6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

/pdf/quantum-mechanical-continuum-solvation-models-3edv963g14.pdf

Quantum mechanical continuum solvation models.

The optical properties of metal nanoparticles have long been of interest in physical chemistry, starting with Faraday's investigations of colloidal gold in the middle 1800s. More recently, new lithographic techniques as well as improvements to classical wet chemistry methods have made it possible to synthesize noble metal nanoparticles with a wide range of sizes, shapes, and dielectric environments. In this feature article, we describe recent progress in the theory of nanoparticle optical properties, particularly methods for solving Maxwell's equations for light scattering from particles of arbitrary shape in a complex environment. Included is a description of the qualitative features of dipole and quadrupole plasmon resonances for spherical particles; a discussion of analytical and numerical methods for calculating extinction and scattering cross-sections, local fields, and other optical properties for nonspherical particles; and a survey of applications to problems of recent interest involving triangula...

/pdf/the-optical-properties-of-metal-nanoparticles-the-influence-16vrpkvhkg.pdf

The Optical Properties of Metal Nanoparticles: The Influence of Size, Shape, and Dielectric Environment

Fundamentals of Plasmonics.- Electromagnetics of Metals.- Surface Plasmon Polaritons at Metal / Insulator Interfaces.- Excitation of Surface Plasmon Polaritons at Planar Interfaces.- Imaging Surface Plasmon Polariton Propagation.- Localized Surface Plasmons.- Electromagnetic Surface Modes at Low Frequencies.- Applications.- Plasmon Waveguides.- Transmission of Radiation Through Apertures and Films.- Enhancement of Emissive Processes and Nonlinearities.- Spectroscopy and Sensing.- Metamaterials and Imaging with Surface Plasmon Polaritons.- Concluding Remarks.

/pdf/plasmonics-fundamentals-and-applications-4syb9877sr.pdf

Plasmonics: Fundamentals and Applications

Localized surface plasmon resonance (LSPR) spectroscopy of metallic nanoparticles is a powerful technique for chemical and biological sensing experiments. Moreover, the LSPR is responsible for the electromagnetic-field enhancement that leads to surface-enhanced Raman scattering (SERS) and other surface-enhanced spectroscopic processes. This review describes recent fundamental spectroscopic studies that reveal key relationships governing the LSPR spectral location and its sensitivity to the local environment, including nanoparticle shape and size. We also describe studies on the distance dependence of the enhanced electromagnetic field and the relationship between the plasmon resonance and the Raman excitation energy. Lastly, we introduce a new form of LSPR spectroscopy, involving the coupling between nanoparticle plasmon resonances and adsorbate molecular resonances. The results from these fundamental studies guide the design of new sensing experiments, illustrated through applications in which researchers use both LSPR wavelength-shift sensing and SERS to detect molecules of chemical and biological relevance.

https://www.photonics.ethz.ch/fileadmin/user_upload/Courses/NanoOptics/willets.pdf

Localized Surface Plasmon Resonance Spectroscopy and Sensing

In 1978 it was discovered, largely through the work of Fleischmann, Van Duyne, Creighton, and their coworkers that molecules adsorbed on specially prepared silver surfaces produce a Raman spectrum that is at times a millionfold more intense than expected. This effect was dubbed surface-enhanced Raman scattering (SERS). Since then the effect has been demonstrated with many molecules and with a number of metals, including Cu, Ag, Au, Li, Na, K, In, Pt, and Rh. In addition, related phenomena such as surface-enhanced second-harmonic generation, four-wave mixing, absorption, and fluorescence have been observed. Although not all fine points of the enhancement mechanism have been clarified, the majority view is that the largest contributor to the intensity amplification results from the electric field enhancement that occurs in the vicinity of small, interacting metal particles that are illuminated with light resonant or near resonant with the localized surface-plasmon frequency of the metal structure. Small in this context is gauged in relation to the wavelength of light. The special preparations required to produce the effect, which include among other techniques electrochemical oxidation-reduction cycling, deposition of metal on very cold substrates, and the generation of metal-island films and colloids, is now understood to be necessary as a means of producing surfaces with appropriate electromagnetic resonances that may couple to electromagnetic fields either by generating rough films (as in the case of the former two examples) or by placing small metal particles in close proximity to one another (as in the case of the latter two). For molecules chemisorbed on SERS-active surface there exists a "chemical enhancement" in addition to the electromagnetic effect. Although difficult to measure accurately, the magnitude of this effect rarely exceeds a factor of 10 and is best thought to arise from the modification of the Raman polarizability tensor of the adsorbate resulting from the formation of a complex between the adsorbate and the metal. Rather than an enhancement mechanism, the chemical effect is more logically to be regarded as a change in the nature and identity of the adsorbate.

Surface-enhanced spectroscopy

A theory for surface enhanced Raman scattering (SERS) is developed Effects due to realistic surface geometry and dielectric properties are included Three sources of enhanced Raman scattering are noted: the image dipole enhancement effect, the increase of local field (’’lightning rod’’ effect), and the resonant excitation of surface plasmons The surface is modeled as a hemispheroid protruding from a conducting plane, although other models are considered The spherical limit is discussed in some detail and molecular orientation effects are considered Cross sections for Mie, Rayleigh, and Raman scattering are derived

Electromagnetic theory of enhanced Raman scattering by molecules adsorbed on rough surfaces

Optical properties of small dielectric spheroids with or without adsorbed molecules are studied theoretically. Expressions for the absorption line shapes, the radiative and nonradiative decay rates, and quantum yields are derived. In the case of a molecule near a spheroid the magnitudes differ dramatically from the corresponding case of a molecule near a plane.

Spectroscopic properties of molecules interacting with small dielectric particles

The enhancements of normal Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on identical, well‐characterized, silver‐island films are reported. The enhancement arises from the electromagnetic interaction between the molecules and the electronic plasma resonance of the silver islands. A hierarchy of enhancement ratios is found, with typical values of 105 for RS, 103 for RRS and 10−1 to 10 for fluorescence, depending on the quantum yield of the molecular fluorescence. A model, developed on heuristic grounds and substantiated using the density matrix formalism, describes the light scattering processes and the effects of the plasma resonance. This model presents a unified picture of the surface‐induced enhancement effects and is consistent with the experimental values. The comparison of all the forms of optical scattering leads to a complete determination of the role of the plasma resonances in the various portions of the scattering process. The excitation of the electronic plasma resonance results in an increased local field at the molecules leading to an increased excitation or absorption rate. Similarly, the excitation of the plasma resonance by the molecular emission dipole results in an increase in the radiative decay rate. However, the electromagnetic coupling of the molecule to the plasma resonance also adds an additional damping channel which can result in a reduction of the absorption or excitation rate as well as the emission yield. The resultant balance of these processes leads to the hierarchy in the measured enhancements. The hierarchy of enhancements is also shown to have important spectroscopic consequences.

The enhancement of Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on a rough silver surface

Preface. List of Tables. Introduction. STRUCTURE OF MATERIALS. Structure of Crystals. Bonding in Solids. Diffraction and the Reciprocal Lattice. Order and Disorder in Solids. PHYSICAL PROPERTIES OF MATERIALS. Phonons. Thermally Activated Processes, Phase Diagrams, and Phase Transitions. Electrons in Solids: Electrical and Thermal Properties. Optical Properties of Materials. Magnetic Properties of Materials. Mechanical Properties of Materials. CLASSES OF MATERIALS. Semiconductors. Metals and Alloys. Ceramics. Polymers. Dielectric and Ferroelectric Materials. Superconductors. Magnetic Materials. Optical Materials. SURFACES, THIN FILMS, INTERFACES, AND MULTILAYERS. Surfaces. Thin Films, Interfaces, and Multilayers. SYNTHESIS AND PROCESSING OF MATERIALS. Synthesis and Processing of Materials. Characterization of Materials. Appendix WA: Thermodynamics. Appendix WB: Statistical Mechanics. Appendix WC: Quantum Mechanics. Materials Index. Index.

The Physics and Chemistry of Materials

A molecule adsorbed on the surface of a conducting prolate ellipsoid will Raman scAtter with an enhanced cross section. The relevance of this fact to the phenomenon of surface enhanced Raman scattering (SERS) is discussed. (AIP)

Joel I. Gersten

Papers

Electromagnetic theory of enhanced Raman scattering by molecules adsorbed on rough surfaces

Spectroscopic properties of molecules interacting with small dielectric particles

The enhancement of Raman scattering, resonance Raman scattering, and fluorescence from molecules adsorbed on a rough silver surface

The Physics and Chemistry of Materials

The effect of surface roughness on surface enhanced Raman scattering