Surface plasmon absorption

Michaelis and Henglein [131] prepared Pd-core/Ag-shell bimetallic nanoparticles by the successive reduction of Ag ions on the surface of Pd nanoparticles (mean radius 4.6 nm) with formaldehyde. The core/shell nanoparticles, however, became larger and deviated from spherical with an increase in the shell thickness. The Pd/Ag bimetallic nanoparticles had a surface plasmon absorption band close to 380 nm when more than 10-atomic layer of Ag are deposited. When the shell thickness is less than 10-atomic layer, the absorption band is located at shorter wavelengths and the band disappears below about three-atomic layer. 

Fig. 1.12 (A) Increase in surface plasmon ab- and from mixtures with lower chitosan concen-sorptionasAu nanoparticles are produced from a tration (ii) or lower HAuCI4 amount (iii) six reaction mixture containing 1 % chitosan, 1 % different self-sustained nanocomposite films acetic acid and 0.01 % tetrachloroauric (III) acid showing the control over the optical properties. (HAuCU) (B) shiftofsurface plasmon absorption Reprinted with permission from [164], 2004, for films prepared from the previous mixture (i), American Chemical Society.

Figure 21.6 Schematic illustration of the dynamics of the photoluminescence from the Au(0) i system. The inset shows the comparison of the Au(0) i surface plasmon absorption peak with the spectral distribution of the Au(0) i emission peakfor excitation at 3.14 eV (395 nm).

Adsorption of ions or molecules on metal clusters markedly affects their optical properties. It was shown that the intensity and the shape of the surface plasmon absorption band of silver nanometric particles, which is close to 380 nm, change upon adsorption of various substances [125]. The important damping of the band generally observed is assigned to the change of the electron density of the thin surface layer of the... 

Differences in surface plasmon absorption among various metals are clearly revealed by imagining the trajectories to be superposed onto the contour plot . Spherical silver and aluminum particles have intense surface plasmon absorption peaks because t" is small at the frequency where c is - 2, whereas gold... 

Surface plasmon absorption has been observed for small particles of several other metals, and many calculations have been published these are too... 

Fig. 83. Surface plasmon absorption band of a 1 x 10 4moldm-3 silver sol (O). Changes in absorption after electron donation (a) and positive hole injection (fc) by free radicals [506]...

Hole injection into the silver particles was accomplished by allowing OH (formed in the pulse radiolysis of N20-saturated, aqueous, 3.0-nm-diameter Ag particle solution (Eqs. 22,23) in the absence of the -OH scavenger, 2-propanol) to extract electrons from the surface of colloidal, metallic silver particles. The process resulted in a red shift, broadening, and a decrease in intensity of the silver plasmon absorption band (see 0 - b change in Fig. 83) [506]. Addition of silver ions to metallic silver colloids elicited a similar change in the absorption spectrum [506]. 

Electron transfer was mediated by metallic silver colloids whose surfaces contained either a strong (SH ) or a weak (CN ) nucleophile [531]. The former case is illustrated by changes in the absorption spectrum of a 1.0 x 10 4 M, deaerated solution of metallic silver particles, subsequent to the consecutive addition of 2.0 x 10 4 M NaSH and 3.0 x 10-4 M anthracene quinone sulfonic acid, AQS (Fig. 85) [506]. The origin of the intensity decrease and the broadening of the silver plasmon absorption band upon the addition of nucleophilic SH is incompletely understood. However, that an absorption... 

The ratio of surface area to bulk volume of the reinforcing particles can have important implications on optical properties, where the contribution of surface states can result in unique properties.56,57 These surface states cause shifts in the plasmon absorption frequencies and can be manipulated by use of different combinations of metals and ceramics.56 Another possibility due to the high surface area of the metal particles is catalysis applications, provided the ceramic matrix contains open pores.19... 

For the same particles, the volume plasmon is located at very high energies (6-9 eV). The surface obviously plays a very important role for the observation of the surface plasmon resonance because it alters the boundary conditions for the polarizability of the metal and therefore shifts the resonance to optical frequencies. In this sense, the surface plasmon absorption is a small particle (or thin layer) effect but is definitely not a quantum size effect [14]. 

Formation of zero-valent copper clusters with glutathione has been studied anaerobically. The ligand has been reported to provide a snbstantial degree of surface passivation. Rednction of a Cu(II)-GSH complex prodnced nanoparticles with a plasmon resonance band at 363 nm. These nanoparticles possessed a diameter of 9.7 4.3nm as demonstrated by TEM analysis. Under aerobic conditions, the nanoparticles oxidatively degrade as evinced by the loss of the plasmon absorption band over time. 

For the smallest of metallic nanoclusters with dimensions ca. < 2 nm, the surface plasmon absorption disappears. Since so few atoms comprise discrete nanoclusters of this size, the spacings between adjacent energy levels (referred to as the Kubo... 

In Eq. (3), is the relevant molecular transition frequency, y is a dam >ing rate, is a polarizability, and (/) is the z-component of the total electric field in the vicinity of the molecule. If (t) were simply of the form i)Cos(fijr), then Eq. (3) is the well-known phenomenological Lorentzian oscillator model of absorption which leads to an approximate Lorentzian form for the absorption cross section [1]. Similar remarks hold for the SP dipole, fi/f), if E t) = ocos(mr), where E t) is the z-component of the total electric field near the SP dipole. The parameters 04,74 and a, in this case are chosen such that the resulting Lorentzian cross section proximates the known exact sur ce plasmon absorption cross section or its appropriate form in the quasistatic (a A=2 tic/cs) limit. Note that I am using a simplified notation compared to the various notations of Refs. [13-15]. (Relative to Ref. [13], for example, my definitions of surface plasmon dipole... 

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