Chem Soc Rev
December 2024
Surface-enhanced Raman spectroscopy (SERS) has evolved significantly over fifty years into a powerful analytical technique. This review aims to achieve five main goals. (1) Providing a comprehensive history of SERS's discovery, its experimental and theoretical foundations, its connections to advances in nanoscience and plasmonics, and highlighting collective contributions of key pioneers.
View Article and Find Full Text PDFPhotons do not carry sufficient momentum to induce indirect optical transitions in semiconducting materials, such as silicon, necessitating the assistance of lattice phonons to conserve momentum. Compared to direct bandgap semiconductors, this renders silicon a less attractive material for a wide variety of optoelectronic applications. In this work, we introduce an alternative strategy to fulfill the momentum-matching requirement in indirect optical transitions.
View Article and Find Full Text PDFMolecules immersed in liquid helium are excellent probes of superfluidity. Their electronic, vibrational, and rotational dynamics provide valuable clues about the superfluid at the nanoscale. Here we report on the experimental study of the laser-induced rotation of helium dimers inside the superfluid He bath at variable temperature.
View Article and Find Full Text PDFWhile most active plasmonic efforts focus on responsive metamaterials to modulate optical response, we present a simple alternative based on applied orientation control that can likely be implemented for many passive plasmonic materials. Passive plasmonic motifs are simpler to prepare but cannot be altered postfabrication. We show that such systems can be easily manipulated through substrate orientation control to generate both active plasmonic and active chiral plasmonic responses.
View Article and Find Full Text PDFThe structure and ultrafast photodynamics of ∼8 nm Au@Pt core-shell nanocrystals with ultrathin (<3 atomic layers) Pt-Au alloy shells are investigated to show that they meet the design principles for efficient bimetallic plasmonic photocatalysis. Photoelectron spectra recorded at two different photon energies are used to determine the radial concentration profile of the Pt-Au shell and the electron density near the Fermi energy, which play a key role in plasmon damping and electronic and thermal conductivity. Transient absorption measurements track the flow of energy from the plasmonic core to the electronic manifold of the Pt shell and back to the lattice of the core in the form of heat.
View Article and Find Full Text PDFAs proof-of-principle of chemically selective, spatially resolved imaging of individual bonds, we carry out electron energy-loss spectroscopy in a scanning transmission electron microscopy instrument on atomically precise, thiolate-coated gold nanoclusters linked with 5,5'-bis(mercaptomethyl)-2,2'-bipyridine dithiol ligands. The images allow the identification of bridging disulfide bonds (R-S-S-R) between clusters, and X-ray photoelectron spectra support the finding.
View Article and Find Full Text PDFTip-enhanced Raman scattering (TERS) with a cobalt tetraphenylporphyrin (CoTPP)- terminated silver tip is used to obtain ion-selective, atomically resolved images of an insulating CuN monolayer grown on Cu(100). Ion selective images are obtained through vibrational frequency shift maps using CoTPP vibrations with oppositely signed Stark tuning rates (STR). The images allow a quantitative analysis of the electrostatic field of the ionic lattice using in situ calibrated STRs.
View Article and Find Full Text PDFThe internal vibrations of molecules drive the structural transformations that underpin chemistry and cellular function. While vibrational frequencies are measured by spectroscopy, the normal modes of motion are inferred through theory because their visualization would require microscopy with ångström-scale spatial resolution-nearly three orders of magnitude smaller than the diffraction limit in optics. Using a metallic tip to focus light and taking advantage of the surface-enhanced Raman effect to amplify the signal from individual molecules, tip-enhanced Raman spectromicroscopy (TER-SM) reaches the requisite sub-molecular spatial resolution, confirming that light can be confined in picocavities and anticipating the direct visualization of molecular vibrations.
View Article and Find Full Text PDFContinuous wave (CW) pump-probe surface-enhanced Raman spectroscopy (SERS) is used to examine a range of plasmon-driven chemical behavior in the molecular SERS signal of trans-1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on individual Au nanosphere oligomers (viz., dimers, trimers, tetramers, etc.).
View Article and Find Full Text PDFMolecular 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.
View Article and Find Full Text PDFThe vibrational spectrum of a single carbon monoxide molecule, adsorbed on the tip apex of a scanning tunneling microscope, is used to image electrostatic fields with submolecular spatial resolution. The method takes advantage of the vibrational Stark effect to image local electrostatic fields and the single-molecule sensitivity of tip-enhanced Raman scattering (TERS) to optically relay the signal. We apply the method to single metalloporphyrins adsorbed on Au(111) to image molecular charges, intramolecular polarization, local photoconductivity, atomically resolved hydrogen bonds, and surface electron density waves.
View Article and Find Full Text PDFUsing two-photon photoemission electron microscopy (2P-PEEM) we image the polarization dependence of coupling and propagation of surface plasmon polaritons (SPPs) launched from edges of a triangular, micrometer size, single-crystalline Ag crystal by linearly or circularly polarized light. 2P-PEEM records interferences between the optical excitation field and SPPs it creates with nanofemto space-time resolution. Both the linearly and circularly polarized femtosecond light pulses excite spatially asymmetric 2PP yield distributions, which are imaged.
View Article and Find Full Text PDFTip-enhanced Raman spectromicroscopy (TERS) with CO-terminated plasmonic tips can probe angstrom-scale features of molecules on surfaces. The development of this technique requires understanding of how chemical environments affect the CO vibrational frequency and TERS intensity. At the scanning tunneling microscope junction of a CO-terminated Ag tip, we show that rather than the classical vibrational Stark effect, the large bias dependence of the CO frequency shift is due to ground-state charge transfer from the Ag tip into the CO π* orbital softening the C-O bond at more positive biases.
View Article and Find Full Text PDFThe tip is key to the successful execution of tip-enhanced Raman scattering (TERS) measurements in the single molecule limit. We show that nanoscopically smooth silver tips, batch produced through field-directed sputter sharpening, reliably attain TERS with enhancement factors that reach 10, as measured by the Raman spectra of single CO molecules attached to the tip apex. We validate the bare tips by demonstrating spectromicroscopy with submolecular spatial resolution and underscore that TERS is a near-field effect that does not obey simple selection rules.
View Article and Find Full Text PDFWe clarify mechanistic questions regarding plasmon-driven chemistry and nanoscale photocatalysis within optically confined near-field plasmonic systems. Using surface-enhanced Raman scattering (SERS), we directly monitor the photoinduced reaction dynamics of 4,4'-bipyridine molecules, localized in plasmonic hot spots within individual gold nanosphere oligomers. Our experiment generates surface electrons from the gold nanoparticle using an intense off-molecular resonance continuous wave pump field, and detects radical anion products via SERS.
View Article and Find Full Text PDFAtomically terminated and nanoscopically smooth silver tips effectively focus light on the angstrom scale, allowing tip-enhanced Raman spectromicroscopy (TER-sm) with single molecule sensitivity and submolecular spatial resolution. Through measurements carried out on cobalt-tetraphenylporphyrin (CoTPP) adsorbed on Au(111), we highlight peculiarities of vibrational spectromicroscopy with light confined on the angstrom scale. Field-gradient-driven spectra, orientational fingerprinting, and sculpting of local fields by atomic morphology of the junction are elucidated through measurements that range from 2D arrays at room temperature to single molecule manipulations at 5 K.
View Article and Find Full Text PDFSurface-enhanced femtosecond stimulated Raman spectroscopy (SE-FSRS) is an ultrafast Raman technique that combines the sensitivity of surface-enhanced Raman scattering with the temporal resolution of femtosecond stimulated Raman spectroscopy (FSRS). Here, we present the first successful implementation of SE-FSRS using a 1 MHz amplified femtosecond laser system. We compare SE-FSRS and FSRS spectra measured at 1 MHz and 100 kHz using both equal pump average powers and equal pump energies to demonstrate that higher repetition rates allow spectra with higher signal-to-noise ratios to be obtained at lower pulse energies, a significant advance in the implementation of SE-FSRS.
View Article and Find Full Text PDFThrough STM images, we show that azobenzene-terminated alkanethiols hover and twirl when confined between the Ag tip and Au(111) substrate of an STM junction. In contrast with mechanisms of activation used to drive molecular rotors, twirling is induced by the effective elimination of lateral corrugation in the energy landscape when molecules hover by their van der Waals attraction to the approaching tip. While in the stationary state the benzenes of the head group lie flat with an inter-ring separation of 7.
View Article and Find Full Text PDFThe resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2.
View Article and Find Full Text PDFWhile exploring photoisomerization of azobenzyl thiols (ABT) adsorbed on Au(111), through joint scanning tunneling microscopy (STM) and tip-enhanced Raman scattering (TERS) studies, the reversible photoisomerization of one molecule is captured in TERS trajectories. The unique signature of single molecule isomerization is observed in the form of anticorrelated flip-flops between two distinct spectra with two discrete, on- and off-levels. The apparently heterogeneously photocatalyzed reaction is assigned to cis-trans isomerization of an outlier, which is chemisorbed on the silver tip of the STM.
View Article and Find Full Text PDFNeuroimaging studies have shown that changes in brain morphology often accompany chronic pain conditions. However, brain biomarkers that are sensitive and specific to chronic pelvic pain (CPP) have not yet been adequately identified. Using data from the Trans-MAPP Research Network, we examined the changes in brain morphology associated with CPP.
View Article and Find Full Text PDFWe demonstrate a conductance switch controlled by the spin-vibronic density of an odd electron on a single molecule. The junction current is modulated by the spin-flip bistability of the electron. Functional images are provided as wiring diagrams for control of the switch's frequency, amplitude, polarity, and duty-cycle.
View Article and Find Full Text PDFElectroluminescence (EL) in scanning tunneling microscopy (STM), which enables spectroscopy with submolecular spatial resolution, is shown to be due to radiative ionization with vibronic shape resonances that carry Fano line profiles. Since Fano progressions retain phase information, the spectra can be transformed to the time domain to reconstruct the vibronic motion. In effect, measurements within a molecule are accessible with joint space-time resolution at the Å-fs limit.
View Article and Find Full Text PDFFabrication of sharp and smooth Ag tips is crucial in optical scanning probe microscope experiments. To ensure reproducible tip profiles, the polishing process is fully automated using a closed-loop laminar flow system to deliver the electrolytic solution to moving electrodes mounted on a motorized translational stage. The repetitive translational motion is controlled precisely on the μm scale with a stepper motor and screw-thread mechanism.
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