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arXiv · 2111.10284

Singlet Triplet-Pair Production and Possible Singlet-Fission in Carotenoids

Dilhan Manawadu·Darren Valentine·Max Marcus·William Barford
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Abstract

Internal conversion from the photoexcited state to a correlated singlet triplet-pair state is believed to be the precursor of singlet fission in carotenoids. We present numerical simulations of this process using a pi-electron model that fully accounts for electron-electron interactions and electron-nuclear coupling. The time-evolution of the electrons is determined rigorously using the time-dependent density matrix renormalization method, while the nuclei are evolved via the Ehrenfest equations of motion. We apply this to zeaxanthin, a carotenoid chain with 22 conjugated carbon atoms (i.e., 11 double bonds). We show that the internal conversion of the photoexcited state to the singlet triplet-pair state occurs adiabatically via an avoided crossing within 100 fs and we predict a yield of ~ 50% We further discuss whether this singlet triplet-pair state will undergo exothermic versus endothermic intra or inter chain singlet fission.

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Dilhan Manawadu, Darren Valentine, Max Marcus, William Barford. 2021-11-19. Singlet Triplet-Pair Production and Possible Singlet-Fission in Carotenoids. https://arxiv.org/abs/2111.10284

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