Unified Definition of Exciton Coherence Length for Exciton-Phonon Coupled Molecular Aggregates.

J Phys Chem Lett

MOE Key Laboratory of Organic OptoElectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, People's Republic of China.

Published: May 2023

Exciton coherence length (ECL) characterizes the spatial extent of coherently delocalized excited states of molecular aggregates. Constructive/destructive superpositions of coherent molecular dipoles lead to superradiance/subradiance, where the radiative rate is enhanced/suppressed compared to that of a single molecule. Longer ECLs correspond to faster/slower radiative rates for superradiant/subradiant aggregates. However, previous ECL definitions fail to produce monotonic relationships when exciton-phonon coupling is considered, even for simple 1D exciton-phonon systems. This problem is exacerbated for 2D aggregates with both constructive and destructive superpositions. In this Letter, we propose a novel ECL definition by virtue of sum rule for oscillator strengths, ensuring a bijective and monotonic relationship between ECL and radiative rate for both 1D/2D superradiant and subradiant aggregates. Using numerically accurate time-dependent matrix product states, we study large-scale, exciton-phonon coupled 2D aggregates and predict the existence of maximum superradiance at finite temperature, in contrast to the previously believed 1/ law. Our results provide new insights into the design and optimization of efficient light emitting materials.

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http://dx.doi.org/10.1021/acs.jpclett.3c00812DOI Listing

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