2021/11/19 by Manawadu, Dilhan, Valentine, Darren, Marcus, Max +1 · 2 citations
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences
paper · doi:10.48550/arxiv.2111.10284
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.