Junction Plasmon Driven Population Inversion of Molecular Vibrations: A Picosecond Surface-Enhanced Raman Spectroscopy Study.

Molecular surface-enhanced Raman spectra recorded at single plasmonic nanojunctions using a 7 ps pulse train exhibit vibrational up-pumping and population inversion. The process is assigned to plasmon-driven, dark, impulsive electron-vibration (e-v) excitation. Both optical (Raman) pumping and hot-electron mediated excitation can be rejected by the characteristic spectra, which allow the simultaneous measurement of vibrational temperature of the molecules and electronic temperature of the metal. Vibrational populations are determined from anti-Stokes to Stokes intensity ratios, while the electron temperature is obtained from the anti-Stokes branch of the electronic Raman scattering continuum. Population inversion survives in high-frequency vibrations that effectively decouple from the metal.

• Publication year

  2018

• Venue

  Nano letters (Print)

• Publication date

  2018-07-31

• Fields of study

  Materials Science, Medicine, Physics

• Identifiers
  DOI 10.1021/acs.nanolett.8b02438PMID 30064221
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

• Frequency-Domain Proof of the Existence of Atomic-Scale SERS Hot-Spots.

  2018cited by this paper
• Coherent Electron Transfer at the Ag/Graphite Heterojunction Interface.

  2018cited by this paper
• Ultrafast Nanoscale Raman Thermometry Proves Heating Is Not a Primary Mechanism for Plasmon-Driven Photocatalysis.

  2018cited by this paper
• Tip-Enhanced Raman Spectromicroscopy of Co(II)-Tetraphenylporphyrin on Au(111): Toward the Chemists' Microscope.

  2017cited by this paper
• Observation of Single Molecule Plasmon-Driven Electron Transfer in Isotopically Edited 4,4'-Bipyridine Gold Nanosphere Oligomers.

  2017cited by this paper
• Linking classical and molecular optomechanics descriptions of SERS.

  2017cited by this paper
• Tip-Enhanced Raman Spectromicroscopy on the Angstrom Scale: Bare and CO-Terminated Ag Tips.

  2017cited by this paper
• Surface-Enhanced Femtosecond Stimulated Raman Spectroscopy at 1 MHz Repetition Rates.

  2016cited by this paper
• Single-molecule optomechanics in “picocavities”

  2016cited by this paper
• Quantum mechanical effects in plasmonic structures with subnanometre gaps

  2016cited by this paper
• Ultrafast Surface-Enhanced Raman Probing of the Role of Hot Electrons in Plasmon-Driven Chemistry.

  2016cited by this paper
• Ultrafast meets ultrasmall: controlling nanoantennas and molecules

  2016cited by this paper
• Competition between Reaction and Degradation Pathways in Plasmon-Driven Photochemistry

  2016cited by this paper
• Ultrafast Coherent Raman Scattering at Plasmonic Nanojunctions

  2016cited by this paper
• Non-fluorescent schemes for single-molecule detection, imaging and spectroscopy

  2015cited by this paper
• Demonstrating Photoluminescence from Au is Electronic Inelastic Light Scattering of a Plasmonic Metal: The Origin of SERS Backgrounds

  2015cited by this paper
• Evaluating Single-Molecule Stokes and Anti-Stokes SERS for Nanoscale Thermometry

  2015cited by this paper
• Atomistic electrodynamics simulations of bare and ligand-coated nanoparticles in the quantum size regime

  2015cited by this paper
• Ultrafast dynamics of single molecules.

  2014cited by this paper
• Coherent anti-Stokes Raman scattering with single-molecule sensitivity using a plasmonic Fano resonance

  2014cited by this paper
• Seeing a single molecule vibrate through time-resolved coherent anti-Stokes Raman scattering

  2014cited by this paper
• Controlling subnanometer gaps in plasmonic dimers using graphene.

  2013cited by this paper
• Surface-Enhanced Hyper-Raman Scattering from Single Molecules

  2013cited by this paper
• Chemical mapping of a single molecule by plasmon-enhanced Raman scattering

  2013cited by this paper
• Single-Molecule Tip-Enhanced Raman Spectroscopy

  2012cited by this paper
• Fano-like resonances arising from long-lived molecule-plasmon interactions in colloidal nanoantennas.

  2012cited by this paper
• Surface-Enhanced Femtosecond Stimulated Raman Spectroscopy.

  2011cited by this paper
• Antennas for light

  2011cited by this paper
• Understanding the Surface-Enhanced Raman Spectroscopy 'Background'

  2010cited by this paper
• The Vibrational Pumping Mechanism in Surface-Enhanced Raman Scattering: A Subpicosecond Time-Resolved Study

  2010cited by this paper
• Single-molecule surface-enhanced Raman spectroscopy of nonresonant molecules.

  2009cited by this paper
• Tip-enhanced Raman spectroscopy and microscopy on single dye molecules with 15 nm resolution.

  2008cited by this paper
• Vibrational pumping in surface enhanced Raman scattering (SERS).

  2008cited by this paper
• A frequency domain existence proof of single-molecule surface-enhanced Raman spectroscopy.

  2007cited by this paper
• Single Molecule Tip-Enhanced Raman Spectroscopy with Silver Tips

  2007cited by this paper
• Interacting metal nanoparticles: Optical properties from nanoparticle dimers to core-satellite systems

  2007cited by this paper
• A conclusive demonstration of vibrational pumping under surface enhanced Raman scattering conditions.

  2006cited by this paper
• Vibrational pumping and heating under SERS conditions: fact or myth?

  2006cited by this paper
• Resonance contributions to anti-Stokes/Stokes ratios under surface enhanced Raman scattering conditions.

  2005cited by this paper
• Temperature-dependent anti-stokes/stokes ratios under surface-enhanced Raman scattering conditions.

  2005cited by this paper
• Ultrafast Electron Dynamics and Optical Nonlinearities in Metal Nanoparticles

  2001cited by this paper
• Advantage of anti-Stokes Raman scattering for high-temperature measurements

  2001cited by this paper
• Can surface-enhanced Raman scattering serve as a channel for strong optical pumping?

  2000cited by this paper
• Surface Enhanced Raman Spectroscopy of Individual Rhodamine 6G Molecules on Large Ag Nanocrystals

  1999cited by this paper
• Electromagnetic scattering by an aggregate of spheres: far field.

  1997cited by this paper
• Probing Single Molecules and Single Nanoparticles by Surface-Enhanced Raman Scattering

  1997cited by this paper
• Population pumping of excited vibrational states by spontaneous surface-enhanced Raman scattering.

  1996cited by this paper
• Femtosecond spectroscopy of electron-electron and electron-phonon energy relaxation in Ag and Au.

  1995cited by this paper
• Femtosecond investigation of electron thermalization in gold.

  1993cited by this paper
• Electron thermalization in gold.

  1992cited by this paper
• Femtosecond thermoreflectivity and thermotransmissivity of polycrystalline and single-crystalline gold films.

  1991cited by this paper
• Femtosecond studies of nonequilibrium electronic processes in metals.

  1987cited by this paper
• Anomalously intense Raman spectra of pyridine at a silver electrode

  1977cited by this paper
• Raman spectra of pyridine adsorbed at a silver electrode

  1974cited by this paper

• Single-particle surface-enhanced coherent anti–Stokes Raman scattering: Nanoparticle design and mechanism

  2026cites this paper
• Optomechanical Pumping of Collective Molecular Vibrations in Plasmonic Nanocavities

  2025cites this paper
• Electron hopping induced phonon pumping in opto-mechanical molecular nanocavities

  2025cites this paper
• Imaging heat transport in suspended diamond nanostructures with integrated spin defect thermometers

  2024cites this paper
• Nanocavities for Molecular Optomechanics: Their Fundamental Description and Applications

  2024cites this paper
• Toward a New Era of SERS and TERS at the Nanometer Scale: From Fundamentals to Innovative Applications

  2023cites this paper
• Surface mass analysis of heterogeneous reactions using low-frequency surface-enhanced Raman scattering

  2023cites this paper
• Giant optomechanical spring effect in plasmonic nano- and picocavities probed by surface-enhanced Raman scattering

  2022cites this paper
• Surface-enhanced coherent anti-Stokes Raman scattering of molecules near metal-dielectric nanojunctions.

  2022cites this paper
• Molecular Optomechanics Approach to Surface-Enhanced Raman Scattering

  2022cites this paper
• Single-Molecule Raman Spectroscopy of a Pentacene Derivative Adsorbed on the Nonflat Surface of a Metallic Tip

  2022cites this paper
• Joule Heating in Single-Molecule Point Contacts Studied by Tip-Enhanced Raman Spectroscopy.

  2022cites this paper
• Excitation and relaxation of nonthermal electron energy distributions in metals with application to gold

  2022cites this paper
• Plasmon resonance, thermal, and optical contributions to anti‐Stokes‐to‐Stokes line strength ratios in continuous wave‐excited surface‐enhanced Raman scattering spectra of molecules at random Ag surface

  2021cites this paper
• Probing energy dissipation in molecular-scale junctions via surface enhanced Raman spectroscopy: vibrational pumping and hot carrier enhanced light emission

  2021cites this paper
• Plasmon-enhanced coherent anti-stokes Raman scattering vs plasmon-enhanced stimulated Raman scattering: Comparison of line shape and enhancement factor.

  2021cites this paper
• Thousand-fold Increase in Plasmonic Light Emission via Combined Electronic and Optical Excitations.

  2021cites this paper
• Effective Electron Temperature Measurement Using Time-Resolved Anti-Stokes Photoluminescence

  2020cites this paper
• In situ surface-enhanced electronic and vibrational Raman scattering spectroscopy at metal/molecule interfaces.

  2020cites this paper
• Electronic and vibrational surface-enhanced Raman scattering: from atomically defined Au(111) and (100) to roughened Au†

  2020cites this paper
• Raman microspectroscopy in biomedical study

  2020cites this paper
• Three-dimensional Differential XYZ-Y Model for Processing Peasurements of Raman Spectra in the Identification of Gold Nanoparticles on Dielectrics

  2020cites this paper
• Laser intensity limits in surface‐enhanced linear and nonlinear Raman micro‐spectroscopy of organic molecule/Au‐nanoparticle conjugates

  2019cites this paper
• A ternary ZnO/ZnS/MoS2 composite as a reusable SERS substrate derived from the polyoxomolybdate/ZIF-8 host–guest framework

  2019cites this paper
• Low-frequency surface-enhanced Raman scattering spectroscopy at metal electrode surfaces

  2019cites this paper
• Coherent Raman scattering with plasmonic antennas

  2019cites this paper
• SERS Study of the Mechanism of Plasmon-Driven Hot Electron Transfer between Gold Nanoparticles and PCBM

  2019cites this paper
• Hot Nanoparticles

  year unknowncites this paper