Quantum dynamics simulation of intramolecular singlet fission in covalently linked tetracene dimer

Abstract

In this work we study singlet fission in tetracene para-dimers, covalently linked by a phenyl group. In contrast to most previous works, we account for the full quantum dynamics of the combined excitonic and vibrational system. For our simulations we choose a numerically unbiased representation of the molecule's wave function enabling us to compare with experiments, exhibiting good agreement. Having access to the full wave function allows us to study in detail the post-quench dynamics of the excitons. Here, one of our main findings is the identification of a time scale $t_0\approx 35\text{fs}$ dominated by coherent dynamics. It is within this time scale that the larger fraction of the singlet fission yield is generated. We also report on a reduced number of phononic modes that play a crucial role for the energy transfer between excitonic and vibrational system. Notably, the oscillation frequency of these modes coincides with the observed electronic coherence time $t_0$. We extended our investigations by also studying the dependency of the dynamics on the excitonic energy levels that, for instance, can be experimentally tuned by means of the solvent polarity. Here, our findings indicate that the singlet fission yield can be doubled while the electronic coherence time $t_0$ is mainly unaffected.

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• Stable bipolarons in open quantum systems
• Chebyshev pseudosite matrix product state approach for the spectral functions of electron-phonon coupling systems
• Signature of preformed pairs in angle-resolved photoemission spectroscopy
• Thermal and optical conductivity in the Holstein model at half filling and at finite temperature in the Luttinger-liquid and charge-density-wave regime
• Electron addition spectral functions of low-density polaron liquids
• Charge density wave breakdown in a heterostructure with electron-phonon coupling