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The emission and excitation spectra of Cr3+ -doped Gd3Ga5O12 (GGG) and Gd3Sc2Ga3O12 (GSGG) are explained in the light of multisite effects. The situation is particularly complicated in the case of GSGG, where the different sites have2E energy levels near each other which overlap with the4A2 4T2 absorption bands. The spectra obtained under selective excitations are interpreted on the multisite assumption. 相似文献
3.
Vaporisation et dissociation thermique des sulfures de phosphore P4S3, P4S7 et P4S10 a l'etat gazeux
J. Bouix R. Hillel H. Vincent Y. Monteil 《Journal of Thermal Analysis and Calorimetry》1977,12(3):371-382
Résumé Nous avons montré par spectrométrie Raman à chaud et mesure des tensions de vapeur que P4S3 se vaporise de façon congruente tandis que P4S7 et P4S10 se dissocient dès le début de leur vaporisation. P4S7 donne réversiblement P4S3 et soufre. P4S10 se dissocie irréversiblement en P4S7 et soufre. A l'état de vapeur non saturante, P4S3 se dissocie au-dessus de 600° avec formation de phosphore, de soufre et d'autres espèces non identifiées.Nous avons mesuré expérimentalement la capacité calorifique de P4S3 liquide, calculé celle de P4S3 gazeux et son entropie standard. Nous avons aussi estimé l'enthalpie standard de vaporisation de P4S3 à l'aide des mesures des tensions de vapeur saturante. Nous en avons déduit l'entropie standard de P4S3 liquide et son point d'ébullition.
Nous remercions Monsieur Letoffe du laboratoire du Professeur J. Bousquet, INSA de Lyon, 20 Avenue Albert Einstein 401, 69621 Villeurbanne, qui a r6alis6 pour nous les déterminations expérimentales des capacités calorifiques de P4S8 liquide. 相似文献
It is shown by Raman spectroscopy at high temperature and by vapor tensimetric measurements that the vaporisation of P4S3 is congruent, whereas P4S7 and P4S10 dissociate at the beginning of vaporisation. P4S7 gives P4S3 and sulfur reversibly. The dissociation of P4S10 into P4S7 and sulfur is irreversible. Above 600°, in non-saturated vapour the dissociation of P4S3 gives phosphorus, sulfur and some unidentified gaseous species. The heat capacity of liquid P4S3 has been measured. That of gaseous P4S3 and its standard entropy have been calculated. The vaporisation standard enthalpy of P4S3 has been estimated from the experimental results on the saturated vapour pressures. The standard entropy of liquid P4S3 and its boiling point have been derived from these data.
Zusammenfassung Mittels Raman-Spektrometrie bei erhöhter Temperatur und durch Messung der Dampfdrucke wurde festgestellt, daß sich P4S3 verflüchtigt, während P4S7 und P4S10 mit Beginn der Verflüchtigung dissoziieren. P4S7 ergibt reversibel P4S3 und Schwefel. Im Zustand ungesättigten Dampfes dissoziiert P4S3 oberhalb von 600° unter Bildung von Phosphor, Schwefel und anderer nicht identifizierter Substanzen.Die Wärmekapazität von flüssigem P4S3 wurde gemessen, während die vom gasförmigem P4S3 sowie seine Standard-Entropie berechnet wurden. Die Standard-Enthalpie der Verflüchtigung des P4S3 wurde durch Messungen der Sättigungs-Dampfdrucke ermittelt. Daraus wurden die Standard-Entropie des flüssigen P4S3 sowie sein Siedepunkt berechnet.
- - , P4S3 , P4S7 P4S10 . P4S7 P4S3 , P4S10 P4S7 . 600° P4S3 , . P4S3, P4S3 . P4S3. P4S3 .
Nous remercions Monsieur Letoffe du laboratoire du Professeur J. Bousquet, INSA de Lyon, 20 Avenue Albert Einstein 401, 69621 Villeurbanne, qui a r6alis6 pour nous les déterminations expérimentales des capacités calorifiques de P4S8 liquide. 相似文献
4.
Behaviour of water-soluble dinuclear rhodium complexes in the hydroformylation reaction of oct-1-ene
The biphasic hydroformylation reaction of oct-1-ene, has been investigated by using the water-soluble dinuclear complex [Rh2(μ-StBu)2(CO)2(TPPTS)2] as precursor. Addition of ethanol as a cosolvent dramatically improved the yields but the good regioselectivity in linear aldehyde observed for neat oct-1-ene—water systems (97%) decreased to 83% (for 22% ethanol w/w). It is shown that the dinuclear framework cannot be maintained, that the mononuclear complex [RhH(CO)(TPPTS)3] is formed, and that thiol and significant amounts of [Rh2(μ-StBu)2(CO)4] move into the organic phase. This reaction from the dinuclear species requires the simultaneous presence of water and carbon monoxide. Introduction of the water-soluble thiol HS(CH2)3NMe2 in the bridging positions affords the complex [Rh2(μ-S(CH 2)3NHMe2)2(CO)2(TPPTS)2]Cl2 which can be kept in the aqueous hase but has a low level of catalytic activity. 相似文献
5.
We study the one-dimensional symmetry of solutions to the nonlinear Stokes equation which are periodic in the d − 1 last variables (living on the torus 𝕋d−1) and globally minimize the corresponding energy in Ω = ℝ × 𝕋d−1, i.e., Namely, we find a class of nonlinear potentials W ≥ 0 such that any global minimizer u of E connecting two zeros of W as x1 → ± ∞ is one-dimensional; i.e., u depends only on the x1 -variable. In particular, this class includes in dimension d = 2 the nonlinearities with w being a harmonic function or a solution to the wave equation, while in dimension d ≥ 3 , this class contains a perturbation of the Ginzburg-Landau potential as well as potentials W having d + 1 wells with prescribed transition cost between the wells. For that, we develop a theory of calibrations relying on the notion of entropy (coming from scalar conservation laws). We also study the problem of the existence of global minimizers of E for general potentials W providing in particular compactness results for uniformly finite energy maps u in Ω connecting two wells of W as x1 → ± ∞ . © 2019 Wiley Periodicals, Inc. 相似文献
6.
7.
Matthew P. Conley Murielle F. Delley Georges Siddiqi Giuseppe Lapadula Sébastien Norsic Vincent Monteil Olga V. Safonova Christophe Copéret 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(7):1903-1907
The insertion of an olefin into a preformed metal–carbon bond is a common mechanism for transition‐metal‐catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal–carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first Cr C bond is formed remain unknown. We synthesized well‐defined dinuclear CrII and CrIII sites on silica. Whereas the CrII material was a poor polymerization catalyst, the CrIII material was active. Poisoning studies showed that about 65 % of the CrIII sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si–(μ‐OH)–CrIII species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at CrIII O bonds. 相似文献
8.
V.?TeboulEmail author S.?Maabou L. C.?Fai A.?Monteil 《The European Physical Journal B - Condensed Matter and Complex Systems》2005,43(3):355-362
We investigate the presence of dynamical heterogeneity in supercooled water with molecular dynamics simulations using the new water model proposed by Mahoney and Jorgensen [M.W. Mahoney, W.L. Jorgensen J. Chem. Phys. 112, 8910 (2000)]. Prompted by recent theoretical results [J.P. Garrahan, D. Chandler, Phys. Rev. Lett. 89, 35704 (2002)] we study the dynamical aggregation of the least and the most mobile molecules. We find dynamical heterogeneity in supercooled water and string-like dynamics for the most mobile molecules. We also find the dynamical aggregation of the least mobile molecules. The two kinds of dynamical aggregation appear however to be very different. Characteristic times are different and evolve differently. String-like motions appear only for the most mobile molecules, a result predicted by the facilitation theory. The aggregation of the least mobile molecules is more organized than the bulk while the opposite is observed for the most mobile molecules. 相似文献
9.
Thierry Monteil 《Journal of statistical physics》2004,114(5-6):1619-1623
A planar polygonal billiard $\mathcal{P}$ is said to have the finite blocking property if for every pair (O, A) of points in $\mathcal{P}$ there exists a finite number of “blocking” points B 1,...,B n such that every billiard trajectory from O to A meets one of the B i 's. As a counter-example to a theorem of Hiemer and Snurnikov, we construct a family of rational billiards that lack the finite blocking property. 相似文献
10.
David Ribour Vincent Monteil Roger Spitz 《Journal of polymer science. Part A, Polymer chemistry》2008,46(16):5461-5470
Thermal treatments under vacuum of conventional supported Ziegler‐Natta precatalysts (MgCl2/TiCl4/Dibutylphthalate) were conducted to gradually remove titanium to modify the active sites distribution. Only limited detitanations of precatalysts were achieved paying attention not to chemically alter the internal donor (T < 150 °C). Used in combination with the required cocatalyst and external donor in the propylene slurry polymerization, the modified precatalysts exhibited a drop of activity versus decreasing titanium content but the distributed polymer properties are almost not affected (a slight narrowing of molecular weight distribution was observed). After a titanium chloride secondary impregnation (possibly done in presence of an additional Lewis base), activity resumed but polymer properties are once again unchanged. These findings highlight the difficulty to separate the different families of active sites and lead us to propose a cluster organization of titanium active sites. Active sites are composed of titanium clusters having a size distribution at the precatalyst surface, possessing a critical operating size and operating collectively in polymerization. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5461–5470, 2008 相似文献