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Non‐Linear Fluorescence Quenching in Molecular Crystals. III. Recombination of Static Excitations
Author(s) -
Benderskii V. A.,
Brikenshtein V. Kh.,
Filippov P. G.,
Shamovskii I. A.
Publication year - 1981
Publication title -
physica status solidi (b)
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.51
H-Index - 109
eISSN - 1521-3951
pISSN - 0370-1972
DOI - 10.1002/pssb.2221060144
Subject(s) - excitation , quenching (fluorescence) , atomic physics , excimer , fluorescence , radius , recombination , chemistry , quantum yield , excited state , dipole , diffusion , analytical chemistry (journal) , molecular physics , physics , thermodynamics , optics , biochemistry , computer security , organic chemistry , quantum mechanics , chromatography , computer science , gene
Non‐linear quenching of the excimer fluorescence of pyrene crystals is investigated. The transition between diffusing ( T > 150 K) and static excitation ( T < 70 K) affects the relationship between the quantum yield of fluorescence Φ and pumping I (from Φ ∞ I −1/2 to Φ ∞ I −2/3 at high I , respectively), and the shape of its initial decreasing portion L (from L ∞ t −1 to L ∞ t −1/2 for a δ‐pulse of pumping). The rate constant of bimolecular excimer recombination γ is (5 × × 1.5) × 10 −11 cm 3 s −1 at 300 K and decreases exponentially with temperature in correspondence with the decreasing diffusion. The Förster radius R 0 corresponding to the measured value of γ is 30 Å and agrees well with the value calculated from the spectral overlap. It is shown that the low‐temperature non‐linear quenching is described quantitatively by the static dipole—dipole excitation recombination model with approximate allowance for the three‐particle correlations. Allowance for higher order correlations is found to be insignificant up to the maximum experimentally attainable excitation density n corresponding to (4π/3) R 0 3n ≈ 8.