Metal clusters condensation

These methods may be used to prepare mixed metal clusters. Simultaneous codeposition of Ag and Cu vapors in Ar at 10-12 K yields a mixture including atomic Ag and Cu, dimers Ag, and Cu, together with AgCu. At 77 K, CuAg4 and Cu,Ag3 clusters occur . The amount of AgCu can be increased by photoexcitation with 305 nm Ag or Cu atomic radiation. The trimer AuAgCu is produced when a mixture of Au, Ag and Cu vapors is condensed at 77 K. 

In the solid state, metal clusters can connect to each other through outer and/ or inner ligands, or by direct condensation of the metal octahedra (Fig. 6.2), to form a variety of frameworks. 

The cluster condensation can be carried on the chains of octahedra sharing edges can be joined to double-strands and finally to layers of octahedra (Fig. 13.18). Every layer consists of metal atoms in two planes arranged in the same way as two adjacent layers of atoms in a closest-packing of spheres. This is simply a section from a metal structure. The X atoms occupy positions between the metal layers and act as insulating layers. Substances like ZrCl that have this structure have metallic properties in two dimensions. 

Previously, intense beams of metal clusters could only be produced for the most volatile metals. The limitation arose from significant materials problems involved in the construction of high temperature ovens. The development of a source that utilizes laser vaporization and subsequent condensation in a rapidly flowing gas eliminated the materials problem and has enabled just about any material to be studi ed(la,8). 

Condensation of metal atoms and/or metal clusters, with or in rare gases at cryogenic temperatures, from either jets or beams... 

Of course, valence electron concentration is not only related to the metal atoms but also to the number and valence of the ligands. Ligand deficiency creates vacant coordination sites at metal atoms and results in cluster condensation, which is the fusion of clusters via short M-M contacts into larger units ranging from zero- to three-dimensional. The chemistry of metal-rich halides of rare earth metals comprises both principles, incorporation of interstitial atoms and cluster condensation, with a vast number of examples [22, 23]. 

The scheme of cluster condensation or cluster fragment condensation leads eventually to structures observed in bulk metals. Particularly through extensive condensation of tetrahedral and octahedral clusters, arrangements closely related to the hexagonal and cubic close-packed structures can be obtained. Condensation also of icosahedral five-fold symmetrical clusters may be related to crystalline and quasicrystalline metallic structures. 

Another contribution is represented by an investigation of a cubic thallium cluster phase of the Bergmann type Na13(TlA.Cdi A.)27 (0.24 < x <0.33) (Li and Corbett 2004). For this phase too the body centred cubic structure (space group Im 3, a = 1587-1599 pm) may be described in terms of multiple endo-hedral concentric shells of atoms around the cell positions 0, 0, 0, and 14,14,14. The subsequent shells in every unit are an icosahedron (formed by mixed Cd-Tl atoms), a pentagonal dodecahedron (20 Na atoms), a larger icosahedron (12 Cd atoms) these are surrounded by a truncated icosahedron (60 mixed Cd-Tl atoms) and then by a 24 vertices Na polyhedron. Every atom in the last two shells is shared with those of like shells in adjacent units. A view of the unit cell is shown in Fig. 4.38. According to Li and Corbett (2004), it may be described as an electron-poor Zintl phase. A systematic description of condensed metal clusters was reported by Simon (1981). 

Circulation flow system, measurement of reaction rate, 28 175-178 Clausius-Clapeyron equation, 38 171 Clay see also specific types color tests, 27 101 compensation behavior, 26 304-307 minerals, ship-in-bottle synthesis, metal clusters, 38 368-379 organic syntheses on, 38 264-279 active sites on montmorillonite for aldol reaction, 38 268-269 aldol condensation of enolsilanes with aldehydes and acetals, 38 265-273 Al-Mont acid strength, 38 270-271, 273 comparison of catalysis between Al-Mont and trifluorometfaanesulfonic acid, 38 269-270... 

On the practical side, we note that nature provides a number of extended systems like solid metals [29, 30], metal clusters [31], and semiconductors [30, 32]. These systems have much in common with the uniform electron gas, and their ground-state properties (lattice constants [29, 30, 32], bulk moduli [29, 30, 32], cohesive energies [29], surface energies [30, 31], etc.) are typically described much better by functionals (including even LSD) which have the right uniform density limit than by those that do not. There is no sharp boundary between quantum chemistry and condensed matter physics. A good density functional should describe all the continuous gradations between localized and delocalized electron densities, and all the combinations of both (such as a molecule bound to a metal surface a situation important for catalysis). 

Several diynyl complexes react with other metal substrates, the proximity of the a-bonded metal to a multimetal system often resulting in further cluster condensation. 

Maitani MM, Daniel TA, Cabarcos OM, Allara DL (2009) Nascent metal atom condensation in self-assembled monolayer matrices coverage-driven morphology transitions from buried adlayers to electrically active metal atom nanofilaments to overlayer clusters during aluminum atom deposition on alkanethiolate/gold monolayers. J Am Chem Soc 131 (23) 8016-8029... 

The radiation-induced method, in the y- or pulse regime [19,20] and, to a certain extent, the photo-induced method [21], provide a particularly powerful means to produce in condensed media, metal, and semiconductor clusters from monomers as precursors, to study their properties and to understand the exotic phenomena which occur whenever a new phase of oligomeric particles is formed in the bulk of a homogeneous mother phase [22-26], phenomena which are therefore rather frequent in physics and chemistry. Unlike a recent review concerning semiconductor clusters [19], the present chapter is specifically focused on metal clusters, induced by ionizing radiation or ultraviolet (UV)-visible photons. 

Figure 1.25 The structures of (a) TijTe (b) Gd2Cl3 and (c) KM03S3 formed by condensation of octahedral metal clusters. (After Simon, 1981.)...

There are several interesting families of inorganic mixed-valence compounds that we have not discussed here (see Yvon, 1979 McCarley, 1982). For example, there are metal-cluster compounds such as the Chevrel phases, M,jMo6X8(X = S or Se) and condensed metal-cluster chain compounds such as TlMojScj, TijTe, NaMo O and M PtjO. TTF halides and TTF-TCNQ complexes (Section 1.9) constitute molecular mixed-valent systems in which the mixed valency is associated with an entire molecule the charge on TTF in such compounds is nonintegral. The structure of TTF-Br(, 79 and... 

Xerogels Ag, Au Two steps (1) gamma radiation initiation of metal-particle growth in a solution containing metal ions and multifunctional silanes (2) xerogels with metal clusters grafted on an oxide network prepared via hydrolysis and condensation 76... 

Matrix isolation studies usually permit spectroscopic observation of the species M(CO), M(CO)2,. M(CO) , the coordinatively saturated molecule. In some early studies, species thought to be simple unsaturated carbonyls were in fact carbonyls of metal clusters Mx(CO) a very low concentration of metal in the matrix (e.g., I mol in 104 mol noble gas) has to be used to prevent clustering. All the partially coordinated carbonyls are only matrix species, that is, they only exist when completely isolated from other molecules of their own kind or from CO. The coordinately saturated carbonyls are of more interest in the context of this review. The following new molecules have been reported Au(CO)2 (84a) Ag(CO)3, Cu2(CO)6 (46, 87) Pd(CO)4 (22), Pt(CO)4 (69) Rh2(CO)g, Ir2(CO)g (37) M(CO)6[M = Pr, Nd, Gd, Ho, Yb (100), Ta (24), U (117)]. The Cu, Pd, Pt, Rh, and Ir carbonyls can be obtained by condensing the metal vapors with pure CO at 40 K and then pumping off excess CO to leave a film of the carbonyl. The Cu, Pd, and Pt carbonyls decompose under vacuum temperatures above -100°C, and the Rh and Ir carbonyls dimerize with loss of CO to give M4(CO)12 above -60°C. The gold and silver carbonyls are not stable outside matrix isolation conditions. Unfortunately, the literature is presently unclear about the stability of the Ta and lanthanide hexacarbonyls outside a matrix. 

Condensation of discrete triangular metal cluster units in the metal cluster plane is another way of building extended solid-state com-... 

The reaction of a carbonylmetalate with a neutral metal carbonyl has been labeled a redox condensation by Chini et al. (40, 41) and has been as widely used as a pyrolysis reaction for synthesizing mixed-metal clusters. Carbonylmetalates usually react rapidly with most neutral carbonyls, even under very mild conditions. A large number of mixed-metal hydride clusters have been formed via this type of reaction, primarily because the initial products are anionic clusters that in many cases may be protonated to yield the neutral hydride derivative. 

---