Metallic clusters excitation

Density-based methods Wave function-based methods Some technical aspects Excitations in various systems Excitations in metal clusters Excitations in semiconductor nanoparticles Excitations in organic and biological systems Identification of structure Dynamics in excited states Conclusions... 

The spherical shell model can only account for tire major shell closings. For open shell clusters, ellipsoidal distortions occur [47], leading to subshell closings which account for the fine stmctures in figure C1.1.2(a ). The electron shell model is one of tire most successful models emerging from cluster physics. The electron shell effects are observed in many physical properties of tire simple metal clusters, including tlieir ionization potentials, electron affinities, polarizabilities and collective excitations [34]. 

Accepting that the electronic structure of the metal clusters is in between the discreet electronic levels of the isolated atoms and the band structure of the metals, it is expectable that under a certain size the particle becomes nonmetallic. Indeed, theoretical estimations [102,105] suggest that the gap between the filled and empty electron states becomes comparable with the energy of the thermal excitations in clusters smaller than 50-100 atoms or 1 nm in size, where the particles start to behave as insulators. A... 

In this Section we want to present one of the fingerprints of noble-metal cluster formation, that is the development of a well-defined absorption band in the visible or near UV spectrum which is called the surface plasma resonance (SPR) absorption. SPR is typical of s-type metals like noble and alkali metals and it is due to a collective excitation of the delocalized conduction electrons confined within the cluster volume [15]. The theory developed by G. Mie in 1908 [22], for spherical non-interacting nanoparticles of radius R embedded in a non-absorbing medium with dielectric constant s i (i.e. with a refractive index n = Sm ) gives the extinction cross-section a(o),R) in the dipolar approximation as ... 

Several characteristics of the metal beam have been studied in detail. It is well known that metal clusters and metal oxides are formed as a result of the ablation process. However, these potentially interfering species have been studied in detail130 and it has been concluded that they do not introduce any doubt as to the validity of the experimental results. Much more important than cluster or oxide formation are the atomic electronic state populations of the metal beams. For each metal reactant, these have been characterized using laser-induced fluorescence (LIF) excitation spectroscopy. For Y, only the two spin-orbit states of the ground electronic state (a Dz/2 and a D-3,/2) were observed.123... 

Presently, the gas phase photofragmentation of several transition metal cluster complexes is reviewed. The techniques employed for these gas phase studies rely on sensitive ionization detection and the use of a broad range of excitation energies. 

The information available is discussed in light of the effects of excitation energy and the environment on the photofragmentation process of several transition metal cluster complexes. The photochemical information provides a data base directly relevant to electronic structure theories currently used to understand and predict properties of transition metal complexes (1,18,19). 

One problem we have had to overcome in developing metal-cluster oxidation-reduction photochemistry is the tendency of excited clusters to dissociate into radical fragments (for... 

In the past few years, the field of metal atom/metal cluster chemistry has taken an interesting turn out of the realm of the ground electronic state into the world of the excited state. This promises to be an intriguing new phase and one with considerable potential for new scientific discovery and technological development. 

It was as a result of investigations of the aforementioned kind that a new kind of excited state metal atom/metal cluster photoprocess was discovered, involving chemical reaction with the support itself (33). A prerequisit for the successful exploitation of this novel kind of chemistry, is a weakly interacting metal atom/metal cluster - cage ground electronic state. Only in... 

Two-photon emission is a process in which electronic transition between quantum levels occurs through the simultaneous emission of two photons. [27] presents more details about two-photon emission. Since metal clusters emit in the near-infrared region, they can be made useful for two-photon imaging with infrared excitation. Two-photon emission of Au25 clusters is observed at 830 nm by exciting at... 

These exciting recent developments are indications that much more new and exciting bare metal cluster chemistry remains to be discovered. 

Although the mechanism of the photo-induced generation of mono- and bimetallic metal clusters, except for the photographic application (Section 20.6), has been studied with considerably less detail than for the radiolytic route, some stable clusters, mostly of noble metals (Ag, Au, Pt, Pd, Rh), have also been prepared by UV excitation of metal ion solutions [129-141]. Generally, halides and pseudo-halides counter anions are known to release, when excited, solvated electrons, which reduce the metal ions up to the zerovalent state. Oxalate excitation yields the strong reducing carbonyl radical COO [30]. Photosensitizers are likewise often added [142]. Metal clusters are photo-induced as well at the surface of photo-excited semiconductors in contact with metal ions [143,144]. 

Figure 1. Experimental set-up for performing transient two-photon ionization spectroscopy on metal clusters. The particles were produced in a seeded beam expansion, their flux detected with a Langmuir-Taylor detector (LTD). The pump and probe laser pulses excited and ionized the beam particles. The photoions were size selectively recorded in a quadrupole mass spectrometer (QMS) and detected with a secondary electron multiplier (SEM). The signals were then recorded as a function of delay between pump and probe pulse.

Stationary spectroscopy on the C and D states of Na3 already indicated the onset of photoinduced fragmentation. Fragmentation becomes more important as the cluster size increases. As a result, nondissociative electronic excitation processes have not yet been observed for free metal clusters larger than trimers [20]. An alternative to conventional spectroscopy of such bound-free transitions was provided by depletion spectroscopy [2]. A deep insight into the dynamics of such photoinduced cluster fragmentation, however, is obtained with ultrafast observation schemes. The principle of such an... 

Electron-electron collisions induce further thermalization and transport excitation energy from the 1 ph modes to 2ph and higher configurations. The collision rate is however much suppressed at low excitation energies due to Pauli blocking of the final scattering states. The relaxation times from these electron-electron collisions thus strongly depend on cluster s temperature. The evaluation of these times in metal clusters is not yet. standard. We rely here on a first attempt, in this direction, performed at a semi-classical level... 

In this contribution, we have reviewed some patterns of the nonlinear dynamical response of metal clusters following strong excitations by ion collisions or femtosecond laser beams. We summarize quickly some of the most prominent features. Both, fast-ion collisions as well as femtosecond laser... 

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