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71.
本文从“同温度层不完全平行于地面,且在变化”的“任意分层”假设出发,导出了水准折光修正公式,并利用光的色散效应在10~(-6)的精度要求下,求得r=r_T=h_1/h_2=(n_(01)-1)/(n_(02)-1)=常数最后指出,研制双波长激光水准仪的必要性和可能性,并提出了研制此种仪器的技术参数. 相似文献
72.
Thomas Unnerstall 《Journal of statistical physics》1989,54(1-2):379-403
The irreversible macroscopic dynamics of the Josephson junction coupled to external wires acting as a current source is derived rigorously from the underlying microscopic Hamiltonian quantum mechanics. The external systems are treated in the singular coupling limit. The use of this limit is explicitly justified via an interpretation of the singular coupling limit in terms of the relative magnitudes of system, reservoir, and coupling energies. The qualitative behavior of the macroscopic dynamical equations is shown to depend sensitively and crucially on the interaction between the wires and the superconductors and on the size of the wires: the dc Josephson effect only happens when one lets Cooper pairs be driven into the junction by collective (i.e., small) reservoirs. 相似文献
73.
Enthalpies of solution have been measured from 5 to 85°C for aqueous tetraethyl- and tetrapropylammonium bromides, and the integral heat method is employed to evaluate
for these electrolytes over a wide temperature range. Data taken from the literature have been used to evaluate
for aqueous Bu4NBr over a similar temperature range. These data, along with similar data for Me4NBr, previously reported, have been used to evaluate absolute ionic heat capacities. While the absolute values agree only qualitatively with two other methods of division, the temperature dependences of the three methods essentially agree up to 65°C. Heat capacities due to structural effects on the solvent, obtained by subtracting the inherent heat capacities of the ions, are extraordinarily positive for all four tetraalkylammonium ions and have negative temperature coefficients, indicating that all four ions, including the tetramethylammonium ion, are structure-making ions. 相似文献
74.
Mössbauer parameters of frozen aqueous solutions of Sn(ClO4)2 in 0.5 M HClO4 did not change with the concentration of NaClO4, so that it was used to keep the ionic strength at the desired level. When NaCl was added into Sn(ClO4)2 solutions, isomer shift did not change, but quadrupole splitting did. Therefore, stability constants were calculated from the quadrupole splitting data, which were in good agreement with the published values. The observed spectra could be resolved into components. 相似文献
75.
Summary The equation for the potential energy of interactions established for gas-liquid chromatography has been confirmed in reversed phase liquid chromatography. Equations derived for molecular polarizabilities of PAHs and their retention data have very high correlation coefficients. The results indicate that the inductive effect between solute and stationary phase is the main one and the dispersive effect is very small compared with the inductive effect but its contribution increases with the carbon chain length of the stationary phase. 相似文献
76.
José Glaüco Ribeiro Tostes 《Theoretical chemistry accounts》1981,59(3):229-235
Certain features of the chemist's molecular structure model, viz. size and shape, are retrieved even in the best non-adiabatic variational calculations thus far carried out for ground states of H
2
+
and H2. Those features do not conflict with the full symmetry of exact molecular eigenstates, once they are properly understood as correlation effects. 相似文献
77.
A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the
and
computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”. 相似文献
78.
在非水溶剂(二甲基亚砜(DMSO)及N,N_二甲基甲酰胺(DMF))中的伏安曲线.呈现三对电流峰,表明存在三个可逆或准可逆酞菁配体的单电子转移过程,而在水溶液中则不呈现准可逆行为,且波形改变很大.此外,还比较了四磺酸基酞菁锌的水溶液在自然光和红光(600~700nm)照射下的循环伏安曲线,其氧化还原峰的数目和峰电位基本不变,但在红光照射下比自然光照射下的峰电流明显增大. 相似文献
79.
Photoacoustic spectroscopy of solids and surfaces 总被引:1,自引:0,他引:1
After briefly reviewing the theory and instrumentation, results from a variety of experiments carried out by the authors on
the photoacoustic spectroscopy of solids and surfaces by employing an indigenous spectrometer are discussed in the light of
the recent literature. Some of the important findings discussed are, phase angle spectroscopy, anomalous behaviour of monolayers,
unusual frequency dependence in small cell volumes, spectra of a variety of solids including amorphous arsenic chalcogenides,
photoacoustic detection of phase transitions and determination of surface areas and surface acidities of oxides. Recent developments
such as piezoelectric photoacoustic spectroscopy, depth profiling and subsurface imaging are also presented.
Contribution No. 124 from the Solid State and Structural Chemistry Unit. 相似文献
80.
Yuh-Wern Wu 《中国化学会会志》1996,43(6):507-509
The relative rates for the addition reactions of tert-butyl radical to 2-substituted ally chlorides I have een determined. The correlation of log k/k0, vs. σm gives a ρ mvalue of 3.59 with correlation coefficient of 0.930. When the substituent CH2Cl is excluded, correlation coefficient raises to 0.990 and ρ value becomes 3.39. The large p value and the deviation of relative rate of substituent CH2C1 are discussed. 相似文献