Modeling of ultrafast time-resolved fluorescence applied to a weakly coupled chromophore pair
We present theory for calculating the third-order non-linear response function of a molecular aggregate in the weak inter-chromophore coupling regime. This approach is based on the perturbative expansion of the system evolution with respect to the resonance coupling, while the system-bath interactio...
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| Published in | The Journal of chemical physics Vol. 143; no. 7; p. 074101 |
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| Main Authors | , , |
| Format | Journal Article |
| Language | English |
| Published |
United States
21.08.2015
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| Online Access | Get more information |
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| Summary: | We present theory for calculating the third-order non-linear response function of a molecular aggregate in the weak inter-chromophore coupling regime. This approach is based on the perturbative expansion of the system evolution with respect to the resonance coupling, while the system-bath interaction is treated non-perturbatively by means of cumulant expansion. An explicit expression for the time-resolved fluorescence signal is then obtained. This allows us to investigate the ultrafast time-dependent Stokes shift, signatures of coherent dynamics, and the excitonic polaron formation in the excited state of the aggregate. Numerical simulations of the time-resolved fluorescence spectra of a pair of coupled molecules demonstrate these effects. |
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| ISSN: | 1089-7690 |
| DOI: | 10.1063/1.4928281 |