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Wavelength Dependence of Plasmon-Induced Vibrational Energy Transfer in Fluorophore–Plasmonic Systems
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    Wavelength Dependence of Plasmon-Induced Vibrational Energy Transfer in Fluorophore–Plasmonic Systems
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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2024, 128, 26, 10784–10789
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    https://doi.org/10.1021/acs.jpcc.4c01142
    Published June 18, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    Understanding, predicting, and controlling plasmon–molecule energy transfer are important for improvements to plasmonic photocatalysis and photothermal therapies. Here, we use continuous wave surface-enhanced anti-Stokes and Stokes Raman spectroscopy to quantify the vibrational kinetic energy, equivalent to a molecular temperature under a Boltzmann approximation, of Raman-active vibrational modes of molecules at plasmonic interfaces. In previous work from our group, we observed an anomalous steady-state reduction in vibrational kinetic energies in benzenethiols absorbed onto the surface of gold nanoparticles. To further explore this effect, here, we quantify the wavelength dependence of vibrational energy in plasmon–fluorophore systems, where molecules can undergo electronic transitions with resonant excitation. We used three excitation wavelengths and three molecules with varying electronic resonance energies. We observe wavelength-dependent vibrational energy distributions, which we attribute to competing effects of on-resonance heating and off-resonance decrease in the population ratio. This work thus quantifies the resonance wavelength dependence of vibrational energy in plasmon molecular systems and helps to suggest future applications of tailored systems with controllable energy transfer pathways.

    Copyright © 2024 American Chemical Society

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    • Additional Raman spectra, UV–visible characterization, Raman instrumentation, data processing, and supporting spectra (PDF)

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    The Journal of Physical Chemistry C

    Cite this: J. Phys. Chem. C 2024, 128, 26, 10784–10789
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpcc.4c01142
    Published June 18, 2024
    Copyright © 2024 American Chemical Society

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