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51.
E. Miyoshi T. Iura Y. Sakai H. Tochihara S. Tanaka H. Mori 《Journal of Molecular Structure》2003,630(1-3):225-232
We investigated the interactions between the Si(111) surface and the Na, Mg, and Al atoms using cluster model calculations. Calculations were performed at levels of complete-active-space self-consistent-field (CASSCF) and multi-reference singly and doubly excited configuration interaction (MRSDCI) calculations using the model core potential method. Our calculations revealed that the most favorable sites of Na, Mg, and Al adsorption on Si(111) are on top (T1), bridge (B2), and 3-fold filled (T4) sites, respectively. The nature of chemical bonds between these metal atoms and the dangling bonds of the surface Si atoms are found to be essentially covalent. 相似文献
52.
The last two decades have seen a dramatic development in the study of metal-metal multiple bonds, particular successes being recorded in the field of organometallic chemistry. Syntheses designed to produce novel transition metal complexes with single, double, triple and quadruple metal-metal bonds occupy a most important place in such research, as also do reactivity studies. A striving to establish general principles has provided much of the motivation for such work, but one less obvious goal—the commercial application of the catalytic properties of metal-metal multiple bonding systems, in the medium and long term—should not be overlooked. All aspects of the investigations of metal-metal multiple bonds also apply to a particular class of compound that has, however, enjoyed little lime-light and thus deserves the present review: complexes with multiple bonds between transition metals and substituent-free (“bare”) main group elements. Although based mostly on accidental discoveries, the few noteworthy examples are now beginning to unfold general concepts of synthesis that are capable of being extended and thus are deserving of exploitation in preparative chemistry. The availability of further structural patterns exhibiting multiple bonds between transition metals and ligand-free main group elements might enable preparative organometallic chemistry to expand in a completely new direction (for instance by the stabilizing or activation of small molecules at the metal complex). This essay discusses the chemistry of complexes of bare carbon, nitrogen, and oxygen ligands (carbido-, nitrido-, and oxo-complexes) and their relationships to higher homologues from both a synthetic and a structural point of view. 相似文献
53.
合成并测定了标题化合物的分子结构,Ca空间群,a=2.1933(2)nm,b=1.2447(3)nm,c=1.5912(5)nm,β=117.02(2)°,I'=3.8679 nm~3,Z=4,最后根据I>3G(I)的2849个独立衍射点的强度数据,把结构精修到R=0.036.在晶体结构测定基础上进行了EHMO计算,以研究其簇骼成键性质,结果表明,该分子虽不存在金属-金属键,但M与μ-O之间除了σ键外,还存在四中心d-ρπ键,它是该类化合物稳定的主要因素。 相似文献
54.
55.
Detlef Gabel Claudia Bauer Mohamed E. El-Zaria Afaf R. Genady Udo Drfler 《Journal of organometallic chemistry》2003,680(1-2):23-26
The preparation and properties of the R1R2NH---B8H11NHR cluster are described. The cluster is stable to aqueous solutions and can be made water-soluble by the introduction of a few hydrophilic groups. This makes the cluster a good candidate as the boron moiety in compounds for boron neutron capture therapy. The chemistry of the cluster preparation, the stability of the cluster, and conditions for reactions of the organic moieties are reviewed. Pyridine derivatives of the cluster show electronic interaction between the cluster and the pyridine. 相似文献
56.
We describe and interpret computer simulations of the time evolution of a binary alloy on a cubic lattice, with nearest neighbor interactions favoring like pairs of atoms. Initially the atoms are arranged at random; the time evolution proceeds by random interchanges of nearest neighbor pairs, using probabilities compatible with the equilibrium Gibbs distribution at temperatureT. For temperatures 0.59Tc, 0.81 Tc, and 0.89T
c, with density of A atoms equal to that in the B-rich phase at coexistence, the density C1 of clusters ofl A atoms approximately satisfies the following empirical formulas: C1 w(1 –)3 andC
1, (1 –)4Q1w1 (2 l 10). Herew is a parameter and we defineQ
l
=
K
e
–E(K)
, where the sum goes over all translationally nonequivalentl-particle clusters andE(K) is the energy of formation of the clusterK. Forl > 10,Q
1 is not known exactly; so we use an extrapolation formulaQ
l
Aw
s
–l
l
– exp(–bl
), wherew
s is the value ofw at coexistence. The same formula (withw > w
s) also fits the observed values of C, (for small values ofl) at densities greater than the coexistence density (forT=0.59Tc): When the supersaturation is small, the simulations show apparently metastable states, a theoretical estimate of whose lifetime is compatible with the observations. For higher supersaturation the system is observed to undergo a slow process of segregation into two coexisting phases (andw therefore changes slowly with time). These results may be interpreted as a more quantitative formulation (and confirmation) of ideas used in standard nucleation theory. No evidence for a spinodal transition is found.Supported by AFOSR Grant No. 73-2430D and by ERDA Contract No. EY-76-C-02-3077*000. 相似文献
57.
The Hexagallane [Ga6{SiMe(SiMe3)2}6] and the closo‐Hexagallanate [Ga6{Si(CMe3)3}4 (CH2C6H5)2]2— — the Transition to an Unusual precloso‐Cluster The closo hexagallanate [Ga6R4(CH2Ph)2]2— (R = SitBu3) as well as the hexagallane Ga6R6 (R = SiMe(SiMe3)2) with only six cluster electron pairs were isolated from reactions of “GaI” with the corresponding silanides. The structure of the latter is derived from an octahedron by a Jahn‐Teller‐distortion and is different from the capped trigonal bipyramidal one expected by the Wade‐Mingos rules. Both compounds were characterized by X‐ray crystallography. The bonding is discussed with simplified Ga6H6 and Ga6H62— models via DFT methods. 相似文献
58.
《Analytica chimica acta》2004,515(1):87-100
The goal of present work is to analyse the effect of having non-informative variables (NIV) in a data set when applying cluster analysis and to propose a method computationally capable of detecting and removing these variables. The method proposed is based on the use of a genetic algorithm to select those variables important to make the presence of groups in data clear. The procedure has been implemented to be used with k-means and using the cluster silhouettes as fitness function for the genetic algorithm.The main problem that can appear when applying the method to real data is the fact that, in general, we do not know a priori what the real cluster structure is (number and composition of the groups).The work explores the evolution of the silhouette values computed from the clusters built by using k-means when non-informative variables are added to the original data set in both a literature data set as well as some simulated data in higher dimension. The procedure has also been applied to real data sets. 相似文献
59.
The closo‐dodecaborate [B12H12]2? is degraded at room temperature by oxygen in an acidic aqueous solution in the course of several weeks to give B(OH)3. The degradation is induced by Ag2+ ions, generated from Ag+ by the action of H2S2O8. Oxa‐nido‐dodecaborate(1?) is an intermediate anion, that can be separated from the reaction mixture as [NBzlEt3][OB11H12] after five days in a yield of 18 %. The action of FeCl3 on the closo‐undecaborate [B11H11]2? in an aqueous solution gives either [B22H22]2? (by fusion) or nido‐B11H13(OH)? (by protonation and hydration), depending on the concentration of FeCl3. In acetonitrile, however, [B11H11]2? is transformed into [OB11H12]? by Fe3+ and oxygen. The radical anions [B12H12] ˙ ? and [B11H11] ˙ ? are assumed to be the primary products of the oxidation with the one‐electron oxidants Ag2+ and Fe3+, respectively. These radical anions are subsequently transformed into [OB11H12]? by oxygen. The crystal structure analysis shows that the structure of [OB11H12]? is derived from the hypothetical closo‐oxaborane OB12H12 by removal of the B3 vertex, leaving a non‐planar pentagonal aperture with a three‐coordinate O vertex, as predicted by NMR spectra and theory. 相似文献
60.