The cohesive energy of the Al–Mn Mackay icosahedron (MI) was estimated for different variants of chemical order, using pair-bonding energies. This problem is related to the nucleation of i-AlMn phase in sequentially deposited thin films. The chemically ordered MI comes out as the thermodynamically most stable configuration. The role of kinetic factors during deposition is also discussed. 相似文献
The electronic structure of the spherical Mackay icosahedral nanosized cluster Pd55(PiPr3)12(μ3-CO)20 is analyzed by using DFT calculations. Results reveal that it can be considered as a regular superatom with a “magic” electron count of 20, characterized by a 1S2 1P6 1D10 2S2jellium configuration. Its open shell nature is associated with partial occupation of non-jellium, 4d-type, levels located on the interior of the Pd55 kernel. This shows that the superatom model can be used to rationalize the bonding and stability of spherical ligated group 10 clusters, despite their apparent 0-electron count. 相似文献
Mackay groups (or compound groups) are considered in the historical context, as one of two possible kinds of multiple antisymmetry. The number of junior Mackay groups of Mm type is calculated for different nonisomorphic antisymmetric characteristics formed by 1 l 4 generators. Combinatorial relationships connecting Mackay and Zamorzaev multiple antisymmetry groups are established. Geometrical applications of Mackay groups making possible direct dimensional transition from n-dimensional symmetry groups to (n + 2) dimensional subperiodic symmetry groups are discussed. Some open problems connected with Mackay groups are given. 相似文献
The authors predict that the magnetic moment of the scandium clusters can not be efficiently enhanced with the encapsulation of Fe atom, which is different from previous works with Fe atom doped in Bn, Sin, and Gen clusters. It was found that starting from n=6, the growth patterns of the ground state structures of the ScnFe clusters are dominated by the octahedron structures with Fe atom falling into the center of the host framework. The calculated results manifest that doping of the Fe atom contributes to strengthening the stabilities of the scandium framework. Maximum peaks are observed for clusters of n=3, 6 and 8 on the size dependence of the second‐order energy differences, implying that these clusters possess relatively higher stability. The HOMO‐LUMO gap of the ScnFe clusters exhibits an oscillational odd‐even character with the local peaks of n=4, 6 and 8. Especially, there is the largest oscillation of the gap with n=4 and 5. Additionally, the doped Fe atom exhibits the antiferromagnetic alignment at n=4, 5, 7 and 9. Also, the quench of the magnetic moments as n=6, 8 and 10 may be ascribed to the model of close‐shell electrons. 相似文献
In this paper, the concept offractal geometry was applied to the growth of icosahedral and polyicosahedral clusters. Fractal dimensions were calculated for high-frequency icosahedral casters, vertex-sharing polyicosahedral clusters, and linked polyicosahedral clusters. These cluster growth pathways were compared with the fractal growth mechanisms of colloidal particles. Close similarities were found despite the tremendous differences in particle sizes and the forces governing their nucleation and growth processes.Dedicated to Prof. Lawrence F. Dahl on his 65th birthday; based in part on a lecture presented by BKT at the Dahl symposium held at the University of Wisconsin, Madison, Wisconsin on September 17, 1994. 相似文献
Geometry, vibrational and NMR spectra of the icosahedral aza-closo-dodecaborane MeNB11H11 are calculated by ab initio methods. The results are compared with experimental data. They are in accord with local C5v symmetry of the cluster unit and local C3v symmetry of the methyl group. The boron atoms B7–B11 are coupled to B12 by the small constant 1J (11B, 11B) = 12 Hz. 相似文献
Hydrogel‐containing core–shell capsules are useful as drug delivery vehicles for many biomedical applications, especially when release of incorporated guests can be controlled. Here, we developed a one‐step organic solvent‐free method to prepare such core–shell capsules using a synthetic and a natural supramolecular hydrogel, for the core and shell, respectively. A solution containing ureido‐pyrimidinone modified poly(ethylene glycol) hydrogelators and calcium chloride was drop‐wise added to an alginate solution, yielding core–shell structures. It was found that the outer shell provides a confined space for the inner supramolecular hydrogel and therefore prevents swelling of the core. This consequently slows down both erosion of the less stable core, and release of dextran guests.
The synthesis of high‐purity and high‐yield Au25 clusters protected by the basic pyridyl ethanethiol (HSCH2CH2Py, 4‐PyET and 2‐PyET) is presented. Single‐crystal X‐ray diffraction of the [Au25(4‐PyET)18]??Na+ clusters has revealed a structure similar to that known for the phenyl ethanethiolate analogue, but with pyridyl‐N coordination to Na+, a more relaxed ligand shell, and a profoundly layered arrangement in the solid state. Because of the pendant Py moiety, the [Au25(PyET)18]? clusters are endowed with unique (de)protonation equilibria, which has been characterized in detail by UV/Vis absorption and 1H NMR spectroscopy. [Au25(PyET)18]? clusters showed an unexpectedly H+‐dependent solubility that is tunable in aqueous and organic solvents. The successful synthesis of the basic Py‐terminated thiolate‐protected Au25 clusters paves the way to realize a new family of metalloid clusters possessing basic properties. 相似文献
We examine low-energy isomeric forms, static polarizabilities, and optical absorption spectra of Agn, n = 2–8, and Aun, n = 2–3, clusters using first principles computations within the static and time-dependent versions of the density functional theory. The noticeable decrease in the static polarizabilities of Ag7 and Ag8 compared to the values characteristic of Agn, n = 2–6, is correlated with the transition from two-dimensional to three-dimensional structures at n = 7. The optical spectra computed within the time-dependent local density approximation for the most stable structures are in good agreement with the available experimental data and the results of earlier theoretical studies. Optical spectra of higher-energy isomers typically present features that are not observed in the experimental spectra. The d electrons affect the spectra of noble metal clusters by quenching the oscillator strengths through screening of the s electrons and by getting directly involved in the excitations. Due to the larger s–d hybridization in Au compared to Ag, these effects are more pronounced in Aun clusters. 相似文献
A series of new heteromultinuclear FeI/RuII clusters are described. The complexes (η6-arene)RuFe2S2(CO)6 (arene = p-cymene 1 , C6Me6 2 ) and Fe2[μ-S (Cp*Ru)(CO)2]2(CO)6 (Cp* = η5-C5Me5) ( 3 ) were prepared by the reduction reactions of (μ-S)2Fe2(CO)6 with 2 equiv of LiHBEt3, followed by treatment (μ-SLi)2Fe2(CO)6 with ruthenium-arene complexes Ru2(μ-Cl)2Cl2(η6-arene)2 or Cp*Ru (CO)2Cl in 22–33% yields. Further reactions of 1 and 2 with 1 equiv of triphenylphosphine in the presence of the decarbonylating agent Me3NO·2H2O, afforded the corresponding monophosphine-substituted FeI/RuII complexes (η6-arene)RuFe2S2(CO)5(Ph3P) (arene = p-cymene 4 , C6Me6 5 ) in 75% and 78% yields. While treatment of parent complex 1 or 2 with 1 equiv of diphosphine Ph2PCH2PPh2 (dppm) in xylene at reflux temperature resulted in the formation of the diphosphine-bridged RuFe2S2(CO)9 derivate RuFe2S2(CO)7(dppm) ( 6 ). The possible pathway for the formation was proposed. Two isomers of novel macrocyclic complexes involve the (η6-arene) Ru-bridged quadruple-butterfly Fe/S clusters [{μ-S (CH2)3S-μ}{(μ-CS2)Fe2(CO)6}2]2[(η6-arene)Ru]2 (arene = p-cymene 7a and 7b , C6Me6 8a and 8b ) were isolated by reactions of two μ-CS2-containing dianion [{μ-S (CH2)3S-μ}{(μ-S=CS)Fe2(CO)6}2]2− with [Ru2(μ-Cl)2Cl2(η6-arene)2], in which the propylene groups are attached to two S atoms by ee and ea types of bonds respectively. All the new complexes 1 – 8 have been characterized by elemental analysis, spectroscopy, and particularly for 1 – 6 , 7b and 8a by X-ray crystallography. In addition, the electrochemical properties of representative complexes 1 – 4 and 6 have been investigated. 相似文献