Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities

In surface-enhanced Raman scattering (SERS), vibrations of molecules couple with optical modes of a plasmonic nanocavity via a molecular optomechanical interaction. This molecule-plasmon coupling gives rise to optomechanical effects such as vibrational pumping-the excitation of molecular vibrations...

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Autores: Jakob, Lukas A., Juan-Delgado, Adrián, Mueller, Niclas Sven, Hu, Shu, Arul, Rakesh, Boto, Roberto A., Esteban, Ruben, Aizpurua, Javier, Baumberg, Jeremy J.
Tipo de documento: artigo
Estado:Versão publicada
Data de publicação:2025
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/388874
Acesso em linha:http://hdl.handle.net/10261/388874
Access Level:Acceso aberto
Palavra-chave:Surface-enhanced Raman scattering
Molecular optomechanic
Vibrational pumping
Collective vibration
NPoM
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dc.title.none.fl_str_mv Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
title Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
spellingShingle Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
Jakob, Lukas A.
Surface-enhanced Raman scattering
Molecular optomechanic
Vibrational pumping
Collective vibration
NPoM
title_short Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
title_full Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
title_fullStr Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
title_full_unstemmed Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
title_sort Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities
dc.creator.none.fl_str_mv Jakob, Lukas A.
Juan-Delgado, Adrián
Mueller, Niclas Sven
Hu, Shu
Arul, Rakesh
Boto, Roberto A.
Esteban, Ruben
Aizpurua, Javier
Baumberg, Jeremy J.
author Jakob, Lukas A.
author_facet Jakob, Lukas A.
Juan-Delgado, Adrián
Mueller, Niclas Sven
Hu, Shu
Arul, Rakesh
Boto, Roberto A.
Esteban, Ruben
Aizpurua, Javier
Baumberg, Jeremy J.
author_role author
author2 Juan-Delgado, Adrián
Mueller, Niclas Sven
Hu, Shu
Arul, Rakesh
Boto, Roberto A.
Esteban, Ruben
Aizpurua, Javier
Baumberg, Jeremy J.
author2_role author
author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
European Research Council
Engineering and Physical Sciences Research Council (UK)
Cambridge Trust
Rutherford Foundation
Agencia Estatal de Investigación (España)
Ministerio de Ciencia, Innovación y Universidades (España)
Royal Society of New Zealand
Trinity College Cambridge
Eusko Jaurlaritza
Nationale Akademie der Wissenschaften Leopoldina
Diputación Foral de Gipuzkoa
Consejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]
dc.subject.none.fl_str_mv Surface-enhanced Raman scattering
Molecular optomechanic
Vibrational pumping
Collective vibration
NPoM
topic Surface-enhanced Raman scattering
Molecular optomechanic
Vibrational pumping
Collective vibration
NPoM
description In surface-enhanced Raman scattering (SERS), vibrations of molecules couple with optical modes of a plasmonic nanocavity via a molecular optomechanical interaction. This molecule-plasmon coupling gives rise to optomechanical effects such as vibrational pumping-the excitation of molecular vibrations due to Stokes scattering. Here, we investigate the influence of vibrational pumping and collective effects on biphenyl-4-thiol (BPT) molecules in nanoparticle-on-mirror nanocavities, both experimentally by pulsed SERS spectroscopy and theoretically with optomechanical modeling. From the anti-Stokes to Stokes ratio of hundreds of individual nanostructures, we provide clear experimental evidence of vibrational pumping in high-wavenumber vibrational modes at room temperature and investigate the emergence of collective vibrational effects experimentally by varying the spacing and number of BPT molecules in the nanocavity. This is achieved by preparing mixed monolayers of different molecular species with distinct vibrational spectra. We show a 3-fold reduction of the vibrational pumping rate in experiments by tuning the collective coupling through the intermolecular spacing. Including the full plasmonic multimode response as well as collective molecular vibrations in the optomechanical theory leads to good agreement with experiments. The optomechanical control of molecular vibrations may thus enable bond-selective plasmonic chemistry, collective parametric instabilities, and phonon lasing.
publishDate 2025
dc.date.none.fl_str_mv 2025
2025
2025
dc.type.none.fl_str_mv info:eu-repo/semantics/article
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info:eu-repo/semantics/publishedVersion
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status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/10261/388874
url http://hdl.handle.net/10261/388874
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
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info:eu-repo/grantAgreement/EC/H2020/829067
info:eu-repo/grantAgreement/EC/H2020/883703
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139579NB-I00
info:eu-repo/grantAgreement/AEI//PRE2020-095013
Jakob, Lukas A.; Juan-Delgado, Adrián; Mueller, Niclas Sven; Hu, Shu; Arul, Rakesh; Boto, Roberto A.; Esteban, Ruben; Aizpurua, Javier; Baumberg, Jeremy J.; 2025; Supporting Information: Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities [Dataset]; American Chemical Society; https://doi.org/10.1021/acsnano.4c16535
https://doi.org/10.1021/acsnano.4c16535
Sí
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dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:DIGITAL.CSIC. Repositorio Institucional del CSIC
instname:Consejo Superior de Investigaciones Científicas (CSIC)
instname_str Consejo Superior de Investigaciones Científicas (CSIC)
reponame_str DIGITAL.CSIC. Repositorio Institucional del CSIC
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spelling Optomechanical pumping of collective molecular vibrations in plasmonic nanocavitiesJakob, Lukas A.Juan-Delgado, AdriánMueller, Niclas SvenHu, ShuArul, RakeshBoto, Roberto A.Esteban, RubenAizpurua, JavierBaumberg, Jeremy J.Surface-enhanced Raman scatteringMolecular optomechanicVibrational pumpingCollective vibrationNPoMIn surface-enhanced Raman scattering (SERS), vibrations of molecules couple with optical modes of a plasmonic nanocavity via a molecular optomechanical interaction. This molecule-plasmon coupling gives rise to optomechanical effects such as vibrational pumping-the excitation of molecular vibrations due to Stokes scattering. Here, we investigate the influence of vibrational pumping and collective effects on biphenyl-4-thiol (BPT) molecules in nanoparticle-on-mirror nanocavities, both experimentally by pulsed SERS spectroscopy and theoretically with optomechanical modeling. From the anti-Stokes to Stokes ratio of hundreds of individual nanostructures, we provide clear experimental evidence of vibrational pumping in high-wavenumber vibrational modes at room temperature and investigate the emergence of collective vibrational effects experimentally by varying the spacing and number of BPT molecules in the nanocavity. This is achieved by preparing mixed monolayers of different molecular species with distinct vibrational spectra. We show a 3-fold reduction of the vibrational pumping rate in experiments by tuning the collective coupling through the intermolecular spacing. Including the full plasmonic multimode response as well as collective molecular vibrations in the optomechanical theory leads to good agreement with experiments. The optomechanical control of molecular vibrations may thus enable bond-selective plasmonic chemistry, collective parametric instabilities, and phonon lasing.We acknowledge support from European Research Council (ERC) under Horizon 2020 research and innovation programme THOR (grant agreement no. 829067), and PICOFORCE (grant agreement no. 883703), and UK EPSRC grants EP/L027151/1, EP/R020965/1. L.A.J. acknowledges support from the Cambridge Trust and EPSRC award 2275079. R.A. acknowledges support from the Rutherford Foundation of the Royal Society Te Apa̅rangi of New Zealand, the Winton Programme for the Physics of Sustainability, and Trinity College, University of Cambridge. N.S.M. acknowledges support from the German National Academy of Sciences Leopoldina. A.J.D., R.E., and J.A. acknowledge support from grant no. PID2022-139579NB-I00 funded by MICIU/AEI/10.13039/501100011033 and by ERDF/EU and grant no. IT 1526-22 from the Dpt. of Education of the Basque Government. A.J.D. acknowledges financial support through the grant PRE2020-095013 funded by MICIU/AEI/10.13039/501100011033 and by “ESF Investing in your future”. R.A.B., R.E. and J.A. acknowledge the Elkartek Project u4Smart, from the Dept. of Economy Development of the Basque Country. R.A.B. acknowledges the Gipuzkoa Quantum project QSEIRA (grant no. 2024-QUAN-000011-01) funded by the Dept. of Economic Development and Strategic Projects of the Provincial Council of Gipuzkoa.Peer reviewedAmerican Chemical SocietyEuropean CommissionEuropean Research CouncilEngineering and Physical Sciences Research Council (UK)Cambridge TrustRutherford FoundationAgencia Estatal de Investigación (España)Ministerio de Ciencia, Innovación y Universidades (España)Royal Society of New ZealandTrinity College CambridgeEusko JaurlaritzaNationale Akademie der Wissenschaften LeopoldinaDiputación Foral de GipuzkoaConsejo Superior de Investigaciones Científicas [https://ror.org/02gfc7t72]202520252025info:eu-repo/semantics/articlehttp://purl.org/coar/resource_type/c_6501Publisher's versioninfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://hdl.handle.net/10261/388874reponame:DIGITAL.CSIC. Repositorio Institucional del CSICinstname:Consejo Superior de Investigaciones Científicas (CSIC)Inglés#PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE##PLACEHOLDER_PARENT_METADATA_VALUE#info:eu-repo/grantAgreement/EC/H2020/829067info:eu-repo/grantAgreement/EC/H2020/883703info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2021-2023/PID2022-139579NB-I00info:eu-repo/grantAgreement/AEI//PRE2020-095013Jakob, Lukas A.; Juan-Delgado, Adrián; Mueller, Niclas Sven; Hu, Shu; Arul, Rakesh; Boto, Roberto A.; Esteban, Ruben; Aizpurua, Javier; Baumberg, Jeremy J.; 2025; Supporting Information: Optomechanical pumping of collective molecular vibrations in plasmonic nanocavities [Dataset]; American Chemical Society; https://doi.org/10.1021/acsnano.4c16535https://doi.org/10.1021/acsnano.4c16535Síinfo:eu-repo/semantics/openAccessoai:digital.csic.es:10261/3888742026-05-22T06:33:51Z
score 15,30478

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