The reaction of [NH4]2[MO2S2], AgI and (n-Bu)4NBr in solid state produced the polyoxometalates [(n-Bu)4N]4[M6O19][Ag2I4] (1, M? Mo; 2, M? W) which were structurally determined. The crystals of 1 and 2 are isomorphous, monoclinic, space group P21/c. 1, a = l.6624(2), b=1.6699(3), c=l.7217(2) nm, β=98.29(1)°, V=4.729(1) nm3, Z=2, R=0.040, Rw“0.037; 2, a = 1.6636(3), b = 1.6733(3), c = 1.7190(3) nm, β=98.25(1)°, V=4.736(l) nm3, Z = 2, R = 0.038, Rw = 0.047. The results of the structure determination showed that the two compounds had the same structures whose skeletons are composed of [Ag2I4]2. and [M6O19]2-. The difference of them and heteropolymetalate compounds synthesized in solution is that the title compounds contain cluster. ion, heteropolymetalate and organic cations, while the latter is only composed of heteropolymetalate and organic cations. 相似文献
The structure of CsPd2F5 has been confirmed from neutron diffraction data on powdered sample. CsPd2F5 crystallizes in the orthorhombic Imma space group. At 100 K, the unit-cell constants are a = 6.473(2) Å, b = 7.853(5) Å, c = 10.718(3) Å and the calculation carried out using the Rietveld method leads to R1 = 0.020. The network is formed of PdF6 octahedra chains containing half of Pd in high-spin configuration, connected one to each other by square planes containing the other half of Pd in low-spin configuration. CsPd2F5 orders antiferromagnetically below TN = 38 K. In the ordered state a weak ferromagnetic component occurs (σ0 = 0.098 μB at 2 K). The magnetic structure determined at 4 K is consistent with the magnetization data and can be described in the Im′m′a′ magnetic group without any doubling of the unit-cell parameters. Within the chains, Pd2+ are coupled antiparallel. The magnetic moments are located in the (x0z) plane, the angle between the moments and the z axis being 18°. 相似文献
In this paper we have reviewed the theoretical framework of the coupled-cluster (cc) based linear response model as a tool
for directly calculating energy differences of spectroscopic interest like excitation energy (ee), ionisation potential (ip)
or electron affinity (ea). In this model, the ground state of a many-electron system is described as in a coupled cluster
theory for closed shells. The electronic ground state is supposed to interact with an external photon field of frequencyw, and the poles of the linear response function as a function ofw furnish with the elementary excitations of the system. Depending on the general form of the coupling term chosen, appropriate
difference energies like ee, ip or EA may be generated. Pertinent derivations of the general working equations are reviewed,
and specific details as well as approximations for ee, ip or ea are indicated. It is shown that the theory bears a close resemblance
to the equation of motion (eom) method but is superior to the latter in that the ground state correlation is taken to all orders and may be looked upon
as essentially a variant of renormalisedtda. A perturbative analysis elucidating the underlying perturbative structure of the formulation is also given which reveals
that the theory has a hybrid structure: the correlation terms are treated akin to an open shellmbpt, while the relaxation terms are treated akin to a Green function theory. A critique of the methodvis-a-vis other cc-based approaches for difference energies forms the concluding part of our review. 相似文献
In a mass spectrometric study, it was found that the saturated vapor over gadolinium tris-hexafluoroacetylacetonate Gd(C5O2HF6)3 contains molecular forms with a mass exceeding the mass of the dimer. The vapor overheated to 250–300°C contains only the monomer form. Simultaneous electron diffraction and mass spectrometric experiment aimed at investigating the structure of the Gd(hfa)3 monomer molecule was carried out at 284(5)°C. The Gd(hfa)3 molecule was found to have the symmetry of the equilibrium D3 configuration. The basic structural parameters are rh1(Gd-O) = 2.291(10) Å, rh1(O-C) = 1.257(10) Å, rh1(C-Cr) = 1.404(6) Å, rh1(CF-F)av = 1.341(3) Å, ∠OGdO = 72.8(0.4)°. The GdO6 coordination polyhedron has the structure of a distorted antiprism. The rotation angle of the O-O-O trigonal faces relative to their position in a regular prism is 18.7(0.9)°. Quantum chemical calculations (HF/SBK, 6-31G*) generally reproduce the experimental structure, but the Gd-O internuclear distance is exaggerated by 0.04 Å. 相似文献
Two inorganic-organic hybrid solids, Zn2(phen)(HPO3)2 (1) and Zn(phen)(HPO3) (2), have been synthesized under solvothermal conditions in the presence of 1,10-phenanthroline (phen) ligands. Their structures were determined by single-crystal X-ray diffraction and further characterized by FTIR, elemental analysis, powder X-ray diffraction, thermogravimetric analysis and fluorescent spectra. Compound 1 crystallizes in the triclnic system, space group P-1, , , , α=75.609(1)°, β=79.145(2)°, γ=67.157(2)°, , Z=2. Compound 2 is monoclinic, C2/c, , , , β=94.175(4)°, , Z=8. Both structures consist of 1D chains constructed from strictly alternating ZnO4 and HPO3 polyhedra through sharing vertices. The chains are further decorated by Zn-centered complex architectures, [Zn(phen)]2+ for 1 and [Zn(phen)2]2+ for 2. The 2D and 3D supramolecular arrays for 1 and 2 are stably stacked via strong π-π interactions of the phen groups, respectively. 相似文献
1 INTRODUCTION Recently the series of compounds M3Ln(BO3)3 (M = Sr, Ba and Ln = LaLu, Sc, Y) with space group P63cm or -3R have been reported[1~5], and some of them exhibit interesting optical properties when doped with the active Cr3+ or Yb3+ ions as laser materials. For example, Yb3+-doped Sr3Y- (BO3)3 crystal is a promising laser material for both tunable and femtosecond laser applications[6~8]. The Ba3Y(BO3)3 crystal melts congruently at 1256 ℃ and has a phase transitio… 相似文献
In recent years, the self-assembled growth of semiconductor nanostructures, that show quantum size effects, has been of considerable interest. Laser devices operating with self-assembled InAs quantum dots (QDs) embedded in GaAs have been demonstrated. Here, we report on the InAs/GaAs system and raise the question of how the shape of the QDs changes with the orientation of the GaAs substrate. The growth of the InAs QDs is understood in terms of the Stranski–Krastanow growth mode. For modeling the growth process, the shape and atomic structure of the QDs have to be known. This is a difficult task for such embedded entities.
In our approach, InAs is grown by molecular beam epitaxy on GaAs until self-assembled QDs are formed. At this point the growth is interrupted and atomically resolved scanning tunneling microscopy (STM) images are acquired. We used preparation parameters known from the numerous publications on InAs/GaAs. In order to learn more about the self-assemblage process we studied QD formation on different GaAs(0 0 1), (1 1 3)A, and (
)B substrates. From the atomically resolved STM images we could determine the shape of the QDs. The quantum “dots” are generally rather flat entities better characterized as “lenses”. In order to achieve this flatness, the QDs are terminated by high-index bounding facets on low-index substrates and vice versa. Our results will be summarized in comparison with the existing literature. 相似文献