The field of nanoparticle research has drawn much attention in the past decade as a result of the search for new materials. Size confinement results in new electronic and optical properties, possibly suitable for many electronic and optoelectronic applications. A characteristic feature of noble metal nanoparticles is the strong color of their colloidal solutions, which is caused by the surface plasmon absorption. This article describes our studies of the properties of the surface plasmon absorption in metal nanoparticles that range in size between 10 and 100 nm. The effects of size, shape, and composition on the plasmon absorption maximum and its bandwidth are discussed. Furthermore, the optical response of the surface plasmon absorption due to excitation with femtosecond laser pulses allowed us to follow the electron dynamics (electron−electron and electron−phonon scattering) in these metal nanoparticles. It is found that the electron−phonon relaxation processes in nanoparticles, which are smaller than t...

Spectral properties and relaxation dynamics of surface plasmon electronic oscillations in gold and silver nanodots and nanorods

Core−shell nanocomposites (R−Au) bearing well-defined gold nanoparticles as surface atoms of variable sizes (8−55 nm) have been synthesized exploiting polystyrene-based commercial anion exchangers. Immobilization of gold nanoparticles, prepared by the Frens method, onto the resin beads in the chloride form is possible by the ready exchange of the citrate-capped negatively charged gold particles. The difficulty of nanoparticle loading, avoiding aggregation, has been solved by stepwise operation. Analysis of the gold particles after immobilization and successive elution confirm the unaltered particle morphology while compared to those of the citrate-capped gold particles in colloidal dispersion. It was observed that the rate of the reaction increases with the increase in catalyst loading, which suggests the catalytic behavior of the gold nanoparticles for the reduction of the aromatic nitrocompounds. The rate constant, k, was found to be proportional to the total surface area of the nanoparticles in the sys...

Synthesis and size-selective catalysis by supported gold nanoparticles: Study on heterogeneous and homogeneous catalytic process

Nonrelativistic and relativistic Hartree–Fock (HF) and configuration interaction (CI) calculations have been performed in order to analyze the relativistic and correlation effects in various diatomic gold compounds. It is found that relativistic effects reverse the trend in most molecular properties down the group (11). The consequences for gold chemistry are described. Relativistic bond stabilizations or destabilizations are dependent on the electronegativity of the ligand, showing the largest bond destabilization for AuF (86 kJ/mol at the CI level) and the largest stabilization for AuLi (−174 kJ/mol). Relativistic bond contractions lie between 1.09 (AuH+) and 0.16 A (AuF). Relativistic effects of various other properties are discussed. A number of as yet unmeasured spectroscopic properties, such as bondlengths (re), dissociation energies (De), force constants (ke), and dipole moments (μe), are predicted.

Relativistic effects in gold chemistry. I. Diatomic gold compounds

The femtosecond optical response of noble metal nanoparticles and its connection to the ultrafast electron dynamics are discussed in light of the results of high-sensitivity femtosecond pump−probe experiments. The physical origins of the nonlinear responses in the vicinity of the surface plasmon resonance and interband transition threshold are analyzed using extension of the theoretical models used in the bulk materials. These responses contain information on the electron interaction processes (electron−electron and electron−phonon scattering) that can thus be directly investigated in the time domain. Their size and environment dependences are discussed, and the results are compared to the ones in the bulk materials. Time-resolved techniques also permit direct study of the vibrational modes of metal nanoparticles and, in particular, the determination of their damping, which is a sensitive probe of the nature of the surrounding matrix and of the interface quality.

Ultrafast Electron Dynamics and Optical Nonlinearities in Metal Nanoparticles

Five massive gold-cluster molecules have been isolated in high yield and have undergone separate structural characterization, and their electronic structure has been deduced by optical absorption spectroscopy. These new molecules are distinguished by a crystalline (or quasicrystalline) core of densely packed Au atoms, ranging in size from ∼1.1 nm (∼40 atoms) to ∼1.9 nm (∼200 atoms), surrounded by a compact monolayer of various thio (RS) adsorbates. They are obtained as the thermally and environmentally stable products of the reductive decomposition of nonmetallic (−AuS(R)−) polymer in solution, are separated according to size by fractional crystallization or column chromatography, as monitored by high-mass spectrometry, and are characterized structurally by methods including X-ray diffraction (small and large angle), high-resolution electron microscopy, and scanning tunneling microscopy. The optical absorption spectra of dilute solutions of these molecules show size-dependent steplike structure with an on...

Isolation of Smaller Nanocrystal Au Molecules: Robust Quantum Effects in Optical Spectra

The energy band structure of gold is calculated by the relativistic augmented-plane-wave (RAPW) method. A nonrelativistic calculation is also presented, and a comparison between this and the RAPW results demonstrates that the shifts and splittings due to relativistic effects are of the same order of magnitude as the gaps (approximately 1 eV). Various integrated functions, density of states, joint density of states, and energy distributions of joint density of states are derived from the RAPW calculation. These functions are used in an interpretation of photoemission and static reflectance measurements. It is shown that the photoemission results are extremely well described in terms of a model assuming all transitions to be direct whereas a nondirect model fails. The ${\ensuremath{\epsilon}}_{2}$ profile calculated in a crude model assuming constant matrix elements matches well the corresponding experimental results. The calculated interband edge ($\ensuremath{\hbar}{\ensuremath{\omega}}_{i}=2.38$ eV) agrees with experimental values, and the absorption tail below the interband edge which is found in experimental traces is also contained in the theoretical curve. By means of a calculation of the Fermi surface and the constant-energy-difference surfaces it has been possible to trace out the regions in $\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}$ space where the edge and tail transitions occur. It is demonstrated that structure in the static reflection curves are not related to critical points in the band structure. The arguments are supported by calculations of temperature shifts of the critical-point energies and comparison to the observed temperature shifts of the elements of structure in the experimental ${\ensuremath{\epsilon}}_{2}$ function. Such structure may originate in extended rather than localized regions of $\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}$ space. In contrast, critical-point transitions show up clearly in modulated reflectance spectra, and all elements of structure are fully accounted for by our band model. The temperature and strain responses in the band structure are determined by performing the RAPW calculation with two lattice constants and estimating the effects of the lattice vibrations by means of an OPW-LCAO (linear combination of atomic orbitals) scheme with pseudopotential Fourier constants reduced by the appropriate Debye-Waller factors. The phonon spectrum has been calculated for the latter purpose.

/pdf/relativistic-band-calculation-and-the-optical-properties-of-4mt6svzzvw.pdf

Relativistic Band Calculation and the Optical Properties of Gold

The electronic energy-band structure of tungsten has been calculated by means of the relativistic-augmented-plane-wave method. A series of mutually related potentials are constructed by varying the electronic configuration and the amount of Slater exchange included. The best band structure is obtained from an ad hoc potential based on a Dirac-Slater atomic calculation for the ground-state configuration and with full Slater exchange in the atomic as well as in the crystal potential. The selection of this best potential is justified by comparing the calculated band structure to Fermi-surface experiments and to optical-reflectance measurements up to 5-eV photon energy. The temperature and strain responses in the band structure are estimated from band calculations with four different lattice constants. The band structure was determined in the entire Brillouin zone and is applied to a calculation of photoemission spectra from W single crystals. The nondirect as well as the direct models for bulk photoemission processes are investigated. The emission from the three low-index surfaces (100), (110), and (111) exhibits strong dependence on direction and acceptance cone. According to the present band model there should essentially be no emission normal to the (110) face for photon energies between 9.4 and 10.6 eV. Experimental observation of emission in this gap, however, implies effects not included in the simple bulk models. In particular, effects arising from surface emission have been considered, i.e., emission of those electrons which are excited in a single-step process from initial states near the surface to final states outside the crystal. The electrons that are emitted from the surface in directions perpendicular to the crystal planes carry information on the one-dimensional surface density of states. The present work includes a crude estimate of this surface density of states, which is derived from the bulk band structure by narrowing the $d$ bands according to an effective number of neighbors per surface atom. Estimates of surface relaxation effects are also included.

/pdf/volume-and-surface-photoemission-from-tungsten-i-calculation-30fn8825xi.pdf

Volume and surface photoemission from tungsten. I. Calculation of band structure and emission spectra

Energy-distribution spectra of photoelectrons emitted normal to three single-crystal faces of tungsten have been measured for photon energies between 7.7 and 21.2 eV. The results are interpreted in terms of one-dimensional electronic properties along the symmetry lines in $k$ space that correspond to the emitting crystal faces. The emitted spectra may be considered to consist of three types of contributions. One part is due to electrons that, after excitation by direct interband transitions in the bulk, have left the crystal unscattered. This contribution may be described by the energy density of a one-dimensional joint density of states along a symmetry line in the Brillouin zone. Another part, evident for photon energies above 12 eV, is due to electrons that have suffered inelastic scattering processes after optical excitation. This part carries information on the density of conduction states along the symmetry line under observation. Finally, a third contribution to the emitted spectrum is assigned to surface emission. This part reflects the surface density of states and bears evidence of a narrowing of the $d$ bands near the surface. A theoretical surface density of states, derived from a simple model that scales the width of the $d$ bands by the square root of an effective number of neighbor atoms, is found to describe the energy distribution of the electrons emitted by the surface effect satisfactorily.

/pdf/volume-and-surface-photoemission-from-tungsten-ii-experiment-1hxwwcjefq.pdf

Volume and surface photoemission from tungsten. II. Experiment

/pdf/angle-resolved-photoemission-from-au-112-33kueezebi.pdf

N. Egede Christensen

Papers

Relativistic Band Calculation and the Optical Properties of Gold

Volume and surface photoemission from tungsten. I. Calculation of band structure and emission spectra

Volume and surface photoemission from tungsten. II. Experiment

Angle-resolved photoemission from Au(112)