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Wavelike electronic energy transfer in donor–acceptor molecular systems through quantum coherence

Nature Nanotechnology volume 17, pages 729–736 (2022)Cite this article

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Abstract

Quantum-coherent intermolecular energy transfer is believed to play a key role in light harvesting in photosynthesis and photovoltaics. So far, a direct, real-space demonstration of quantum coherence in donor–acceptor systems has been lacking because of the fragile quantum coherence in lossy molecular systems. Here, we precisely control the separations in well-defined donor–acceptor model systems and unveil a transition from incoherent to coherent electronic energy transfer. We monitor the fluorescence from the heterodimers with subnanometre resolution through scanning tunnelling microscopy induced luminescence. With decreasing intermolecular distance, the dipole coupling strength increases and two new emission peaks emerge: a low-intensity peak blueshifted from the donor emission, and an intense peak redshifted from the acceptor emission. Spatially resolved spectroscopic images of the redshifted emission exhibit a σ antibonding-like pattern and thus indicate a delocalized nature of the excitonic state over the whole heterodimer due to the in-phase superposition of molecular excited states. These observations suggest that the exciton can travel coherently through the whole heterodimer as a quantum-mechanical wavepacket. In our model system, the wavelike quantum-coherent transfer channel is three times more efficient than the incoherent channel.

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Fig. 1: Intermolecular energy transfer in a constructed PtPc–ZnPc dimer at a relatively large distance of ~2.21 nm.
Fig. 2: Hopping-like FRET at relatively large distances (d ≥ 1.72 nm).
Fig. 3: Dipole-orientation-dependent quantum-coherent energy transfer in a constructed PtPc–ZnPc heterodimer in close contact (d = 1.41 nm).
Fig. 4: Comparison of EET efficiencies between coherent and incoherent channels through constructing molecular networks.
Fig. 5: Quantum-coherent energy transfer in a linear trimer.

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Data availability

Source data are provided with this paper. All other data that support the findings of this study are available from the corresponding authors upon reasonable request.

Code availability

The code used to calculate the results shown in this work is available from the corresponding authors upon reasonable request.

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Acknowledgements

We thank B. Wang, Y. X. Weng, P. W. Du and Y. Zeng for helpful discussions. This work was supported by the National Key R&D Program of China (Grant No. 2017YFA0303500 and 2016YFA0200600), the National Natural Science Foundation of China (Grant No. 21790352, 21973087, 22174135 and 21622309), the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB36000000), Anhui Initiative in Quantum Information Technologies (Grant No. AHY090000), Innovation Program for Quantum Science and Technology (Grant No. 2021ZD0303301) and the Fundamental Research Funds for the Central Universities.

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  1. These authors contributed equally: Fan-Fang Kong, Xiao-Jun Tian.

Authors and Affiliations

  1. Hefei National Research Center for Physical Sciences at the Microscale and Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei, China

    Fan-Fang Kong, Xiao-Jun Tian, Yang Zhang, Yao Zhang, Gong Chen, Yun-Jie Yu, Shi-Hao Jing, Hong-Ying Gao, Yi Luo, Jin-Long Yang, Zhen-Chao Dong & J. G. Hou

  2. School of Physics and Department of Chemical Physics, University of Science and Technology of China, Hefei, China

    Yang Zhang, Yao Zhang, Yi Luo, Jin-Long Yang & Zhen-Chao Dong

  3. Hefei National Laboratory, Hefei, China

    Yang Zhang, Yao Zhang, Yi Luo, Jin-Long Yang & Zhen-Chao Dong

  4. School of Chemical Engineering and Technology, Tianjin University, Tianjin, China

    Hong-Ying Gao

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Contributions

Yang Zhang, Z.-C.D. and J.G.H. conceived and designed the experiments. F.-F.K., X.-J.T., S.-H.J., Y.-J.Y. and H.-Y.G. performed experiments and analysed the data. Yao Zhang and G.C. performed theoretical simulations. F.-F.K., Yang Zhang, Yao Zhang, J.-L.Y., Y.L., Z.-C.D. and J.G.H. contributed to the data interpretation. F.-F.K., Yang Zhang, Yao Zhang, Z.-C.D. and J.G.H. co-wrote the manuscript. All authors discussed the results and commented on the manuscript.

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Correspondence to Yang Zhang, Zhen-Chao Dong or J. G. Hou.

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Nature Nanotechnology thanks Konstantin E. Dorfman, Yousoo Kim and Takashi Kumagai for their contribution to the peer review of this work.

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Extended data

Extended Data Fig. 1 Estimation on the intermolecular distances for different heterodimer configurations constructed artificially.

a, STM image of a single PtPc and a single ZnPc adsorbed on 3ML-NaCl/Ag(100) (7 nm × 7 nm). To identify the molecular adsorption configurations, the STM image was acquired with different scanning conditions: the upper part was acquired at –2.1 V and 2 pA to highlight the molecular skeleton structure, while the lower part was acquired at 0.1 V and 500 pA to resolve the chlorine ions of the NaCl surface. The PtPc center is found to adsorb above a sodium ion with the molecular axes roughly aligned along the [010] or [001] direction, whereas the ZnPc center adsorbs above a chlorine ion with the molecular axes aligned along the [011] or \([01\bar 1]\) direction. The configuration of a PtPc–ZnPc heterodimer is specified with the vector connecting the molecular centers from PtPc to ZnPc. The unit vector i (j) is defined along the [011] (\([01\bar 1]\)) direction between two nearest chlorines. As an example, the PtPc–ZnPc heterodimer in this STM image is noted as (8.5, 6.5) configuration. b, STM images of a series of PtPc–ZnPc heterodimers with different configurations. Scale bars, 1 nm. c, Estimation of the distances between the PtPc and ZnPc molecules (d), as detailed in Methods. The numbers in parentheses represent the uncertainty of standard deviations. We note that the minimum displacement in molecular manipulation is about 0.40 nm in either i or j direction, which is limited by the distance between two nearest chlorines of the NaCl (100) surface.

Source data

Extended Data Fig. 2 Comparisons of dI/dV data for isolated molecules and heterodimers.

a, dI/dV spectra acquired at the lobes of an isolated PtPc (ZnPc) and PtPc–ZnPc dimers for d = 2.21 nm and d = 1.41 nm, with the measurement position marked by the dots in the inset STM images. The dI/dV spectra are offset for clarity. The inset shows the corresponding STM images (–2.8 V, 2 pA). b, dI/dV images of an isolated PtPc or ZnPc on the NaCl surface. c, dI/dV image of the PtPc–ZnPc dimer for d = 2.21 nm. d, dI/dV image of the PtPc–ZnPc dimer for d = 1.41 nm. The dI/dV signals (images) were measured using the lock-in technique with the tunneling gap set at –2.5 V and 10 pA (–2.8 V and 30 pA). The dI/dV images were acquired with a closed feedback loop. Scale bars, 1 nm.

Source data

Extended Data Fig. 3 Spatial distribution of experimental peak intensities and simulated photon image pattern for the Pdimer emission of the PtPc–ZnPc heterodimer at d = 1.41 nm.

a, Spatial distribution of Pdimer peak intensities obtained from the STML spectroscopic image (–2.8 V, 30 pA, 1 s per pixel). b, Simulated photon image pattern for the Pdimer emission. We note that the simulated image in b considers the emission process alone, without taking the electron excitation into account. Scale bars, 1 nm. Also detailed in Supplementary Section 11.

Source data

Extended Data Fig. 4 Spatial distribution of experimental peak energies and simulated photonic Lamb shifts (Δω) for the Pdimer emission of the PtPc–ZnPc heterodimer at d = 1.41 nm.

a, Spatial distribution of Pdimer peak energies obtained from the STML spectroscopic image (–2.8 V, 30 pA, 1 s per pixel). b, Simulated photonic Lamp shifts (Δω) for the Pdimer emission. Note that, in the STML measurements, molecular specific emission peaks can only be identified over the molecular area that can be directly excited by tunneling electrons. Scale bars, 1 nm. Also detailed in Supplementary Section 11.

Source data

Supplementary information

Supplementary Information

Supplementary Sections 1–14.

Source data

Source Data Fig. 1

Spectra and images for Fig. 1.

Source Data Fig. 2

Spectra and images for Fig. 2.

Source Data Fig. 3

Spectra and images for Fig. 3.

Source Data Fig. 4

Spectra and images for Fig. 4.

Source Data Fig. 5

Spectra and images for Fig. 5.

Source Data Extended Data Fig. 1

Images for Extended Data Fig. 1.

Source Data Extended Data Fig. 2

Spectra and images for Extended Data Fig. 2.

Source Data Extended Data Fig. 3

Images for Extended Data Fig. 3.

Source Data Extended Data Fig. 4

Images for Extended Data Fig. 4.

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Kong, FF., Tian, XJ., Zhang, Y. et al. Wavelike electronic energy transfer in donor–acceptor molecular systems through quantum coherence. Nat. Nanotechnol. 17, 729–736 (2022). https://doi.org/10.1038/s41565-022-01142-z

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