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31.
P. E. M. Siegbahn 《Theoretical chemistry accounts》1994,88(6):413-424
Summary The ground state structures and bond energies have been obtained for the triatomic MHX systems where M is the entire sequence of second row transition metal atoms and X is a halide. The most interesting results of this study appear when these systems are compared to the triatomic MH2 and MX2 systems. It turns out that the structure of the MHX systems are quite similar to the corresponding MH2 systems in general. Most of the MHX systems to the right thus have bent low-spin ground states, indicating large covalent contributions to the bonding. RuHX is a special case and has a high-spin linear ground state. For the systems to the left ionicity dominates the bonding. An important result, with implications for halide ligand effects on carbonyl and olefin insertion into M-H and M-R bonds, is that the M-H bonds for the systems to the right have a different character and are significantly weaker for the MHX than for the MH2 systems. A similar effect is noted when the M-Cl bond strengths of MCl2 are compared to the ones in MHCl. Both these effects can be explained by a more cationic metal with mores
0-state character when halide ligands are present. 相似文献
32.
The question about the definition of the “internal pressure” concept is being discussed. It is shown that the previously found differential relation between the cohesion energy density and the internal pressure is one of the examples of an absolutely general interrelation between definitely connected differential functions. It is ascertained that the ratio (the internal pressure divided by the cohesion energy density) is a structuresensitive parameter inherent to the calorific (thermal) equation of a liquid state. 相似文献
33.
Sergey P. Gladchenko Yurii Z. Kovdrya Viktor A. Nikolaenko 《Journal of Molecular Liquids》2005,120(1-3):175-179
Conductivity of electrons in a quasi-one-dimensional (Q1D) system over liquid helium in narrow channels with the parabolic profile of the potential well has been investigated at temperature T, from 0.4 to 1.8 K, for different driving electric fields and radius of channel curvature. The interval of linear electron densities varied from 2.18×103 up to 1.7×106 cm−1.
The inverse mobility (1/μeff) in the electron-ripplon scattering region at the high linear densities of charges in the channel increases with temperature decreasing. This anomalous behavior of the electron transport in the low-temperature region has been explained by either the electron ordering or the polaronic effects in confined conducting channels. The nonlinear behavior of the electron velocity as a function of a driving electric field is supposed to be due to Breg–Cherenkov radiation of the ripplons. The radiation occurred if the velocity of electrons in the channel approaches to the critical value. 相似文献
34.
针对高频地波雷达系统OSMAR2000海流测向中海流元数不易估计的问题,利用四阶谱累积量MUSIC算法的空间谱结构特点,采用试探法确定信号源数并估计信号源的位置.通过对模拟海流和实测数据的处理实验表明,利用该算法可以较准确地估计出海流元的个数和方位,并且比传统MUSIC方法获得更小的角度估计方差,有效地反演了海洋表面流信息. 相似文献
35.
36.
37.
Nadya Dencheva Teresa G. Nunes M. Jovita Oliveira Zlatan Denchev 《Journal of Polymer Science.Polymer Physics》2005,43(24):3720-3733
The crystalline structure of polyamide‐12 (PA12) was studied by solid‐state 13C nuclear magnetic resonance (NMR) as well as by synchrotron wide‐ and small‐angle X‐ray scattering (WAXS and SAXS). Isotropic and oriented PA12 showed different NMR spectra ascribed to γ‐ and γ′‐crystalline modifications, respectively. On the basis of the position of the first diffraction peak, the isotropic γ‐form and the oriented γ′‐form were shown to be with hexagonal crystalline lattice at room temperature. When heated, the two PA12 polymorphs demonstrated different behaviors. Above 140 °C, the isotropic γ‐PA12 partially transformed into α‐modification. No such transition was observed with the oriented γ′‐PA12 phase even after annealing at temperatures close to melting. A γ′–γ transition was observed here only after isotropization by melting point. Various structural parameters were extracted from the WAXS and SAXS patterns and analyzed as a function of temperature and orientation: the degree of crystallinity, the d‐spacings, the Bragg's long spacings, the average thicknesses of the crystalline (lc) and amorphous (la) phases, and the linear crystallinity xcl within the lamellar stacks. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3720–3733, 2005 相似文献
38.
We have studied the temperature dependence of the radiative deactivation of the Pd-porphine triplet states in Shpol’skii matrices
in the temperature range 1.2–210 K. A substantial transformation of the phosphorescence spectra is observed as the temperature
increases and is due to the inclusion of thermally activated Pd-porphine states in the radiative deactivation processes. The
activation energy Ea of these Pd-porphine states is measured in matrices of n-octane and n-nonane. The splitting of the lowest quasidegenerate
triplet state ΔE(T2−T1) is determined for planar and distorted conformations of the Pd-porphine macrocycle in the n-octane matrix as 40 and 57 cm−1, respectively. The ability to use the temperature dependence of the phosphorescence properties of Pd-porphine to fabricate
molecular thermometers for the low-temperature range is analyzed.
__________
Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 460–464, July–August, 2007. 相似文献
39.
Ya.G. Groda P. Argyrakis G.S. Bokun V.S. Vikhrenko 《The European Physical Journal B - Condensed Matter and Complex Systems》2003,32(4):527-535
The selfconsistent diagram approximation (SCDA) is generalized for three-dimensional lattice gases with nearest neighbor repulsive
interactions. The free energy is represented in a closed form through elementary functions. Thermodynamical (phase diagrams,
chemical potential and mean square fluctuations), structural (order parameter, distribution functions) as well as diffusional
characteristics are investigated. The calculation results are compared with the Monte Carlo simulation data to demonstrate
high precision of the SCDA in reproducing the equilibrium lattice gas characteristics. It is shown that similarly to two-dimensional
systems the specific statistical memory effects strongly influence the lattice gas diffusion in the ordered states.
Received 7 August 2002 / Received in final form 22 January 2003 Published online 24 April 2003 相似文献
40.
We study a system of quasilinear equations describing one-dimensional flow of a viscous compressible heat-conducting medium with a nonmonotone state function and mass force. The large-time behavior of solutions is considered for arbitrarily large initial data. In spite of possible nonuniqueness and discontinuity of the stationary solution, we prove L2-stabilization for the stress and heat flux as t → ∞ along with corresponding global energy estimates for them. The new method of proof utilizes a combination of energy type equalities for the stress and heat flux. Consequently, H1-stabilization of the velocity and temperature along with global estimates for their derivatives are valid as well. 相似文献