Alkali metal clusters

Herrmann A, Leutwyler S, Schumacher E and Woste L 1978 On metal-atom clusters IV. Photoionization thresholds and multiphoton ionization spectra of alkali-metal molecules Hel. Chim. Acta 61 453... 

The structures observed in the mass spectra of fullerene molecules covered with alkaline earth metals, as described in the previous section, all seem to have a geometric origin, resulting in particularly stable cluster configurations every time a highly symmetrical layer of metal atoms around a central fullerene molecule was completed. When replacing the alkaline earth metals by an alkali metal (i.e., Li, Na, K, Rb, or Cs), a quite different situation arises. 

Also listed in Table 1 are the shell closings observed in pure alkali metal clusters[9,21,23]. These values and the ones observed for the Cs-covered Qo have been arranged In the table in such a way as to show that... 

Such a simple model, without the barrier due to the Qo at the center, has been used to calculate the electronic shell structure of pure alkali metal clusters[9]. 

See text. The first two columns give the numbers of metal atoms at which electronic shell closings have been observed in experiment for Cs-covered C o and for pure alkali metal clusters, respectively. The columns on the right list the number of electrons required for shell closings in an infinitely deep potential well with and without a central barrier. The numbers in the different columns are mainly arranged in a manner to show correlations. 

In coating fullerenes with alkali metals, the stability of the cluster seemed to be determined primarily by the electronic configuration. The units C qM and C7oMg, where M is any alkali metal, proved to be exceptionally stable cluster building blocks. Coating a fullerene with more than 7 alkali metal atoms led to an even-odd alternation in the mass spectra, inter-... 

In the reactions of 10.13a with alkali metal terr-butoxides cage expansion occurs to give the sixteen-atom cluster 10.15, in which two molecules of MO Bu (M = Na, K) are inserted into the dimeric structure. The cluster 10.13a also undergoes transmetallation reactions with coinage metals. For example, the reactions with silver(I) or copper(I) halides produces complexes in which three of the ions are replaced by Ag" or Cu" ions and a molecule of lithium halide is incorporated in the cluster. ... 

By incorporation of alkali metal halides in the reaction mix, materials of composition M4-[MfiXig] can be produced in which each MgXn unit has a further six X atoms attached to its apices, so forming discrete clusters. 

Lower formal oxidation states are stabilized, however, by M-M bonding in ternary chalcogenides such as M MeQn, M4M6Q13 (M = alkali metal M = Re, Tc Q = S, Se) and the recently reported M gMeS. Their structures are all based on the face-capped, octahedral MeXg cluster unit found in Chevrel phases (p. 1018) and in the dihalides of Mo and W... 

Because of possible catalytic and biological relevance of metal-sulfur clusters, several such compounds of cobalt have been prepared. The action of H2S or M2S (M = alkali metal) on a non-aqueous solution of a convenient cobalt compound (often containing, or in the presence of, a phosphine) is a typical route. Diamagnetic [Co6Ss(PR3)6] (R = Et, Ph) comprise an octahedral array of metal atoms (Co-Co in the range 281.7 to 289.4pm), all faces capped by atoms,and show facile redox behaviour... 

Since the demonstration by Schumacher et al ) of the use of alkali metal vapor inclusion into a supersonic beam to produce clusters, there have been a number of attempts to generalize the approach. It has recently been recognized that instead of high temperature ovens, with their concommitant set of complex experimental problems, an intense pulsed laser beam focused on a target could be effectively used to produce metal atoms in the throat of a supersonic expansion valve. ) If these atoms are injected into a high pressure inert gas, such as helium, nucleation to produce clusters occurs. This development has as its most important result that clusters of virtually any material now can be produced and studied with relative ease. 

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 ... 

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