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991.
Nuclear spin-spin coupling constant J
HD
of the deuterated hydrogen molecule is determined by minimizing the self-coupling energy evaluated with the Gregson, Hall and Rees operator. The family of variational functions used is suggested by the form of the hydrogen-like atomic orbitals perturbed by this operator.The comparison of the results with those previously obtained with a different family of functions shows that it is necessary for those calculations to use a perturbated function which is as perfectly adapted to the perturbation in the immediate neighbourhood of the nucleus, as in the remainder of the molecular domain. 相似文献
992.
Oswald Schier Wolfgang Nübling Walter Steidle Jacques Valls 《Angewandte Chemie (International ed. in English)》1970,9(8):599-604
The Documentation Ring of the chemical and pharmaceutical industries uses a punched card system to record chemical reactions. The starting materials and the end products are encoded with a fragmentation code, and the bonds that change during the reaction are recorded in the same way. Reaction modifiers and physical data can also be stored. In the case of multistage reactions, both the individual stages and various groups of stages are recorded. 相似文献
993.
Mantel C Baffert C Romero I Deronzier A Pécaut J Collomb MN Duboc C 《Inorganic chemistry》2004,43(20):6455-6463
The isolation, structural characterization, and electronic properties of a series of high-spin mononuclear five-coordinated Mn(II) complexes, [Mn(terpy)(X)(2)] (terpy = 2, 2':6',2' '-terpyridine; X = I(-) (1), Br(-) (2), Cl(-) (3), or SCN(-) (4)), are reported. The X-ray structures of the complexes reveal that the manganese ion lies in the center of a distorted trigonal bipyramid for complexes 1, 2, and 4, while complex 3 is better described as a distorted square pyramid. The electronic properties of 1-4 were investigated by high-field and high-frequency EPR spectroscopy (HF-EPR) performed between 5 and 30 K. The powder HF-EPR spectra have been recorded in high-field-limit conditions (95-285 GHz) (D < gbetaB). The spectra are thus simplified, allowing an easy interpretation of the experimental data and an accurate determination of the spin Hamiltonian parameters. The magnitude of D varies between 0.26 and 1.00 cm(-)(1) with the nature of the anionic ligand. Thanks to low-temperature EPR experiments, the sign of D was unambiguously determined. D is positive for the iodo and bromo complexes and negative for the chloro and thiocyano ones. A structural correlation is proposed. Each complex is characterized by a significant rhombicity with E/D values between 0.17 and 0.29, reflecting the distorted geometry observed around the manganese. Finally, we compared the spin Hamiltonian parameters of our five-coordinated complexes and those previously reported for other analogous series of dihalo four- and six-coordinated complexes. The effect of the coordination number and of the geometry of the Mn(II) complexes on the spin Hamiltonian parameters is discussed. 相似文献
994.
Résumé Les résultats de divers travaux montrent que la valeurE
e
de l'énergie activation expérimentale tirée des diagrammes d'Arrhénius varie avec la pression, dans le cas de réactions de décompositions endothermiques.L'analyse de divers modèles permet d'expliquer cette constatation en montrant que la grandeurE
e
n'a pas le sens d'une énergie d'activation mais est une fonction de nombreux paramètres. Deux d'entre eux ont été retenus dans le cadre de cette étude: le terme d'écart à l'équilibre et le terme de gradient thermique, provoqué par l'endothermicité du phénomène.Cette analyse permet d'établir une prévision de la fonctionE
e
(P) conforme aux résultats expérimentaux.
The results from various investigations show that the experimental activation energy valueE e derived from the Arrhenius diagrams varies with pressure for endothermic decomposition reactions.The analysis of various models allows this fact to be accounted for by showing thatE e should be regarded not in its fundamental formulation, but as being a function of numerous parameters. Two of these were taken into account in the present study, i.e. deviation from equilibrium and a thermal gradient due to the fact that the phenomenon is endothermic.FunctionE e (P) fitting the experimental results may be predicted by such an analysis.
Zusammenfassung Die Ergebnisse verschiedener Untersuchungen zeigen, dass die aus den Arrhenius-Diagrammen abgeleiteten experimentellen Werte der AktivierungsenergieE e bei endothermen Zersetzungsreaktionen mit dem Druck variieren.Die Analyse verschiedener Modelle ermöglicht eine Erklärung dieser Tatsache, indem gezeigt wird, dassE e nicht in ihrer grundliegenden Formulierung betrachtet werden darf, sondern als Funktion einer Anzahl von Parametern. Zwei dieser Parameter wurden in der vorliegenden Untersuchung berücksichtigt d.h. die Abweichung von dem Gleichgewicht und der thermische Gradient, welcher infolge der endothermen Beschaffenheit der Erscheinung auftritt.Eine den Versuchsergebnissen entsprechende FunktionE e (P) kann mittels einer solchen Analyse vorausgesagt werden.
, e, , . , ee , . , : , , . e (), , .相似文献
995.
Jacques Simon 《Letters in Mathematical Physics》1975,1(1):23-29
Given a Banach representation of a Hilbert Lie group, the Lie algebra \(\mathfrak{G}\) of which is the closure of the union of an increasing sequence of finite dimensional subalgebras, we construct a Gårding domain on which we differentiate the group representation to a representation of a dense subalgebra of \(\mathfrak{G}\) . 相似文献
996.
Jacques Hurtubise 《Communications in Mathematical Physics》1989,120(4):613-641
By studying a construction of Nahm, we compute the moduli spaces of monopoles with maximal symmetry breaking at infinity forSU(N),SO(N) andSp(N); these are found to be equivalent to spaces of holomorphic maps from 1 into flag manifolds.Research supported in part by NSERC grant A8361 and FCAR grant EQ3518 相似文献
997.
We give a detailed proof, under slightly weaker conditions on the objective function, that a modified Frank-Wolfe algorithm based on Wolfe's away step strategy can achieve geometric convergence, provided a strict complementarity assumption holds.Research supported by FCAC (Québec) and NSERC (Canada). 相似文献
998.
Jacques Simon 《Annali di Matematica Pura ed Applicata》1986,146(1):65-96
Summary A characterization of compact sets in Lp (0, T; B) is given, where 1P and B is a Banach space. For the existence of solutions in nonlinear boundary value problems by the compactness method, the point is to obtain compactness in a space Lp (0,T; B) from estimates with values in some spaces X, Y or B where XBY with compact imbedding XB. Using the present characterization for this kind of situations, sufficient conditions for compactness are given with optimal parameters. As an example, it is proved that if {fn} is bounded in Lq(0,T; B) and in L
loc
1
(0, T; X) and if {fn/t} is bounded in L
loc
1
(0, T; Y) then {fn} is relatively compact in Lp(0,T; B), p相似文献
999.
The protonation of an aqueous solution of two ampholytes AH and BH next to a gel buffered by immobilized acid moieties IH has been studied by finite element simulation in an iterative scheme. A ten species model has been formulated, taking into account transient diffusion and equilibrium kinetics of the two amphoteric species AH and BH, of water and of the immobilized species IH. This model has been developed to illustrate the pH evolution between an ampholyte solution and an Immobiline gel, and to study the influence of the Immobiline concentration on protons and ampholyte distributions. It has been demonstrated that a minimum initial Immobiline concentration of 10(-2) M is necessary to maintain the pH in the gel in contact with a closed chamber, when the difference between the isoelectric points of AH and BH is 4 and when the initial concentration of the ampholytes in solution is in the micromolar range. This approach provides a first theoretical framework for the recently developed Off-Gel trade mark electrophoresis. 相似文献
1000.
Nonadiabatic dynamics in the title reaction have been investigated by 2+1 REMPI detection of the Cl(2P(3/2)) and Cl*(2P(1/2)) products. Reaction was initiated by photodissociation of CH(3)I at 266 nm within a single expansion of a dilute mixture of CH(3)I and HCl in argon, giving a mean collision energy of 7800 cm(-1) in the center-of-mass frame. Significant production of Cl* was observed, with careful checks made to ensure that no additional photochemical or inelastic scattering sources of Cl* perturbed the measurements. The fraction of the total yield of Cl(2P(J)) atoms formed in the J=1/2 level at this collision energy was 0.150+/-0.024, and must arise from nonadiabatic dynamics because the ground potential energy surface correlates to CH(4)+Cl(2P(3/2)) products. 相似文献