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arXiv:2601.06190

Theoretical investigation of non-Förster exciton transfer mechanisms in perylene diimide donor, phenylene bridge, and terrylene diimide acceptor systems

Lei Yang, Seogjoo J. Jang

physics.chem-phcond-mat.mtrl-sciquant-phSubmitted Jan 8, 2026• Announced Jan 9, 2026
arXivHTMLPDF

Abstract

The rates of exciton transfer within dyads of perylene diimide and terrylene diimide connected by oligophenylene bridge units have been shown to deviate significantly from those of Förster's resonance energy transfer theory, according to single molecule spectroscopy experiments. The present work provides a detailed computational and theoretical study investigating the source of such discrepancy. Electronic spectroscopy data are calculated by time-dependent density function theory and then compared with experimental results. Electronic couplings between exciton donor and acceptor are estimated based on both transition density cube method and transition dipole approximation. These results confirm that the delocalization of exciton to the bridge parts contribute to significant enhancement of donor-acceptor electronic coupling. Mechanistic details of exciton transfer are examined by estimating the contributions of the bridge electronic states, vibrational modes of the dyads commonly coupled to both donor and acceptor, inelastic resonance energy transfer mechanism, and dark exciton states. These analyses suggest that the contribution of common vibrational modes serves as the main source of deviation from Förster's spectral overlap expression.

Journal reference
The Journal of Chemical Physics 153, 144305 (2020)
DOI
10.1063/5.0023709
Comments
14 pages, 7 figures

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The rates of exciton transfer within dyads of perylene diimide and terrylene diimide connected by oligophenylene bridge units have been shown to deviate significantly from those of Förster's resonance energy transfer theory, according to single molecule spectroscopy experiments. The present work provides a detailed computational and theoretical study investigating the source of such discrepancy. Electronic spectroscopy data are calculated by time-dependent density function theory and then compared with experimental results. Electronic couplings between exciton donor and acceptor are estimated based on both transition density cube method and transition dipole approximation. These results confirm that the delocalization of exciton to the bridge parts contribute to significant enhancement of donor-acceptor electronic coupling. Mechanistic details of exciton transfer are examined by estimating the contributions of the bridge electronic states, vibrational modes of the dyads commonly coupled to both donor and acceptor, inelastic resonance energy transfer mechanism, and dark exciton states. These analyses suggest that the contribution of common vibrational modes serves as the main source of deviation from Förster's spectral overlap expression.
We study the dynamics of excitonic states in one dimensional, dimer and trimer, and two dimensional arrangements of colloidal quantum dots using a density-matrix approach.The dots are coupled via a dipole-dipole interaction akin to the Förster mechanism.Coherent oscillations of tuned donor dots are shown to appear as plateaus in the acceptor dots, and therefore in their optical response.This behavior provides one with an interesting and unique handle to monitor the quantum state of clusters in an eavesdroping arrangement.A trimer cluster in a symmetrical loop shows steady states in a shorter characteristic time than the typical radiative lifetime of the dots.Breaking the symmetry of the loop results again in damping oscillatory states in the donor dots and plateaus in the eavesdropping/acceptor dot.The use of realistic parameters allows direct comparison with recent experiments and indicates that coherent state monitoring is possible in real experiments.Estimates of the Förster coupling V F are obtained from a microscopic description of the exciton levels in the quantum dot.We present results for different materials CdS, CdSe, GaAs, and InP as function of dot features.V F shows a nonmonotonic variation with dot sizes and a maximum value that depends on the specific dot sizes, material parameters, and dot separation.We also study the effect of the orientation factor on coherent energy transfer from a donor quantum dot to an acceptor quantum dot by calculating the polarization of the acceptor dot.We study how the measurement of the ac-ceptor polarization can be used to determine the relative orientation between the donor-acceptor pair.We also find that Förster coupling between dots results in a polarization memory transfer.
Accurate information on the distance dependence of resonance energy transfer (RET) is crucial for its utilization as a spectroscopic ruler \re{of} nanometer scale distances. In this regard, understanding the effects of donor-acceptor quantum coherence and non-Markovian bath, which become significant at short distances, has significant implications. The present work investigates this issue theoretically by comparing results from a theory of coherent RET (CRET) with a nonequilibrium version of Förster's RET (FRET) theory, both accounting for non-Markovian bath effects. Even for a model where the donor-acceptor electronic coupling is of transition dipole interaction form, it is shown that the RET rate in general deviates from the inverse sixth power distance dependence as opposed to the prediction of the original FRET. It is shown that the donor-acceptor quantum coherence makes the \re{distance} dependence steeper than the sixth power although detailed manner of enhancement is sensitive to specific values of parameters. On the other hand, the non-Markovian bath effects make the \re{distance} dependence more moderate than the sixth power for both CRET and nonueqilibrium FRET because finite time scale of the bath causes the rate to be smaller than the prediction of original FRET. While these effects are \re{demonstrated clearly} in the population dynamics at sub-picosecond time scales, their contributions to the conventional RET efficiency are relatively minor. This indicates that the actual detection of such effects through conventional RET efficiency measurement requires either high precision or utilization of a donor with fast spontaneous decay rate of excitation.
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The signals generated by various third-order nonlinear spectroscopies (transient absorption, transient grating, and three-pulse photon echo peak shift) on energy transfer systems are investigated by carrying out model calculations. Focusing on the understanding of basic features, we employ a simple model system consisting of pairs of energy donors and acceptors. We assume that energy transfer occurs via the Förster mechanism (weak electronic coupling). Static disorder in the transition energies of the chromophores induces inhomogeneities in the rate of energy transfer and in the optical response. The interplay between these two processes is discussed. We show that the peak shift experiment has advantages over the other types of experiment in clarifying the nature of disorder which affects the mechanism and time scale of energy transfer. For example, the peak shift technique can reveal the extent to which disorder is correlated in individual chromophore assemblies, and the extent to which energy transfer can correlate the energies of donors and acceptors. Finally the ability of the peak shift method to distinguish and quantify diagonal and off-diagonal disorder in energy transfer systems is discussed.
By studying the transfer of excitation energy between dye molecules confined within an optical microcavity, we demonstrate experimentally that Förster energy transfer is influenced by the local photonic mode density. Locating donor and acceptor molecules at well-defined positions allows the transfer rate to be determined as a function of both mutual separation and cavity length. The results show that the Förster transfer rate depends linearly on the donor emission rate and hence photonic mode density, providing the potential to control energy transfer by modification of the optical environment.
In a molecular system of energy donors and acceptors, resonance energy transfer is the primary mechanism by means of which electronic energy is redistributed between molecules, following the excitation of a donor. Given a suitable geometric configuration it is possible to completely inhibit this energy transfer in such a way that it can only be activated by application of an off-resonant laser beam: this is the principle of optically controlled resonance energy transfer, the basis for an all-optical switch. This paper begins with an investigation of optically controlled energy transfer between a single donor and acceptor molecule, identifying the symmetry and structural constraints and analyzing in detail the dependence on molecular energy level positioning. Spatially correlated donor and acceptor arrays with linear, square, and hexagonally structured arrangements are then assessed as potential configurations for all-optical switching. Built on quantum electrodynamical principles the concept of transfer fidelity, a parameter quantifying the efficiency of energy transportation, is introduced and defined. Results are explored by employing numerical simulations and graphical analysis. Finally, a discussion focuses on the advantages of such energy transfer based processes over all-optical switching of other proposed forms.