnappinger, Thomas; Marazzi, Marco; Ma, Sebastian; Monari, Antonio; Gonzalez, Leticia; Vivie-Riedle, Regina de (2018): Intersystem Crossing as a Key Component of the Nonadiabatic Relaxation Dynamics of Bithiophene and Terthiophene. In: Journal of Chemical Theory and Computation, Vol. 14, No. 9: pp. 4530-4540
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Abstract

We present a nonadiabatic dynamics study concerning the subpicosecond 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.