Unraveling the mechanism of tip-enhanced molecular energy transfer

Coane, Colin V.; Romanelli, Marco; Dall’Osto, Giulia; Di Felice, Rosa; Corni, Stefano

doi:10.1038/s42004-024-01118-1

Title: Unraveling the mechanism of tip-enhanced molecular energy transfer

Journal Article · 15 February 2024 · Communications Chemistry

DOI: https://doi.org/10.1038/s42004-024-01118-1 · OSTI ID:2472324

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Univ. degli Studi di Padova (Italy); Univ. of Southern California, Los Angeles, CA (United States); OSTI
Univ. degli Studi di Padova (Italy)
Univ. of Southern California, Los Angeles, CA (United States); CNR Institute of Nanoscience, Modena (Italy)
Univ. degli Studi di Padova (Italy); CNR Institute of Nanoscience, Modena (Italy)

Electronic Energy Transfer (EET) between chromophores is fundamental in many natural light-harvesting complexes, serving as a critical step for solar energy funneling in photosynthetic plants and bacteria. The complicated role of the environment in mediating this process in natural architectures has been addressed by recent scanning tunneling microscope experiments involving EET between two molecules supported on a solid substrate. These measurements demonstrated that EET in such conditions has peculiar features, such as a steep dependence on the donor-acceptor distance, reminiscent of a short-range mechanism more than of a Förster-like process. By using state of the art hybrid ab initio/electromagnetic modeling, here we provide a comprehensive theoretical analysis of tip-enhanced EET. In particular, we show that this process can be understood as a complex interplay of electromagnetic-based molecular plasmonic processes, whose result may effectively mimic short range effects. Therefore, the established identification of an exponential decay with Dexter-like effects does not hold for tip-enhanced EET, and accurate electromagnetic modeling is needed to identify the EET mechanism.

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Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); European Union's Horizon 2020; Defense Advanced Research Projects Agency (DARPA)

Grant/Contract Number:: SC0019432

OSTI ID:: 2472324

Journal Information:: Communications Chemistry, Journal Name: Communications Chemistry Journal Issue: 1 Vol. 7; ISSN 2399-3669

Publisher:: Springer NatureCopyright Statement

Country of Publication:: United States

Language:: English

References (70)

Orientation Dependence of Energy Transfer in an Anthracene–Porphyrin Donor–Acceptor System This work was supported by CSIR and DST (New Delhi, India). We thank Dr. T. P. Radhakrishnan for many helpful discussions. Giribabu, L.; Ashok Kumar, A.; Neeraja, V. Angewandte Chemie International Edition, Vol. 40, Issue 19 https://doi.org/10.1002/1521-3773(20011001)40:19<3621::AID-ANIE3621>3.0.CO;2-D	journal	October 2001
Absolute Optical Cross Section of Individual Fluorescent Molecules Kastrup, Lars; Hell, Stefan W. Angewandte Chemie International Edition, Vol. 43, Issue 48 https://doi.org/10.1002/anie.200461337	journal	December 2004
Photochemical Conversion of Solar Energy Balzani, Vincenzo; Credi, Alberto; Venturi, Margherita ChemSusChem, Vol. 1, Issue 1-2 https://doi.org/10.1002/cssc.200700087	journal	February 2008
Gmsh: A 3-D finite element mesh generator with built-in pre- and post-processing facilities Geuzaine, Christophe; Remacle, Jean-François International Journal for Numerical Methods in Engineering, Vol. 79, Issue 11 https://doi.org/10.1002/nme.2579	journal	September 2009
Investigation of electronic excited states in single-molecule junctions Xu, Wei; Li, Ruihao; Wang, Chenhao Nano Research, Vol. 15, Issue 6 https://doi.org/10.1007/s12274-022-4102-3	journal	March 2022
Light Absorption and Energy Transfer in the Antenna Complexes of Photosynthetic Organisms Mirkovic, Tihana; Ostroumov, Evgeny E.; Anna, Jessica M. Chemical Reviews, Vol. 117, Issue 2 https://doi.org/10.1021/acs.chemrev.6b00002	journal	March 2016
Electronic Dynamics of a Molecular System Coupled to a Plasmonic Nanoparticle Combining the Polarizable Continuum Model and Many-Body Perturbation Theory Marsili, Margherita; Corni, Stefano The Journal of Physical Chemistry C, Vol. 126, Issue 20 https://doi.org/10.1021/acs.jpcc.2c02209	journal	May 2022
Real-Time Description of the Electronic Dynamics for a Molecule Close to a Plasmonic Nanoparticle Pipolo, Silvio; Corni, Stefano The Journal of Physical Chemistry C, Vol. 120, Issue 50 https://doi.org/10.1021/acs.jpcc.6b11084	journal	December 2016
Influence of the Chemical Structure on Molecular Light Emission in Strongly Localized Plasmonic Fields Zhang, Yao; Dong, Zhen-Chao; Aizpurua, Javier The Journal of Physical Chemistry C, Vol. 124, Issue 8 https://doi.org/10.1021/acs.jpcc.9b10256	journal	January 2020
Plasmon-Coupled Resonance Energy Transfer Hsu, Liang-Yan; Ding, Wendu; Schatz, George C. The Journal of Physical Chemistry Letters, Vol. 8, Issue 10 https://doi.org/10.1021/acs.jpclett.7b00526	journal	May 2017
Matching Nanoantenna Field Confinement to FRET Distances Enhances Förster Energy Transfer Rates Ghenuche, Petru; Mivelle, Mathieu; de Torres, Juan Nano Letters, Vol. 15, Issue 9 https://doi.org/10.1021/acs.nanolett.5b02535	journal	August 2015
Coupling of Molecular Emitters and Plasmonic Cavities beyond the Point-Dipole Approximation Neuman, Tomáš; Esteban, Ruben; Casanova, David Nano Letters, Vol. 18, Issue 4 https://doi.org/10.1021/acs.nanolett.7b05297	journal	March 2018
Many-Body State Description of Single-Molecule Electroluminescence Driven by a Scanning Tunneling Microscope Miwa, Kuniyuki; Imada, Hiroshi; Imai-Imada, Miyabi Nano Letters, Vol. 19, Issue 5 https://doi.org/10.1021/acs.nanolett.8b04484	journal	January 2019
Probing the Mechanisms of Strong Fluorescence Enhancement in Plasmonic Nanogaps with Sub-nanometer Precision Song, Boxiang; Jiang, Zhihao; Liu, Zerui ACS Nano, Vol. 14, Issue 11 https://doi.org/10.1021/acsnano.0c01973	journal	October 2020
Quenching, Plasmonic, and Radiative Decays in Nanogap Emitting Devices Faggiani, Rémi; Yang, Jianji; Lalanne, Philippe ACS Photonics, Vol. 2, Issue 12 https://doi.org/10.1021/acsphotonics.5b00424	journal	November 2015
Effect of the orientation of donor and acceptor on the probability of energy transfer involving electronic transitions of mixed polarization Haas, Elisha; Katchalski-Katzir, Ephraim; Steinberg, Izchak Z. Biochemistry, Vol. 17, Issue 23 https://doi.org/10.1021/bi00616a032	journal	November 1978
Plasmonic Nanoantennas: Fundamentals and Their Use in Controlling the Radiative Properties of Nanoemitters Giannini, Vincenzo; Fernández-Domínguez, Antonio I.; Heck, Susannah C. Chemical Reviews, Vol. 111, Issue 6 https://doi.org/10.1021/cr1002672	journal	June 2011
Quantum Mechanical Continuum Solvation Models Tomasi, Jacopo; Mennucci, Benedetta; Cammi, Roberto Chemical Reviews, Vol. 105, Issue 8 https://doi.org/10.1021/cr9904009	journal	August 2005
Fluorescent Chemosensors Based on Energy Migration in Conjugated Polymers: The Molecular Wire Approach to Increased Sensitivity Zhou, Qin; Swager, Timothy M. Journal of the American Chemical Society, Vol. 117, Issue 50 https://doi.org/10.1021/ja00155a023	journal	December 1995
Distance and Orientation Dependence of Excitation Transfer Rates in Conjugated Systems: Beyond the Förster Theory Wong, Kim F.; Bagchi, Biman; Rossky, Peter J. The Journal of Physical Chemistry A, Vol. 108, Issue 27 https://doi.org/10.1021/jp037724s	journal	July 2004
Semiempirical (ZINDO-PCM) Approach to Predict the Radiative and Nonradiative Decay Rates of a Molecule Close to Metal Particles Caricato, Marco; Andreussi, Oliviero; Corni, Stefano The Journal of Physical Chemistry B, Vol. 110, Issue 33 https://doi.org/10.1021/jp0626418	journal	July 2006
Plasmon-Controlled Förster Resonance Energy Transfer Zhao, Lei; Ming, Tian; Shao, Lei The Journal of Physical Chemistry C, Vol. 116, Issue 14 https://doi.org/10.1021/jp300916a	journal	March 2012
Plasmon Enhanced Light Harvesting: Multiscale Modeling of the FMO Protein Coupled with Gold Nanoparticles Andreussi, Oliviero; Caprasecca, Stefano; Cupellini, Lorenzo The Journal of Physical Chemistry A, Vol. 119, Issue 21 https://doi.org/10.1021/jp509870b	journal	December 2014
Distance and Orientation Dependence of Excitation Energy Transfer: From Molecular Systems to Metal Nanoparticles Saini, Sangeeta; Srinivas, Goundla; Bagchi, Biman The Journal of Physical Chemistry B, Vol. 113, Issue 7 https://doi.org/10.1021/jp806536w	journal	February 2009
Fluorescence Enhancement of Chromophores Close to Metal Nanoparticles. Optimal Setup Revealed by the Polarizable Continuum Model Vukovic, Sinisa; Corni, Stefano; Mennucci, Benedetta The Journal of Physical Chemistry C, Vol. 113, Issue 1 https://doi.org/10.1021/jp808116y	journal	December 2008
Beyond Förster Resonance Energy Transfer in Biological and Nanoscale Systems Beljonne, David; Curutchet, Carles; Scholes, Gregory D. The Journal of Physical Chemistry B, Vol. 113, Issue 19 https://doi.org/10.1021/jp900708f	journal	May 2009
Evaluation of Solvent Effects in Isotropic and Anisotropic Dielectrics and in Ionic Solutions with a Unified Integral Equation Method: Theoretical Bases, Computational Implementation, and Numerical Applications Mennucci, B.; Cancès, E.; Tomasi, J. The Journal of Physical Chemistry B, Vol. 101, Issue 49 https://doi.org/10.1021/jp971959k	journal	December 1997
Plasmon-Controlled Fluorescence: Beyond the Intensity Enhancement Ming, Tian; Chen, Huanjun; Jiang, Ruibin The Journal of Physical Chemistry Letters, Vol. 3, Issue 2 https://doi.org/10.1021/jz201392k	journal	January 2012
Strong Enhancement of the Radiative Decay Rate of Emitters by Single Plasmonic Nanoantennas Muskens, O. L.; Giannini, V.; Sánchez-Gil, J. A. Nano Letters, Vol. 7, Issue 9 https://doi.org/10.1021/nl0715847	journal	September 2007
Exciton Energy Transfer in Pairs of Single-Walled Carbon Nanotubes Qian, Huihong; Georgi, Carsten; Anderson, Neil Nano Letters, Vol. 8, Issue 5 https://doi.org/10.1021/nl080048r	journal	May 2008
Controlling Spontaneous Emission with Plasmonic Optical Patch Antennas Belacel, C.; Habert, B.; Bigourdan, F. Nano Letters, Vol. 13, Issue 4 https://doi.org/10.1021/nl3046602	journal	March 2013
Efficient photodiodes from interpenetrating polymer networks Halls, J. J. M.; Walsh, C. A.; Greenham, N. C. Nature, Vol. 376, Issue 6540, p. 498-500 https://doi.org/10.1038/376498a0	journal	August 1995
Visualizing coherent intermolecular dipole–dipole coupling in real space Zhang, Yang; Luo, Yang; Zhang, Yao Nature, Vol. 531, Issue 7596 https://doi.org/10.1038/nature17428	journal	March 2016
Real-space investigation of energy transfer in heterogeneous molecular dimers Imada, Hiroshi; Miwa, Kuniyuki; Imai-Imada, Miyabi Nature, Vol. 538, Issue 7625 https://doi.org/10.1038/nature19765	journal	October 2016
FRET imaging Jares-Erijman, Elizabeth A.; Jovin, Thomas M. Nature Biotechnology, Vol. 21, Issue 11 https://doi.org/10.1038/nbt896	journal	October 2003
Lessons from nature about solar light harvesting Scholes, Gregory D.; Fleming, Graham R.; Olaya-Castro, Alexandra Nature Chemistry, Vol. 3, Issue 10 https://doi.org/10.1038/nchem.1145	journal	September 2011
Quantum mechanical effects in plasmonic structures with subnanometre gaps Zhu, Wenqi; Esteban, Ruben; Borisov, Andrei G. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11495	journal	June 2016
Sub-nanometre control of the coherent interaction between a single molecule and a plasmonic nanocavity Zhang, Yao; Meng, Qiu-Shi; Zhang, Li Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms15225	journal	May 2017
Plasmon-induced photonic and energy-transfer enhancement of solar water splitting by a hematite nanorod array Li, Jiangtian; Cushing, Scott K.; Zheng, Peng Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3651	journal	October 2013
Exciton dynamics of C60-based single-photon emitters explored by Hanbury Brown–Twiss scanning tunnelling microscopy Merino, P.; Große, C.; Rosławska, A. Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms9461	journal	September 2015
Plasmon-induced resonance energy transfer for solar energy conversion Li, Jiangtian; Cushing, Scott K.; Meng, Fanke Nature Photonics, Vol. 9, Issue 9 https://doi.org/10.1038/nphoton.2015.142	journal	August 2015
Both electronic and vibrational coherences are involved in primary electron transfer in bacterial reaction center Ma, Fei; Romero, Elisabet; Jones, Michael R. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-08751-8	journal	February 2019
Strong plasmon-molecule coupling at the nanoscale revealed by first-principles modeling Rossi, Tuomas P.; Shegai, Timur; Erhart, Paul Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-11315-5	journal	July 2019
Vibronic mixing enables ultrafast energy flow in light-harvesting complex II Arsenault, Eric A.; Yoneda, Yusuke; Iwai, Masakazu Nature Communications, Vol. 11, Issue 1 https://doi.org/10.1038/s41467-020-14970-1	journal	March 2020
Energy funnelling within multichromophore architectures monitored with subnanometre resolution Cao, Shuiyan; Rosławska, Anna; Doppagne, Benjamin Nature Chemistry, Vol. 13, Issue 8 https://doi.org/10.1038/s41557-021-00697-z	journal	May 2021
Single-molecule tautomerization tracking through space- and time-resolved fluorescence spectroscopy Doppagne, Benjamin; Neuman, Tomáš; Soria-Martinez, Ruben Nature Nanotechnology, Vol. 15, Issue 3 https://doi.org/10.1038/s41565-019-0620-x	journal	January 2020
Wavelike electronic energy transfer in donor–acceptor molecular systems through quantum coherence Kong, Fan-Fang; Tian, Xiao-Jun; Zhang, Yang Nature Nanotechnology, Vol. 17, Issue 7 https://doi.org/10.1038/s41565-022-01142-z	journal	June 2022
Sub-nanometre resolution in single-molecule photoluminescence imaging Yang, Ben; Chen, Gong; Ghafoor, Atif Nature Photonics, Vol. 14, Issue 11 https://doi.org/10.1038/s41566-020-0677-y	journal	August 2020
Multiscale modelling of photoinduced processes in composite systems Mennucci, Benedetta; Corni, Stefano Nature Reviews Chemistry, Vol. 3, Issue 5 https://doi.org/10.1038/s41570-019-0092-4	journal	April 2019
Design principles of photosynthetic light-harvesting Fleming, Graham R.; Schlau-Cohen, Gabriela S.; Amarnath, Kapil Faraday Discuss., Vol. 155 https://doi.org/10.1039/C1FD00078K	journal	January 2012
Optical tuning of plasmon-enhanced photoluminescence Wang, Yunxia; Ding, Tao Nanoscale, Vol. 11, Issue 22 https://doi.org/10.1039/C9NR03725J	journal	January 2019
Can we control the electronic energy transfer in molecular dyads through metal nanoparticles? A QM/continuum investigation Angioni, Ambra; Corni, Stefano; Mennucci, Benedetta Physical Chemistry Chemical Physics, Vol. 15, Issue 9 https://doi.org/10.1039/c2cp44010e	journal	January 2013
Conformational disorder in energy transfer: beyond Förster theory Nelson, Tammie; Fernandez-Alberti, Sebastian; Roitberg, Adrian E. Physical Chemistry Chemical Physics, Vol. 15, Issue 23 https://doi.org/10.1039/c3cp50857a	journal	January 2013
Enhanced response properties of a chromophore physisorbed on a metal particle Corni, S.; Tomasi, J. The Journal of Chemical Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.1342241	journal	February 2001
Lifetimes of electronic excited states of a molecule close to a metal surface Corni, S.; Tomasi, J. The Journal of Chemical Physics, Vol. 118, Issue 14 https://doi.org/10.1063/1.1558036	journal	April 2003
Excitation energy transfer (EET) between molecules in condensed matter: A novel application of the polarizable continuum model (PCM) Iozzi, Maria Francesca; Mennucci, Benedetta; Tomasi, Jacopo The Journal of Chemical Physics, Vol. 120, Issue 15 https://doi.org/10.1063/1.1669389	journal	April 2004
Phosphorescence and Fluorescence of Phthalocyanines Vincett, P. S.; Voigt, E. M.; Rieckhoff, K. E. The Journal of Chemical Physics, Vol. 55, Issue 8 https://doi.org/10.1063/1.1676714	journal	October 1971
Radiative and nonradiative decay rates of a molecule close to a metal particle of complex shape Andreussi, Oliviero; Corni, Stefano; Mennucci, Benedetta The Journal of Chemical Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.1806819	journal	November 2004
Excitation energy-transfer in functionalized nanoparticles: Going beyond the Förster approach Gil, G.; Corni, S.; Delgado, A. The Journal of Chemical Physics, Vol. 144, Issue 7 https://doi.org/10.1063/1.4941565	journal	February 2016
Hybrid theoretical models for molecular nanoplasmonics Coccia, E.; Fregoni, J.; Guido, C. A. The Journal of Chemical Physics, Vol. 153, Issue 20 https://doi.org/10.1063/5.0027935	journal	November 2020
Role of metal-nanostructure features on tip-enhanced photoluminescence of single molecules Romanelli, Marco; Dall’Osto, Giulia; Corni, Stefano The Journal of Chemical Physics, Vol. 155, Issue 21 https://doi.org/10.1063/5.0066758	journal	December 2021
Surface-enhanced Raman scattering and fluorescence near metal nanoparticles Johansson, Peter; Xu, Hongxing; Käll, Mikael Physical Review B, Vol. 72, Issue 3 https://doi.org/10.1103/PhysRevB.72.035427	journal	July 2005
Single-Molecule Investigation of Energy Dynamics in a Coupled Plasmon-Exciton System Imada, Hiroshi; Miwa, Kuniyuki; Imai-Imada, Miyabi Physical Review Letters, Vol. 119, Issue 1 https://doi.org/10.1103/PhysRevLett.119.013901	journal	July 2017
Vibrationally Resolved Fluorescence Excited with Submolecular Precision Qiu, X. H. Science, Vol. 299, Issue 5606 https://doi.org/10.1126/science.1078675	journal	January 2003
Energy Transfer Across a Metal Film Mediated by Surface Plasmon Polaritons Andrew, P. Science, Vol. 306, Issue 5698 https://doi.org/10.1126/science.1102992	journal	November 2004
Current-Induced Hydrogen Tautomerization and Conductance Switching of Naphthalocyanine Molecules Liljeroth, Peter; Repp, Jascha; Meyer, Gerhard Science, Vol. 317, Issue 5842, p. 1203-1206 https://doi.org/10.1126/science.1144366	journal	August 2007
Coherent Intrachain Energy Migration in a Conjugated Polymer at Room Temperature Collini, E.; Scholes, G. D. Science, Vol. 323, Issue 5912 https://doi.org/10.1126/science.1164016	journal	January 2009
Polymer Photovoltaic Cells: Enhanced Efficiencies via a Network of Internal Donor-Acceptor Heterojunctions Yu, G.; Gao, J.; Hummelen, J. C. Science, Vol. 270, Issue 5243, p. 1789-1791 https://doi.org/10.1126/science.270.5243.1789	journal	December 1995
Optical properties of metallic films for vertical-cavity optoelectronic devices Rakić, Aleksandar D.; Djurišić, Aleksandra B.; Elazar, Jovan M. Applied Optics, Vol. 37, Issue 22, p. 5271-5283 https://doi.org/10.1364/AO.37.005271	journal	January 1998
Recent Progress on Plasmon-Enhanced Fluorescence Dong, Jun; Zhang, Zhenglong; Zheng, Hairong Nanophotonics, Vol. 4, Issue 4 https://doi.org/10.1515/nanoph-2015-0028	journal	December 2015

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