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991.
O. N. Bakharev N. Zelders H. B. Brom A. Schnepf H. Schnöckel L. Jos de Jongh 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):101-104
We present
69,71Ga-NMR experiments on
microcrystalline samples of the recently discovered
supramolecular compound Ga
84
[
N
(
SiMe
3
)
2
]
20
Li
6
Br
2
(
thf
)
20
.
2
toluene, which is composed of
ligand-coordinated Ga84 metal clusters,
packed together in a fully ordered crystalline matrix. The
compound is highly conducting and even shows superconductivity
below T
c
~ 7.2 K. Our preliminary
results between 10-300 K show a metallic-like behavior: the
nuclear spin-lattice relaxation rate T
1
-1
follows the Korringa law
69
(
T
1
T
)
-1
= 0.36 s
-1
K
-1
, but with a relaxation rate approximately three
times smaller than in bulk -Ga
metal. No quantum-size effects are observed, the Korringa law
being followed down to 10 K, whereas the quantum-gaps for
individual clusters should amount to ~
10
3
K. These results therefore suggest a transport process based on
intermolecular charge transfer, similar as in alkali-doped
fullerenes and silicon-clathrates. 相似文献
992.
G. B. Parravicini A. Stella M. C. Ungureanu P. G. Merli A. Migliori P. Cheyssac R. Kofman 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2003,24(1-3):219-222
Both theoretical and experimental works give evidence that
gallium exhibits solid phases labelled , , , besides the
stable phase strongly dependent both on the size and the
confinement conditions. An experimental technique was used based
on capacitance and conductance measurements
vs. temperature in the
audiofrequency range. This technique is particularly sensitive
to the conditions of the investigated particle surface that
plays a fundamental role in the melting and more generally in
the phase transition processes. In particular the strict
relation between the derivative of the capacitance with respect
to the temperature, dC/dT, and the entropy of the system is
considered. In gallium nanoparticles 20 nm in radius, only the
phase is shown to occur. Further the transition to liquid phase
was detected. The melting process was found to start about 65 K
below the full melting temperature value. In the case of
particles 10 nm in radius, where different metastable phases may
occur, the capacitance vs.
temperature curve was found to display abrupt changes of the
slope. The singularities are associated to a well defined
transition temperature. 相似文献
993.
A survey is given of NMR studies of colossal magnetoresistive manganese perovskites (RE,Ca,Sr,Ba)MnO3 (RE = rare earth) and the interstitially modified permanent magnet materials, RE2Fe17A
x
(A = N,C,H) at ambient pressure and at applied pressures of up to 10 kbar. The different pressure behavior of the Mn hyperfine field found in the metallic and in the insulating manganite compounds is discussed and related to the micro- and macroscopic properties of these magnetically inhomogeneous materials. In the RE2Fe17A
x
compounds a different pressure behavior of the hyperfine field at the RE sites with different number and type of interstitial atom neighbors is discussed in terms of local compressibility. The influence of the interstitial modification and the applied pressure on the RE hyperfine field and quadrupole splitting is analyzed and the impact of the chemical pressure and covalent effects on these quantities is compared. A comparison of the behavior of the magnetic state of the 4f electron shell with pressure and with interstitial modification is made and the relation to the magnetocrystalline anisotropy is discussed. 相似文献
994.
Amorphous, nanocrystalline, and bulk AlO(OH) · xH2O crystals have six fundamental modes (FM) of vibration in a nonlinear AlO(OH) molecular structure. Most of them appear in groups of four IR and Raman bands. Their positions and relative intensities differ significantly in three specimens. The nanocrystals (monoclinic structure with z=8 molecules per unit cell) have four OH stretching bands at values enhanced by up to 360 cm−1 at 3120, 3450, 3560 cm−1 in comparison to those in bulk crystals or amorphous specimens. The first two bands are broad, bandwidth Δν1/2200 to 350 cm−1, while the other two are sharp, Δν1/290 cm−1. The sharp bands shift to 3525 and 3595 cm−1 after heating the sample at 100°C. They no longer appear after heating at 300 or 500°C for 2 h (the specimen decomposes to Al2O3), leaving behind only two bands at 3100 and 3400 cm−1. A Δν1/2 value of 500 cm−1 appears in the 3400 cm−1 in a delocalized distribution of H atoms. Two bands also occur at 3098 and 3300 cm−1 in bulk crystals (orthorhombic structure with z=4) or at 2990 and 3515 cm−1 in an amorphous sample. More than one bands appear in a FM vibration in occurrence of sample in more than one conformers. The amorphous sample has approximately the same conformer structure as the bulk crystals. An amorphous surface structure exists in nanocrystals with a group of three bands at 1420, 1510 and 1635 cm−1 in an interconnected network structure. It encapsulates the nanocrystals in an amorphous shell. Its volume fraction, 33% estimated from the integrated intensity in three bands, determines 2.2 nm thickness in the shell in spherical shape of nanocrystals in 35 nm diameter. 相似文献
995.
K. Dahmouche C.V. Santilli E. Lafontaine P. Judeinstein A.F. Craievich 《Journal of Sol-Gel Science and Technology》2000,19(1-3):429-433
Hybrid transparent and flexible siloxane-polypropyleneglycol (PPG) materials with covalent bonds between the inorganic (siloxane) and organic (polymeric) phases were prepared by sol-gel process. In order to improve the quality of the mechanical properties of these materials, different amounts of methyltriethoxysilane (MTES) were added to the initial sol. The effect of MTES addition on the structure of the composites was studied by Small-Angle X-Ray Scattering (SAXS) and 29Si Nuclear Magnetic Resonance (29Si NMR). In absence of MTES, SAXS spectra exhibit a peak that is assigned to spatial correlation due to short range order between the siloxane clusters embedded in the polymeric phase. The experimental results indicate that, for low MTES concentrations ([MTES]/[O] 0.8, O: ether-type oxygen of PPG), the silicon species resulting from hydrolysis and condensation of MTES fill the open spaces between polymeric chains, interacting with the ether-type oxygens. For larger MTES content ([MTES]/[O] 0.8), the number of free ether-type oxygen sites avalaible for reaction with such silicon species is not large enough. Consequently, a fraction of silicon species resulting from MTES addition graft to siloxane clusters formed by hydrolysis and condensation of the hybrid precursor. For all MTES concentrations the condensation degree of the siloxane phase, determined from 29Si NMR spectroscopy, is high (>69%), as expected under neutral pH synthesis conditions. 相似文献
996.
The crystal structures of two amine base salts, the hydrazinium, 1, and the hydroxylammonium, 2, of dinitramide have been determined. 1 crystallizes in the monoclinic space group P 21/c with cell dimensions a = 8.312(3), b = 5.654(1), c = 10.659(3) Å, = 93.73(3)°, while 2 crystallizes in the orthorhombic space group Pcab (nonstandard setting of Pbca) with cell dimensions a = 6.439(2), b = 12.470(4), c = 30.816(14) Å. The structures of 1 and 2 contain protonated amine cations and dinitramide anions linked by hydrogen bonding. In addition, in 2 there are both neutral and zwitterionic hydroxylamine moieties involved in the hydrogen bonding scheme. Thus in 2 the complete formula unit is (NH3
+OH)2[N3O4
–]2 · (NH2OH) middot; (NH3
+O–), and in this structure the hydroxylamine exists in its three possible forms: protonated, neutral, and zwitterionic. In both structures the conformations adopted by the dinitramine anions can be related to the types of hydrogen bonds it forms with the surrounding amine cations. 相似文献
997.
The results of FEM investigation of the triaxial stress state in multilayer structural elements subjected to axial and bending loads are presented. The distribution regularities of the stiffness and stresses or strains depending on the geometric and mechanical characteristics of layers and their position in the cross section of beams and bars are examined. The optimization of these elements is carried out using the dependences of the Bareisis—Paulauskas method and the Optim-98 computer program created by the present authors. As the optimization criteria, the strength, stiffness, mass, and cost of the structural elements are considered. 相似文献
998.
Ollerenshaw J McClung RE 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2000,144(2):255-265
A magnetic resonance imaging method is presented for imaging of heterogeneous broad linewidth materials. This method allows for distortionless relaxation weighted imaging by obtaining multiple phase encoded k-space data points with each RF excitation pulse train. The use of this method, turbo spin echo single-point imaging-(turboSPI), leads to decreased imaging times compared to traditional constant-time imaging techniques, as well as the ability to introduce spin-spin relaxation contrast through the use of longer effective echo times. Imaging times in turboSPI are further decreased through the use of low flip angle steady-state excitation. Two-dimensional images of paramagnetic doped agarose phantoms were obtained, demonstrating the contrast and resolution characteristics of the sequence, and a method for both amplitude and phase deconvolution was demonstrated for use in high-resolution turboSPI imaging. Three-dimensional images of a partially water-saturated porous volcanic aggregate (T(2L) approximately 200 ms, Deltanu(1/2) approximately 2500 Hz) contained in a hardened white Portland cement matrix (T(2L) approximately 0.5 ms, Deltanu(1/2) approximately 2500 Hz) and a water-saturated quartz sand (T(2) approximately 300 ms, T(2)(*) approximately 800 microseconds) are shown. 相似文献
999.
A. I. Belousova Yu. E. Lozovikb 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2000,8(2):251-264
A two dimensional (2D) classical system of dipole particles confined by a quadratic potential is studied. This system can
be used as a model for rare electrons in semiconductor structures near a metal electrode, indirect excitons in coupled quantum
dots etc. For clusters of N ≤ 80 particles ground state configurations and appropriate eigenfrequencies and eigenvectors for the normal modes are found.
Monte-Carlo and molecular dynamic methods are used to study the order-disorder transition (the “melting” of clusters). In
mesoscopic clusters (N < 37) there is a hierarchy of transitions: at lower temperatures an intershell orientational disordering of pairs of shells
takes place; at higher temperatures the intershell diffusion sets in and the shell structure disappears. In “macroscopic”
clusters (N > 37) an orientational “melting” of only the outer shell is possible. The most stable clusters (having both maximal lowest
nonzero eigenfrequencies and maximal temperatures of total melting) are those of completed crystal shells which are concentric
groups of nodes of 2D hexagonal lattice with a number of nodes placed in the center of them. The picture of disordering in
clusters is compared with that in an infinite 2D dipole system. The study of the radial diffusion constant, the structure
factor, the local minima distribution and other quantities shows that the melting temperature is a nonmonotonic function of
the number of particles in the system. The dynamical equilibrium between “solid-like” and “orientationally disordered” forms
of clusters is considered. 相似文献
1000.