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Electronic excitations at the plasmon–molecule interface - Nature.com

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Abstract

The recent rise of plasmonic materials for solar-to-chemical energy conversion places a focus on the mechanisms associated with charge and energy flow at the metal–molecule interface. Understanding the connection between these effects and their roles in the plasmonic excitations of adsorbed molecules has been challenging. In this Review, we strive to provide a general framework—based on the concept of electron scattering—that encompasses the most important effects at the plasmonic metal–molecule interface. First we use the model of adsorbate-induced surface resistivity to understand the chemical specificity of the electron scattering process. We then analyse two of the most prominent effects in plasmonics through the lens of the electron scattering model: chemical interface damping and the chemical model of surface-enhanced Raman scattering. We show how most metal–adsorbate charge- or energy-transfer interactions can be mapped into two major classes—electron scattering through molecular resonances and direct non-resonant electron scattering.

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Fig. 1: Timeline of the development of the field of plasmonic catalysis.
Fig. 2: Four different phenomena arising at the metal–molecule interface due to electron scattering.
Fig. 3: RES and NRES at the metal–adsorbate interface.
Fig. 4: Comparison of adsorbate-induced surface resistivity and CID.
Fig. 5: Vibrational pumping probed by SERS.

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Acknowledgements

We acknowledge funding and support from the Deutsche Forschungsgemeinschaft (DFG) under Germany´s Excellence Strategy—grant number EXC 2089/1—390776260 e-conversion excellence research cluster, the Bavarian programme Solar Technologies Go Hybrid (SolTech), the Center for NanoScience (CeNS) and the European Commission through the ERC Starting Grant CATALIGHT (grant number 802989). A.S. acknowledges support from the Alexander von Humboldt foundation. P.N. and N.J.H. acknowledge support from the Robert A. Welch Foundation under grant numbers C-1222 and C-1220. N.J.H., P.N. and E.C. acknowledge the Institute for Advanced Study (IAS) from Technische Universität München (TUM) for financing the focus group on ‘Sustainable photocatalysis using plasmons and 2D materials (SusPhuP2M)’ as part of the Hans Fisher Senior Fellowships programme. We thank J. Knott for assistance with the figures.

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Authors and Affiliations

  1. Nanoinstitute Munich, Faculty of Physics, University of Munich (LMU), Munich, Germany

    Andrei Stefancu & Emiliano Cortes

  2. Department of Chemistry, Rice University, Houston, TX, USA

    Naomi J. Halas

  3. Department of Electrical and Computer Engineering, Rice University, Houston, TX, USA

    Naomi J. Halas & Peter Nordlander

  4. Department of Physics and Astronomy, Rice University, Houston, TX, USA

    Naomi J. Halas & Peter Nordlander

  5. Technical University of Munich (TUM) Institute for Advanced Study (IAS), Garching, Germany

    Naomi J. Halas & Peter Nordlander

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  1. Andrei Stefancu
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  4. Emiliano Cortes
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All authors contributed equally to all aspects of the Review.

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Correspondence to Emiliano Cortes.

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Stefancu, A., Halas, N.J., Nordlander, P. et al. Electronic excitations at the plasmon–molecule interface. Nat. Phys. (2024). https://ift.tt/poyWhdt

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