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11.
M. Mikoŀajczyk J. Michalski A. Halpern R. Sochaxcka 《Monatshefte für Chemie / Chemical Monthly》1969,100(4):1266-1273
Zusammenfassung An den Modellverbindungen Dialkylchlorthiophosphat (RO)2P(S)Cl (R=Me, Et, n-Pr) und Diphenylchlorthiophosphat (PhO)2P(S)Cl wurde der Austausch Chlorid—Radiochlorid am Thiophosphorylzentrum untersucht. Die bimolekularen Geschwindigkeitskonstanten, die Aktivierungsenergien und Aktivierungsentropien wurden berechnet. Der Einfluß von Substituenten auf bimolekulare Substitutionsreaktionen am vierfach koordinierten Phosphoratom wurde diskutiert.
Mit 3 Abbildungen 相似文献
Chlorine isotopic exchange at phosphorus atoms, I.: Chloridothiophosphates
The chloride—radiochloride ion exchange at the thiophosphoryl centre has been studied using dialkylchloridothiophosphates (RO)2P(S)Cl (R=Me, Et, n-Pr) and diphenylphosphorochloridothionate, (PhO)2P(S)Cl, as model compounds. The bimolecular rate constants, energies and entropies of activation have been calculated. Effects of the substituents in the bimolecular displacement reaction on four-coordinated phosphorus atom have been discussed.
Mit 3 Abbildungen 相似文献
12.
Krzysztof Ciesielski 《Periodica Mathematica Hungarica》1995,31(1):11-20
In the paper we prove that the complex analytic functions are (ordinarily) density continuous. This stays in contrast with the fact that even such a simple function asG:22,G(x,y)=(x,y
3
), is not density continuous [1]. We will also characterize those analytic functions which are strongly density continuous at the given pointa . From this we conclude that a complex analytic functionf is strongly density continuous if and only iff(z)=a+bz, wherea, b andb is either real or imaginary. 相似文献
13.
M. Pekaŀa R. Cloots H. Bougrine E. Maka M. Ausloos 《Zeitschrift für Physik B Condensed Matter》1995,97(1):67-75
The electrical resistivity, thermoelectric power and the Nernst effect have been studied as a function of temperature and magnetic field for a typical superconductor DyBa2Cu3O7– magnetically textured in situ at 1035°C. The three transport coefficients show hybrid microscopic features. In particular, we show the anisotropy with respect to the field direction (H//a,H//c) in all transport coefficients. We verify that Tinkham's law is obeyed for the broadening of the resistive transition in a magnetic field. Similarly we obtainanisotropic broadening exponents for each integrated excess property. From Arrhenius plots we obtain orders of magnitude for the activation energies characterizing each property. They are markedly different from each other. 相似文献
14.
Bozena Nerlo-Pomorska Krzysztof Pomorski 《Zeitschrift für Physik A Hadrons and Nuclei》1994,348(3):169-172
A new formula for the nuclear charge radius is proposed, dependent on the mass numberA and neutron excessN-Z in the nucleus. It is simple and it reproduces all the experimentally available mean square radii and their isotopic shifts of even-even nuclei much better than other frequently used relations.This work is partly supported by the Polish Committee of Scientific Research under contract No. 203119101 相似文献
15.
A symmetry-adapted perturbation theory based on Kohn-Sham determinants [SAPT(KS)] and utilizing asymptotically corrected exchange-correlation potentials has been applied to the He2, Ne2, (H2O)2, and (CO2)2 dimers. It is shown that SAPT(KS) is able to recover the electrostatic, first-order exchange, second-order induction, and exchange-induction energies with an accuracy approaching and occasionally surpassing that of regular SAPT at the currently programmed theory level. The use of the asymptotic corrections is critical to achieve this accuracy. The SAPT(KS) results can be obtained at a small fraction of the time needed for regular SAPT calculations. The robustness of the SAPT(KS) method with respect to the basis set size is also demonstrated. A theoretical justification for high accuracy of SAPT(KS) predictions for the electrostatic, first-order exchange, and second-order induction energies has been provided. 相似文献
16.
Kazimierz Wŀodarczyk 《Monatshefte für Mathematik》1985,99(2):153-160
In this paper regions of variability are determined and a distortion theorem is proved for iterations of holomorphic maps of bounded symmetric homogeneous domains inJ
*-algebras. 相似文献
17.
Krzysztof P Rybakowski 《Journal of Differential Equations》1984,51(2):182-212
Consider the following nonlinear Dirichlet boundary value problems: (1.1) (1.2) . (1.3) In all of these equations, f: R → R is a locally Lipschitzian asymptotically linear function with positive asymptotic slope, f(0) = 0, and L is a self-adjoint, negativedefinite and strongly elliptic second-order differential operator on a smooth domain Ω in Rn. The solutions of (1.1) and (1.2) generate semiflows which are not pointdissipative and whose equilibria are determined by solutions of (1.3). In this paper, using an extension (due to the present author) of Conley's Morse index theory to noncompact spaces, we prove not only the existence of positive solutions of (1.3) (a result shown earlier by Peitgen and Schmitt using different methods), but also show the existence of (nonconstant) heteroclinic orbits of (1.1) and (1.2) joining two sets of equilibria. 相似文献
18.
19.
Intermolecular potential energy surface and spectra of He-HCl with generalization to other rare gas-hydrogen halide complexes 总被引:3,自引:0,他引:3
A two-dimensional (rigid monomer) intermolecular potential energy surface (PES) of the He-HCl complex has been obtained from ab initio calculations utilizing the symmetry-adapted perturbation theory (SAPT) and an spdfg basis set including midbond functions. The bond length in HCl was chosen to be equal to the expectation value in the ground vibrational state of isolated HCl. The rigid-monomer potential should be a very good approximation to the complete (three-dimensional) potential for H-Cl distances corresponding to the lowest vibrational levels of the monomer since the He-HCl interaction energy was found to be only weakly dependent on the HCl bond length in this region, at least as compared to systems such as Ar-HF. The calculated points were fitted using an analytic function with ab initio computed asymptotic coefficients. As expected, the complex is loosely bound, with the dispersion energy providing the majority of the attraction. Our SAPT PES agrees with the semiempirical PES of Willey et al. [J. Chem. Phys. 96, 898 (1992)], in finding that, atypically for rare gas-hydrogen halide complexes including the lighter halide atoms, the global minimum is on the Cl side (with intermonomer separation 3.35 A and depth of 32.8 cm(-1)), rather than on the H side, where there is only a local minimum (3.85 A, 30.8 cm(-1)). The ordering of the minima was confirmed by single-point calculations in larger basis sets and complete basis set extrapolations, and also using higher levels of theory. We show that the opposite findings in the recent calculations of Zhang and Shi [J. Mol. Struct: THEOCHEM 589, 89 (2002)] are due to the lack of midbond functions in their basis set. Despite the closeness in depth of the two linear minima, the existence of a relatively high barrier between them invalidates the assumption of isotropy, a feature of some literature potentials. The trends concerning the locations of minima within the family of rare gas-hydrogen halide complexes are rationalized in terms of the physical components of the intermolecular forces and related to monomer properties. The accuracy of the SAPT PES was tested by performing calculations of rovibrational levels. The transition frequencies obtained were found to be in excellent agreement (to within 0.02 cm(-1)) with the measurements of Lovejoy and Nesbitt [J. Chem. Phys. 93, 5387 (1990)]. The SAPT PES predicts a dissociation energy for the complex of 7.74 cm(-1) which is probably more accurate than the experimental value of 10.1+/-1.2 cm(-1). Our analysis of the ground-state rovibrational wave function shows that the He-HCl configuration is favored over the He-ClH configuration despite the ordering of minima. This is due to the greater volume of the well in the former case. We have also determined positions and widths of three low-lying resonance states through scattering calculations. These predictions are expected to be more accurate than values derived from experiment. 相似文献
20.
Adam S. Paziak Lech Celewicz Krzysztof Ciszewski Krzysztof Golankiewicz 《Journal of mass spectrometry : JMS》1993,28(5):643-646
The electron impact mass spectra of 6-methyltetrazolo[1,5-c]pyrimidin-5(6H)-one, its 7- and 8-methyl derivatives, three 8-halo derivatives and two related nucleosides are reported. On the basis of the high-resolution data and detected metastable ions, the fragmentation routes of their molecular ions are proposed. Coexistence of the tautomeric forms of the title compounds of cyclic (tetrazole) or linear (azide) structure can be suggested owing to the fragmentation pathways identified for the bases. Decomposition of the related nucleosides lies in the breaking of nucleoside bonds to produce the appropriate base and sugar fragments. 相似文献