Unraveling the Mechanism of Tip-Enhanced Molecular Energy Transfer

Fuente: arXiv
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Main Authors: Coane, Colin, Romanelli, Marco, Dall'Osto, Giulia, Di Felice, Rosa, Corni, Stefano
Format: Preprint
Published: 2023
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_version_ 1866911769354567680
author Coane, Colin
Romanelli, Marco
Dall'Osto, Giulia
Di Felice, Rosa
Corni, Stefano
author_facet Coane, Colin
Romanelli, Marco
Dall'Osto, Giulia
Di Felice, Rosa
Corni, Stefano
contents 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 (STM) 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 Forster-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.
format Preprint
id arxiv_https___arxiv_org_abs_2305_17265
institution arXiv
publishDate 2023
record_format arxiv
spellingShingle Unraveling the Mechanism of Tip-Enhanced Molecular Energy Transfer
Coane, Colin
Romanelli, Marco
Dall'Osto, Giulia
Di Felice, Rosa
Corni, Stefano
Chemical Physics
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 (STM) 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 Forster-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.
title Unraveling the Mechanism of Tip-Enhanced Molecular Energy Transfer
topic Chemical Physics
url https://arxiv.org/abs/2305.17265