The manifestation of specific features of T-exciton migration in the shape of low field resonances (LFRs) in the magnetic field effects on the TT-annihilation in molecular crystals is studied in detail. The LFRs are shown to be caused by avoided crossing of spin-levels of T-excitons in magnetic fields nearly parallel to the axis of the zero field splitting interaction tensor. Simple and accurate formulas for the shape of the LFR-line are derived within the hopping model of T-exciton migration. With these formulas, we demonstrate that the LFR-line shape is fairly sensitive to the anisotropy of T-exciton migration, in particular, in quasi-one-dimensional (quasi-1D) and quasi-two-dimensional (quasi-2D) limits of exciton migration. The analysis of the shape is shown to allow for obtaining the magnitude of the small rate of jumps out of 1D and 2D spaces of fast migration in the cases quasi-1D and quasi-2D migration, respectively. In addition, this analysis enables one to obtain the spin relaxation rate of T-excitons.
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http://dx.doi.org/10.1063/1.5127666 | DOI Listing |
J Chem Phys
December 2019
Institute of Chemical Physics, Russian Academy of Sciences, GSP-1, Kosygin St. 4, Moscow 119991, Russian Federation and Moscow Institute of Physics and Technology, Institutsky Lane 9, Dolgoprudny 141700, Moscow Region, Russian Federation.
The manifestation of specific features of T-exciton migration in the shape of low field resonances (LFRs) in the magnetic field effects on the TT-annihilation in molecular crystals is studied in detail. The LFRs are shown to be caused by avoided crossing of spin-levels of T-excitons in magnetic fields nearly parallel to the axis of the zero field splitting interaction tensor. Simple and accurate formulas for the shape of the LFR-line are derived within the hopping model of T-exciton migration.
View Article and Find Full Text PDFJ Chem Phys
July 2019
Institute of Chemical Physics, Russian Academy of Sciences, 119991, GSP-1, Kosygin St. 4, Moscow, Russian Federation and Moscow Institute of Physics and Technology, Institutsky Lane 9, Dolgoprudny 141700, Moscow Region, Russian Federation.
Kinetics of singlet fission (SF) in organic semiconductors, associated with spontaneous splitting of the excited singlet state (S) into a pair of triplet (T) excitons, is known to be strongly affected by geminate annihilation of generated TT-pairs. In this work, we analyze in detail the SF-kinetics within lattice-migration (hopping), diffusion-migration, and exponential-kinetics two-state models (TSMs), which allow us to accurately describe the effects of relative T-exciton migration in TT-pairs. In the proposed TSMs, the migration effects are treated within the approximation of kinetic coupling of two states: [TT]-state of interacting TT-pairs and [T + T]-state of freely migrating T-excitons.
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