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41.
火花激发原子发射光谱法应用于直径小于8mm的不锈钢线材的分析,对此类试样应用了一种特制的夹具,用块状标准样品制作工作曲线。由于线状试样和块状标准样品之间的形状差异所产生的系统不确定度借采用同类型标样作校正,对共存元素的相互干扰也采用了相应的校正方法。其它分析条件,包括严格的制样工序,氩气的纯度要求及其流量控制,以及光源的最佳条件等,作了深入的试验。按所提出的方法测定了不锈钢线材试样中碳、硅、锰、磷、硫、铬、镍及钛等8个元素。经校正后的结果与化学法测得结果相符。  相似文献   
42.
We use a driving field, of the type first suggested by Evans, to generate a steady heat current in the simplest possible system, a two-dimensional periodic fluid of three hard disks. Hard-disk motion equations can be conveniently derived from repulsive constant-force or linear-force potentials by considering the infinitely repulsive limit of these potentials. We show that the isoenergetic and isokinetic forms of the nonequilibrium equations of motion generate steady-state heat conductivities differing by terms of order 1/N, whereN is the number of particles. The resulting conductivities appear to vary as the logarithm of the driving field strength. Even at low fields, the three-body periodic-system results lie well below Enskog's infinite-system prediction.  相似文献   
43.
Heterogeneous kinetics are shown to differ drastically from homogeneous kinetics. For the elementary reaction A + A products we show that the diffusion-limited reaction rate is proportional tot h[A]2 or to [A]x, whereh=1- d s/2, X=1+2/d s =(h-2)(h-1), andd s is the effective spectral dimension. We note that ford = d s =1, h =1/2 andX = 3, for percolating clustersd s = 4/3,h = 1/3 andX = 5/2, while for dust ds <1, 1 >h > 1/2 and >X > 3. Scaling arguments, supercomputer simulations and experiments give a consistent picture. The interplay of energetic and geometric heterogeneity results in fractal-like kinetics and is relevant to excitation fusion experiments in porous membranes, films, and polymeric glasses. However, in isotopic mixed crystals, the geometric fractal nature (percolation clusters) dominates.  相似文献   
44.
Both the homometal cluster [P(ph4)]2[Mo2O2(μ-S)2(S2)2] (1) and [Mo2O2(μ-S)2(Et2dtc)2] (2) (Et2dtc=diethyl-dithiocarbamate) were successfully synthesized by low-temperature solid-state reactions. X-ray single-crystal diffraction studies suggest that compound (1) is a dinuclear anion cluster, and compound (2) is a dinuclear neutral cluster. The two compounds were characterized by elemental analyses, IR spectra and UV-Vis spectra. The third-order non-linear optical (NLO) properties of the clusters were also investigated and all exhibited nice non-linear absorption and self-defocusing performance with moduli of the hyperpolarizabilities 5.145×10−30 esu for (1) and 5.428×10−30 esu for (2).  相似文献   
45.
The influence of internal excitation on the reactions of O 2 + + CH4 and of CO 2 + + NO has been investigated using a slow flow drift tube. The rate coefficients for these reactions obtained as a function of relative kinetic energy in various buffer gases like He, Ne, Ar, and Kr showed higher values under conditions where the internal excitation of the reactant ions was enhanced. For both reactions the lowest reactivity at all kinetic energies was observed to occur in He, indicating that He is the least effective buffer for collisionally inducing internal excitation of molecular ions.  相似文献   
46.
A new mechanism is suggested for the anionic polymerization of isoprene. The key moment of this mechanism is thermal electron excitation of the complex of a living polymer with a monomer to the low lying S1 (T1) state involving a charge (electron) and (Li+) cation transfer from the terminal unit to the monomer molecule. It is stated that the probability of chemical bonding depends on the spin density on the radical centers of reactant molecules and on the geometry of the reaction complex. The semiempirical AM1 and ab initio 6-31G* quantum-chemical calculations revealed strong interaction for the ground electronic state of the complex (5-10 kcal/mole) and low energies of the excited triplet levels (<10 kcal/mole).  相似文献   
47.
The hydrothermal reaction of CuBr2 and CuBr with phen·H2O (phen= 1,10-phenanthroline) in a molar ratio of 1:1:1.5 gave birth to the first copper-halo cationic cluster [Cu2^Ⅱ Cu2^Br4 (phen)4 ] ^2+(1) with tetranuclear anionic cluster [Cu4Br6]^2-. Changing the precursors or their molar ratios, two mononuclear complexes [Cu(phen)2Br]Br·H2O (2) and [Ni(phen)3][CuCl2]2 (3) as well as two unusual copper-halo chains found in polymers [Cu2Br2(phen)]∞ (4) and [Cu^ⅡCu3^ⅠBr2Ⅰ3 (phen)2 ]∞ (5) were obtained. The (Cu2Br2)∞ chain of 4 looks like a linearar ray of hexagons based on fused Cu3Br3 units, and the linear (Cu3Ⅰ3Br^-)∞ chain of 5 is an alternate combination of the rhombic Cu2I2 cores and the Cu4I4Br2^2- units. In addition, the hydrothermal reaction of CuBr2 with NA(NA=nicotinic acid) or INA (INA =isonicotinic acid) resulted in the syntheses of two compounds [CuBr(NA)] (6) and [CuBr(INA)]∞(7) containing staircase chain. Among them the third-order non-linear optical properties of 2, 5, 6 and 7 were investigated and all exhibit the reverse saturable absorption (α2〉0) and self-defocusing performance (n2〈0).  相似文献   
48.
利用现代NMR的1D、2D技术对一个混合物进行了分析。结果表明:混合物由两种化合物组成。为了同时准确确定两种化合物的结构,本工作应用了1D-TOCSY技术,利用该技术选择性强的特点来补充常规的1D、2DHMR实验所提供的分子结构的信息。在没有进行预分离的条件下,顺利地完成了样品中两种化合物的核磁信号归属,并最终确定了它们的结构。  相似文献   
49.
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   
50.
A prerequisite for every biological system to develop and to continue to function (“to live”) is an effective communication between its components, i.e. its cells. This intercellular communication is essentially of a chemical nature: It employs neurotransmitters and hormones as messengers, and receptors as the receivers of transmitted signals. As is typical for all communication systems, biological signal processes usually also utilize only relatively small amounts of material. This general rule, however, does not apply to some synaptic communication systems. One typical exception, for instance, is the nerve-muscle synapse and, in particular, its special form, the nerve-electroplaque synapse of electric fish. These systems, therefore, lend themselves to biochemical studies permitting investigation of the molecular basis of biological communication processes. Thus, the acetylcholine receptor of the plasma membrane of the postsynaptic cell was established as a structurally and functionally rather complicated “transducer system” responsible for both the reception of the chemical message and its conversion into an electrical activity of the receiving cell.  相似文献   
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