Search

A liquid-based surface-enhanced Raman spectroscopy assay termed PSALM is developed for the selective sensing of neurotransmitters (NTs) with a limit of detection below the physiological range of NT concentrations in urine. This assay is formed by quick and simple nanoparticle (NP) "mix-and-measure" protocols, in which FeIII bridges NTs and gold NPs inside the sensing hotspots. Detection limits of NTs from PreNP PSALM are significantly lower than those of PostNP PSALM, when urine is pretreated by affinity separation. Optimized PSALM enables the long-term monitoring of NT variation in urine in conventional settings for the first time, allowing the development of NTs as predictive or correlative biomarkers for clinical diagnosis.

Plasmonic nanoantennas can focus light at nanometer length scales providing intense field enhancements. For the tightest optical confinements (0.5-5 nm) achieved in plasmonic gaps, the gap spacing, refractive index, and facet width play a dominant role in determining the optical properties making tuning through antenna shape challenging. We show here that controlling the surrounding refractive index instead allows both efficient frequency tuning and enhanced in-/output coupling through retardation matching as this allows dark modes to become optically active, improving widespread functionalities.

Resistive switches, which are also known as memristors, are low-power, nanosecond-response devices that are used in a range of memory-centric technologies. Driven by an externally applied potential, the switching mechanism of valence change resistive memories involves the migration, accumulation and rearrangement of oxygen vacancies within a dielectric medium, leading to a change in electrical conductivity. The ability to look inside these devices and understand how morphological changes characterize their function has been vital in their development. However, current technologies are often destructive and invasive. Here, we report a non-destructive optical spectroscopy technique that can detect the motion of a few hundred oxygen vacancies with nanometre-scale sensitivity. Resistive switches are arranged in a nanoparticle-on-mirror geometry to exploit the high optical sensitivity to morphological changes occurring in tightly confined plasmonic hotspots within the switching material. Using this approach, we find that nanoscale oxygen bubbles form at the surface of a strontium titanate memristor film, leading ultimately to device breakdown on cycling. A nanoplasmonic technique was used to investigate in operando the switching properties of materials used in redox random access memories, providing insight into the operation and potential breakdown mechanisms of the devices.

Gold nanoparticles used in many types of nanostructure are mostly stabilized by citrate ligands. Fully understanding their dynamic surface chemistry is thus essential for applications, particularly since aging is frequently a problem. Using surface-enhanced Raman spectroscopy in conjunction with density functional theory calculations, we are able to determine Au-citrate coordination in liquid with minimal invasiveness. We show that citrate coordination is mostly bidentate and simply controlled by its protonation state. More complex binding motifs are caused by interfering chloride ions and gold adatoms. With increasing age of stored gold nanoparticle suspensions, gold adatoms are found to move atop the Au facets and bind to an additional terminal carboxylate of the citrate. Aged nanoparticles are fully refreshed by removing these adatoms, using etching and subsequent boiling of the gold nanoparticles.

The properties of nanoplasmonic structures depend strongly on their geometry, creating the need for high-precision control and characterization. Here, by exploiting the low activation energy of gold atoms on nanoparticle surfaces, we show how laser irradiation reshapes nanoparticle dimers. Time-course dark-field microspectroscopy allows this process to be studied in detail for individual nanostructures. Three regimes are identified: facet growth, formation of a conductive bridge between particles, and bridge growth. Electromagnetic simulations confirm the growth dynamics and allow measurement of bridge diameter, found to be highly reproducible and also self-limiting. Correlations in spectral resonances for the initial and final states give insight into the energy barriers for bridge growth. Dark-field microscopy shows that coalescence of multiple gaps in nanoparticle clusters can be digitally triggered, with each gap closing after discrete increases in irradiation power. Such control is important for light-induced nanowire formation or trimming of electronic and optoelectronic devices.

We report methods to synthesize sub-micron- and micron-sized patchy silica particles with fluorescently labeled hemispherical titania protrusions, as well as routes to efficiently characterize these particles and self-assemble these particles into non-close-packed structures. The synthesis methods expand upon earlier work in the literature, in which silica particles packed in a colloidal crystal were surface-patterned with a silane coupling agent. Here, hemispherical amorphous titania protrusions were successfully labeled with fluorescent dyes, allowing for imaging by confocal microscopy and super-resolution techniques. Confocal microscopy was exploited to experimentally determine the numbers of protrusions per particle over large numbers of particles for good statistical significance, and these distributions were compared to simulations predicting the number of patches as a function of core particle polydispersity and maximum separation between the particle surfaces. We self-assembled these patchy particles into open percolating gel networks by exploiting solvophobic attractions between the protrusions.

Metal/organic-molecule interactions underpin many key chemistries but occur on sub-nm scales where nanoscale visualisation techniques tend to average over heterogeneous distributions. Single molecule imaging techniques at the atomic scale have found it challenging to track chemical behaviour under ambient conditions. Surface-enhanced Raman spectroscopy can optically monitor the vibrations of single molecules but understanding is limited by the complexity of spectra and mismatch between theory and experiment. We demonstrate that spectra from an optically generated metallic adatom near a molecule of interest can be inverted into dynamic sub-Å metal-molecule interactions using a comprehensive model, revealing anomalous diffusion of a single atom. Transient metal-organic coordination bonds chemically perturb molecular functional groups > 10 bonds away. With continuous improvements in computational methods for modelling large and complex molecular systems, this technique will become increasingly applicable to accurately tracking more complex chemistries., We acknowledge financial support from EPSRC grant EP/G060649/1, EP/L027151/1, EP/G037221/1, EP/R013012/1, EPSRC NanoDTC, and EU grant THOR 829067 and ERC starting grant BioNet 757850. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. We acknowledge use of the Rosalind computing facility at King’s College London. We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC 397 (EP/P020194/1).

Funder: Leverhulme Trust, Funder: Trinity College, University of Cambridge, Funder: Isaac Newton Trust, Transient atomic protrusions in plasmonic nanocavities confine optical fields to sub-1-nm3 picocavities, allowing the optical interrogation of single molecules at room temperature. While picocavity formation is linked to both the local chemical environment and optical irradiation, the role of light in localizing the picocavity formation is unclear. Here, we combine information from thousands of picocavity events and simultaneously compare the transient Raman scattering arising from two incident pump wavelengths. Full analysis of the data set suggests that light suppresses the local effective barrier height for adatom formation and that the initial barrier height is decreased by reduced atomic coordination numbers near facet edges. Modeling the system also resolves the frequency-dependent picocavity field enhancements supported by these atomic scale features.

Understanding the interactions between molecules and metal surfaces is of widespread importance in electrochemistry, sensing, medical imaging/targeting, molecular electronics and spintronics. Although many techniques have characterized the molecule-metal transient bonds, conflicting conclusions arise from their buried location and heterogeneity, while single-molecule probes are scarce. Confinement of optical fields to picometre length-scales around adatoms (termed picocavities [1] , Fig. 1a ) has enabled tip-enhanced and surface-enhanced Raman spectroscopies (TERS and SERS, Fig. 1e ) of single-molecules. However how adatoms change with molecule-metal interactions, with light (both key ingredients in photocatalysis), and how they link to picocavity formation in metal nanogaps is not understood.

External-stimuli controlled reversible formation of radical species is of great interest for synthetic and supramolecular chemistry, molecular machinery, as well as emerging technologies ranging from (photo)catalysis and photovoltaics to nanomedicine. Here we show a novel hybrid colloidal system for light-driven reversible reduction of chemical species that, on their own, do not respond to light. This is achieved by the unique combination of photo-sensitive plasmonic aggregates and temperature-responsive inorganic species generating radicals that can be finally accepted and stabilised by non-photo-responsive organic molecules. In this system Au nanoparticles (NPs) self-assembled via sub-nm precise molecular spacers (cucurbit[n]urils) interact strongly with visible light to locally accelerate the decomposition of dithionite species (S(2)O(4)(2–)) close to the NP interfaces. This light-driven process leads to the generation of inorganic radicals whose electrons can then be reversibly picked up by small organic acceptors, such as the methyl viologen molecules (MV(2+)) used here. During light-triggered plasmon- and heat-assisted generation of radicals, the S(2)O(4)(2–) species work as a chemical ‘fuel’ linking photo-induced processes at the NP interfaces with redox chemistry in the surrounding water environment. By incorporating MV(2+) as a Raman-active reporter molecule, the resulting optically-controlled redox processes can be followed in real-time.

Irreproducibility in surface-enhanced Raman spectroscopy (SERS) due to variability among substrates is a source of recurrent debate within the field. It is regarded as a major hurdle towards the widespread adoption of SERS as a sensing platform. Most of the literature focused on developing substrates for various applications considers reproducibility of lower importance. Here, we address and analyse the sources of this irreproducibility in order to show how these can be minimised. We apply our findings to a simple substrate demonstrating reproducible SERS measurements with relative standard deviations well below 1% between different batches and days. Identifying the sources of irreproducibility and understanding how to reduce these can aid in the transition of SERS from the lab to real world applications.

Nucleation and growth is a technique widely used to prepare colloids, in which droplets are adsorbed onto substrate particles. Changing the contact angle of the substrates can greatly alter the morphology of the product particles. Here, we investigate the nucleation and growth of 3-methacryloxypropyltrimethoxysilane (MPTMS) both onto Stöber spheres and onto (cross-linked) MPTMS* spheres. The former results in ‘snowman’ particles with a cap-shaped MPTMS* compartment, and we show that their morphology is highly controllable via the MPTMS content in the reaction mixture. The contact angle of the MPTMS* compartment decreases with droplet diameter, suggesting that this wetting process is affected not only by surface tension but also by line tension. In contrast to Stöber spheres, MPTMS* substrate particles yield highly reproducible and tuneable ‘engulfed-sphere’ colloids with an internal reference axis (but a homogeneous mass distribution). These engulfed-sphere particles can be fully index-matched for confocal microscopy on account of their homogeneous refractive index. Suitable index-matching mixtures of polar and of low-polar media are presented, where cyclohexyl iodide (CHI) is introduced as a new medium for colloids of high refractive index. Finally, the index-matched engulfed-sphere colloids are self-assembled into (close-packed and long-range) plastic phases, and the particles’ rotational diffusion inside the crystal phases is tracked via confocal microscopy.

Plasmonic nanostructures can focus light far below the diffraction limit, and the nearly thousandfold field enhancements obtained routinely enable few- and single-molecule detection. However, for processes happening on the molecular scale to be tracked with any relevant time resolution, the emission strengths need to be well beyond what current plasmonic devices provide. Here, we develop hybrid nanostructures incorporating both refractive and plasmonic optics, by creating SiO 2 nanospheres fused to plasmonic nanojunctions. Drastic improvements in Raman efficiencies are consistently achieved, with (single-wavelength) emissions reaching 10 7 counts⋅mW −1 ⋅s −1 and 5 × 10 5 counts∙mW −1 ∙s −1 ∙molecule −1 , for enhancement factors >10 11 . We demonstrate that such high efficiencies indeed enable tracking of single gold atoms and molecules with 17-µs time resolution, more than a thousandfold improvement over conventional high-performance plasmonic devices. Moreover, the obtained (integrated) megahertz count rates rival (even exceed) those of luminescent sources such as single-dye molecules and quantum dots, without bleaching or blinking.

In this work, we demonstrate that coordination interactions between Fe\(^{3+}\) and cucurbit[7]uril (CB[7]) can be utilised to build up defined nanoscale spacing layers in metallic nanosystems. We begin by characterising the layer-by-layer deposition of CB[7] and FeCl\(_3\)·6H\(_2\)O coordination layers through the use of a QuartzCrystal Microbalance (QCM) and contact angle measurements. We then apply this layered structure to accurately control the spacing, and thus optical properties, of gold nanoparticles in a Nanoparticle-on-Mirror (NPoM) structure, which is demonstrated via normalising plasmon resonance spectroscopy.

Lipid bilayers assembled on solid substrates have been extensively studied with single-molecule resolution as the constituent molecules diffuse in 2D; however, the out-of-plane motion is typically ignored. Here we present the subnanometer out-of-plane diffusion of nanoparticles attached to hybrid lipid bilayers (HBLs) assembled on metal surfaces. The nanoscale cavity formed between the Au nanoparticle and Au film provides strongly enhanced optical fields capable of locally probing HBLs assembled in the gaps. This allows us to spectroscopically resolve the nanoparticles assembled on bilayers, near edges, and in membrane defects, showing the strong influence of charged lipid rafts. Nanoparticles sitting on the edges of the HBL are observed to flip onto and off of the bilayer, with flip energies of ∼10 meV showing how thermal energies dynamically modify lipid arrangements around a nanoparticle. We further resolve the movement of individual lipid molecules by doping the HBL with low concentrations of Texas Red (TxR) dye-labeled lipids.

The dynamic restructuring of metal nanoparticle surfaces is known to greatly influence their catalytic, electronic transport, and chemical binding functionalities. Here we show for the first time that non-equilibrium atomic-scale lattice defects can be detected in nanoparticles by purely optical means. These fluctuating states determine interface electronic transport for molecular electronics but because such rearrangements are low energy, measuring their rapid dynamics on single nanostructures by X-rays, electron beams, or tunnelling microscopies, is invasive and damaging. We utilise nano-optics at the sub-5nm scale to reveal rapid (on the millisecond timescale) evolution of defect morphologies on facets of gold nanoparticles on a mirror. Besides dynamic structural information, this highlights fundamental questions about defining bulk plasma frequencies for metals probed at the nanoscale., Dynamic restructuring of metal nanoparticle surfaces greatly influences their catalytic, electronic transport, and chemical binding functionalities. Here, the authors show that non-equilibrium atomic-scale lattice defects can be detected in nanoparticles by using nano-optics at the sub-5nm scale.

Molecular electronics promises a new generation of ultralow-energy information technologies, based around functional molecular junctions. Here, we report optical probing that exploits a gold nanoparticle in a plasmonic nanocavity geometry used as one terminal of a well-defined molecular junction, deposited as a self-assembled molecular monolayer on flat gold. A conductive transparent cantilever electrically contacts individual nanoparticles while maintaining optical access to the molecular junction. Optical readout of molecular structure in the junction reveals ultralow-energy switching of ∼50 zJ, from a nano-electromechanical torsion spring at the single molecule level. Real-time Raman measurements show these electronic device characteristics are directly affected by this molecular torsion, which can be explained using a simple circuit model based on junction capacitances, confirmed by density functional theory calculations. This nanomechanical degree of freedom is normally invisible and ignored in electrical transport measurements but is vital to the design and exploitation of molecules as quantum-coherent electronic nanodevices., The development of molecular electronics at single molecule level calls for new tools beyond electrical characterisation. Kos et al. show an optical probe of molecular junctions in a plasmonic nanocavity geometry, which supports in situ interrogation of molecular configurations.

In order to optimize surface-enhanced Raman scattering (SERS) of noble metal nanostructures for enabling chemical identification of analyte molecules, careful design of nanoparticle structures must be considered. We spatially map the local SERS enhancements across individual micro-aggregates comprised of monodisperse nanoparticles separated by rigid monodisperse 0.9 nm gaps and show the influence of depositing these onto different underlying substrates. Experiments and simulations show that the gaps between neighbouring nanoparticles dominate the SERS enhancement far more than the gaps between nanoparticles and substrate.

Quantitative applications of surface enhanced Raman spectroscopy (SERS) often rely on surface partition layers grafted to SERS substrates to collect and trap solvated analytes that would not otherwise adsorb onto metals. Such binding layers drastically broaden the scope of analytes that can be probed. However, excess binding sites introduced by this partition layer also trap analytes outside the plasmonic †hot-spots'. We show that by eliminating these binding sites, limits of detection (LODs) can effectively be lowered by more than an order of magnitude. We highlight the effectiveness of this approach by demonstrating quantitative detection of controlled drugs down to sub-nanomolar concentrations in aqueous media. Such LODs are low enough to screen, for example, urine at clinically relevant levels. These findings provide unique insights into the binding behavior of analytes, which are essential when designing high performance SERS substrates.

Sylwester Gawinkowski opened discussion of the paper by Javier Aizpurua: How many electrons are transferred by one ultrashort pulse? If you are thinking about applications in electronics, then it seems that this number may be too small. Is simply increasing the pulse energy and therefore significantly increasing the number of such emitted electrons possible?

The resonance wavelength of a coupled plasmonic system is extremely sensitive to the distance between its metallic surfaces, resulting in "plasmon rulers". We explore this behavior in the subnanometer regime using self-assembled monolayers of bis-phthalocyanine molecules in a nanoparticle-on-mirror (NPoM) construct. These allow unprecedented subangstrom control over spacer thickness via choice of metal center, in a gap-size regime at the quantum-mechanical limit of plasmonic enhancement. A dramatic shift in the coupled plasmon resonance is observed as the gap size is varied from 0.39 to 0.41 nm. Existing theoretical models are unable to account for the observed spectral tuning, which requires inclusion of the quantum-classical interface, emphasizing the need for new treatments of light at the subnanoscale.

International audience; (600:[600]600) Sylwester Gawinkowski opened a general discussion of the paper by Jorge Salmon-Gamboa: Why you are using SiO 2 nanoparticles? Do they have any function or are they only the substrate to attach other active nano-particles to? You have shown that only gold nanoparticles attached to silica nanoparticles do not inuence the rate of reaction signicantly. You have also demonstrated that adding platinum decorations on the gold nanoparticles causes a strong increase in the reaction rate. The signicance of the gold nanoparticles would be more clearly shown with a simple experiment in which you have no gold nanoparticles but still have platinum decorations. Jorge Salmon-Gamboa replied: Silica nanoparticles were chosen as a nano-sized inert substrate for Au nanoparticles. This choice of substrate provides a larger surface area covered with the active Au-Pt nanoparticles, in contrast to the situation when the active particles are placed directly onto a at substrate. Aiming for applications, the SiO 2-Au-Pt nanoparticles can then in turn be attached onto a at surface, forming a solid device that can be submerged into water, avoiding the problem of water contamination by nanoparticles. The role of the Au nano-particles was investigated. Under illumination in the LSP spectral band (556-566 nm), SiO 2-Pt did not enhance the reaction rate. In contrast, under the same conditions, SiO 2-Au-Pt showed a considerably enhanced rate, proving that hot carriers were generated in Au (see Fig. 1 below). (601:[601]601) Yuri Diaz Fernandez continued the discussion: I have two questions: (1) Can you comment on the dispersity of the size distribution of metal and SiO 2 particles and how well controlled are these in your system?

Reproducible confinement of light on the nanoscale is essential for the ability to observe and control chemical reactions at the single-molecule level. Here we reliably form millions of identical nanocavities and show that the light can be further focused down to the subnanometer scale via the creation of picocavities, single-adatom protrusions with angstrom-level resolution. For the first time, we stabilize and analyze these cavities at room temperatures through high-speed surface-enhanced Raman spectroscopy on specifically selected molecular components, collecting and analyzing more than 2 million spectra. Data obtained on these picocavities allows us to deduce structural information on the nanoscale, showing that thiol binding to gold destabilizes the metal surface to optical irradiation. Nitrile moieties are found to stabilize picocavities by 10-fold against their disappearance, typically surviving for >1 s. Such constructs demonstrate the accessibility of single-molecule chemistry under ambient conditions., We acknowledge financial support from EPSRC Grants EP/L027151/1 and EP/N020669/1. C.C. acknowledges support from NPL PO443073. B.d.N. acknowledges support from the Leverhulme Trust and Isaac Newton Trust. R.C. acknowledges financial support from a Junior Research Fellowship of Trinity College.

Reproducible confinement of light on the nanoscale is essential for the ability to observe and control chemical reactions at the single-molecule level. Here we reliably form millions of identical nanocavities and show that the light can be further focused down to the subnanometer scale via the creation of picocavities, single-adatom protrusions with angstrom-level resolution. For the first time, we stabilize and analyze these cavities at room temperatures through high-speed surface-enhanced Raman spectroscopy on specifically selected molecular components, collecting and analyzing more than 2 million spectra. Data obtained on these picocavities allows us to deduce structural information on the nanoscale, showing that thiol binding to gold destabilizes the metal surface to optical irradiation. Nitrile moieties are found to stabilize picocavities by 10-fold against their disappearance, typically surviving for1 s. Such constructs demonstrate the accessibility of single-molecule chemistry under ambient conditions.

In recent years, single-molecule sensitivity achievable by surface-enhanced Raman spectroscopy (SERS) has been widely reported. We use this to investigate supramolecular host-guest chemistry with the macrocyclic host cucurbit[7]uril, on a few-to-single-molecule level. A nanogap geometry, comprising individual gold nanoparticles on a planar gold surface spaced by a single layer of molecules, gives intense SERS signals. Plasmonic coupling between the particle and the surface leads to strongly enhanced optical fields in the gap between them, with single-molecule sensitivity established using a modification of the well-known bianalyte method. Changes in the Raman modes of the host molecule are observed when single guests included inside its cavity internally stretch it. Anisotropic intermolecular interactions with the guest are found which show additional distinct features in the Raman modes of the host molecule.

Nanoparticle assemblies can be investigated in 3 dimensions using electron tomography. However, it is not straightforward to obtain quantitative information such as the number of particles or their relative position. This becomes particularly difficult when the number of particles increases. We propose a novel approach in which prior information on the shape of the individual particles is exploited. It improves the quality of the reconstruction of these complex assemblies significantly. Moreover, this quantitative Sparse Sphere Reconstruction approach yields directly the number of particles and their position as an output of the reconstruction technique, enabling a detailed 3D analysis of assemblies with as many as 10 000 particles. The approach can also be used to reconstruct objects based on a very limited number of projections, which opens up possibilities to investigate beam sensitive assemblies where previous reconstructions with the available electron tomography techniques failed.

Small numbers of surface-bound molecules are shown to behave as would be expected for optomechanical oscillators placed inside plasmonic nanocavities that support extreme confinement of optical fields. Pulsed Raman scattering reveals superlinear Stokes emission above a threshold, arising from the stimulated vibrational pumping of molecular bonds under pulsed excitation shorter than the phonon decay time, and agreeing with pulsed optomechanical quantum theory. Reaching the parametric instability (equivalent to a phonon laser or “phaser” regime) is, however, hindered by the motion of gold atoms and molecular reconfiguration at phonon occupations approaching unity. We show how this irreversible bond breaking can ultimately limit the exploitation of molecules as quantum-mechanical oscillators, but accesses optically driven chemistry., We acknowledge financial support from EPSRC Grants No. EP/G060649/1, No. EP/K028510/1, No. EP/L027151/1, No. EP/G037221/1, No. EPSRC NanoDTC EP/L015978/1, and ERC Grant No. LINASS 320503. M. K. S. and J. A. acknowledge support from MINECO Project No. FIS2016-80174-P and the COST Action MP1403 “Nanoscale Quantum Optics” supported by COST (European Cooperation in Science and Technology). M. S. acknowledges support from the Australian Research Council (ARC) Discovery Project No. DP160101691. F. B. acknowledges support from the Winton Programme for the Physics of Sustainability. We thank Dr. Guolei Xiang (University of Cambridge, Chemistry Department) for support with the TGA measurements.

Discussions.

Single nanoparticles are shown to develop a localized acoustic resonance, the bouncing mode, when placed on a substrate. If both substrate and nanoparticle are noble metals, plasmonic coupling of the nanoparticle to its image charges in the film induces tight light confinement in the nanogap. This yields ultrastrong ``acoustoplasmonic'' coupling with a figure of merit 7 orders of magnitude higher than conventional acousto-optic modulators. The plasmons thus act as a local vibrational probe of the contact geometry. A simple analytical mechanical model is found to describe the bouncing mode in terms of the nanoscale structure, allowing transient pump-probe spectroscopy to directly measure the contact area for individual nanoparticles.

Plasmonic nanocavities with sub-5-nm gaps between nanoparticles support multiple resonances possessing ultra-high-field confinement and enhancements. Here we systematically compare the two fundamentally different resonant gap modes: transverse waveguide (s) and antenna modes (l), which, despite both tightly confining light within the gap, have completely different near-field and far-field radiation patterns. By varying the gap size, both experimentally and theoretically, we show how changing the nanoparticle shape from sphere to cube alters coupling of s and l modes, resulting in strongly hybridized (j) modes. Through rigorous group representation analysis we identify their composition and coupling. This systematic analysis of the Purcell factors shows that modes with optical field perpendicular to the gap are best to probe the optical properties of cavity-bound emitters, such as single molecules.

The first page of this article is displayed as the abstract., Rohit Chikkaraddy opened the discussion of the Introductory Lecture: Regarding quantifying the chemical enhancement, you showed a systematic change in the SERS enhancement for halide substituted molecules due to charge transfer from the metal. Is the extra enhancement due to an inherent increase in the Raman cross-section of the molecule? How do you go about referencing, as the charge transfer changes the vibrational frequency? Richard Van Duyne answered: The extra enhancement is not due to an increase in the Raman cross section, as that is ratioed out in the calculation of the enhancement factor. The charge transfer (CT) process does not transfer a complete electron, it is a fractional degree of CT. Thus the change in vibrational frequency is small. DFT calculations that provide eigenvectors allow one to reference the vibrational modes of the free molecule with those of the adsorbed molecule. Sylwester Gawinkowski asked: You have shown that the enhancement factor curve is redshifted relative to the plasmon resonance band and has a maximum at about 800 nm. This means that the SERS signal should be strongest for excitations in the near infrared spectral region. Why do most SERS reports, particularly related to single molecule SERS, have the excitation in the green or red spectral range and not in the near infrared?

Discussions.