ArticlePhysical chemistry chemical physics : PCCP2017
Detection of electron tunneling across plasmonic nanoparticle-film junctions using nitrile vibrations.
Article in Physical chemistry chemical physics : PCCP, 2017. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 10 papers.
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Who cites it
10 citing papers in PubMed.
- The Impact of Electric Fields on Processes at Electrode Interfaces.Chemical reviews · 2025Review
- Local electric field in nanocavities dictates the vibrational relaxation dynamics of interfacial molecules.Chemical science · 2024Article
- Investigating the Role of Plasmonics in Electrospun Fibers by Combined Photothermal Heterodyne Imaging and Raman Measurements.The journal of physical chemistry. C, Nanomaterials and interfaces · 2024Article
- Classical vs. quantum plasmon-induced molecular transformations at metallic nanojunctions.Proceedings of the National Academy of Sciences of the United States of America · 2024Article
- Investigation of SERS Frequency Fluctuations Relevant to Sensing and Catalysis.The journal of physical chemistry. C, Nanomaterials and interfaces · 2022Article
- Vibrational Stark Effects: Ionic Influence on Local Fields.The journal of physical chemistry letters · 2022Article
- Spectrally Resolved Surface-Enhanced Raman Scattering Imaging Reveals Plasmon-Mediated Chemical Transformations.ACS nanoscience Au · 2021Article
- From SERS to TERS and Beyond: Molecules as Probes of Nanoscopic Optical Fields.The journal of physical chemistry. C, Nanomaterials and interfaces · 2020Article
- Surface Enhanced Raman Scattering Selectivity in Proteins Arises from Electron Capture and Resonant Enhancement of Radical Species.The journal of physical chemistry. C, Nanomaterials and interfaces · 2020Article
- Photothermal Microscopy of Coupled Nanostructures and the Impact of Nanoscale Heating in Surface Enhanced Raman Spectroscopy.The journal of physical chemistry. C, Nanomaterials and interfaces · 2017Article
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Authors and funding
4 authors.
Funding
Abstract
The significant electric field enhancements that occur in plasmonic nanogap junctions are instrumental in boosting the performance of spectroscopy, optoelectronics and catalysis. Electron tunneling, associated with quantum effects in small junctions, is reported to limit the electric field enhancement. However, observing and quantitatively determining how tunneling alters the electric fields within small gaps is challenging due to the nanoscale dimensions and heterogeneity present experimentally. Here, we report the use of a nitrile probe placed in the nanoparticle-film gap junctions to demonstrate that the change in the nitrile stretching band associated with the vibrational Stark effect can be directly correlated with the local electric field environment modulated by gap size variations. The emergence of Stark shifts correlates with plasmon resonance shifts associated with electron tunneling across the gap junction. Time dependent changes in the nitrile band with extended illumination further support a build up of charge associated with optical rectification in the coupled plasmon system. Computational models agree with our experimental observations that the frequency shifts arise from a vibrational Stark effect. Large local electric fields associated with the smallest gap junctions give rise to significant Stark shifts. These results indicate that nitrile Stark probes can measure the local field strengths in plasmonic junctions and monitor the subtle changes in the local electric fields resulting from electron tunneling.
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