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41.
Linus Pauling 《Mineralogy and Petrology》1965,10(1-4):379-384
Summary It is shown that a completely tetrahedral structure for Cu3VS4 would be unstable because of a large residual electric charge on the vanadium atom. The observed structure of sulvanite places six copper atoms, as well as four sulfur atoms, within bonding distance of each vanadium atom. The consideration of alternative valence-bond structures that are compatible with the electroneutrality principle (atomic charges restricted to the range between–1 and +1) leads to the bond numbers 0.50 for Cu–S and 0.29 for V–Cu, with 1.00 assumed for V–S. These bond numbers correspond reasonably well with the observed bond lengths and with electroneutrality (charges-0.27 for Cu, +0.06 for V, +0.19 for S). The bond angles at the sulfur atom indicate some bond-bending strain, estimated at 0.85 kcal mole–1 per sulfur atom. This study of the sulvanite structure thus provides an explanation of the concentration of the four bonds formed by the sulfur atom into a small solid angle on one side of the atom.
With 1 Figure
Dedicated to ProfessorF. Machatschki on the occasion of his 70th birthday. 相似文献
Zusammenfassung Es wird gezeigt, daß eine Struktur mit durchgehend tetraedrischer Koordination für Cu3VS4 wegen der großen Restladung des Vanadiumatoms instabil wäre. In der beobachteten Struktur des Sulvanites liegen sowohl vier Schwefelatome wie sechs Kupferatome im Bindungsabstand zu jedem Vanadiumatom. Die Betrachtung anderer kovalenter Strukturen, die mit dem Elektroneutralitäts-Prinzip (Atomladungen auf den Bereich zwischen –1 und +1 beschränkt) verträglich sind, führt auf Bindungszahlen 0,50 für Cu–S und 0.29 für V–Cu, wenn 1,00 für V–S angenommen wird. Diese Bindungszahlen entsprechen den beobachteten Bindungslängen und der Elektroneutralität (Ladungen –0,27 für Cu, +0,06 für V, +0,19 für S) ziemlich gut. Die Bindungswinkel am Schwefelatom deuten auf eine gewisse Spannung durch Verbiegung der Bindungen hin, die auf 0,85 kcal·mol–1 pro Schwefelatom geschätzt wird. Diese Untersuchung der Sulvanitstruktur liefert so eine Erklärung für die Konzentration der vier von Schwefel ausgehenden Bindungen in einem kleinen räumlichen Winkelbereich an einer Seite des Atoms.
With 1 Figure
Dedicated to ProfessorF. Machatschki on the occasion of his 70th birthday. 相似文献
42.
Xianfeng Yao Xiao Hu Lixin Yi Xinxiang Zeng Linus Zhang 《Environmental Earth Sciences》2017,76(24):826
In the region of Three Gorges Reservoir (TGR) in China, there has been occurrence of several frequent earthquakes of moderate intensity since reservoir impounding occurred in 2003. These earthquakes are generally believed to be induced by reservoir impoundment and water-level variations. Usually, the geo-stress will change, when natural earthquakes occur. Following this principle, this paper adopted the rate and state theory to simulate and estimate Coulomb stress changes in the TGR region and obtained the pattern of Coulomb stress changes with time and the event sequence as well as the distribution of Coulomb stress changes in space. First, the TGR regional catalogue was analyzed and processed, leading to quantification of the magnitude of completeness and all of the parameters that are used in the stress–seismicity inversion process, including the reference seismicity rates, characteristic relaxation time, fault constitutive parameters, and stress rates. Second, the temporal evolution of the stress changes in different time windows was computed and analyzed, and it was found that there is an association between the Coulomb stress changes and rates of increase in the cumulative number of earthquakes. In addition, the earthquake occurred in November 2008 (M S = 4.1) was analyzed and attempted to simulate the distribution of stress changes in space through the stress–seismicity inversion model. The results proved that the modeled area coincides with the historical area of earthquakes that occurred after 2008. Finally, a prediction was made about the earthquake productivity rates after 2015, which showed a declining earthquake rate over time that ultimately returned to the background seismicity. This result is essentially in agreement with Omori’s law. To conclude, it is rational to use the stress-inversion method to analyze the relationship between induced earthquake seismicity and local stress changes as well as to simulate the area of earthquake occurrence and productivity rates of reservoir-induced earthquakes. 相似文献
43.
Linus Magnusson Magdalena Alonso-Balmaseda Susanna Corti Franco Molteni Tim Stockdale 《Climate Dynamics》2013,41(9-10):2393-2409
This study discusses and compares three different strategies used to deal with model error in seasonal and decadal forecasts. The strategies discussed are the so-called full initialisation, anomaly initialisation and flux correction. In the full initialisation the coupled model is initialised to a state close to the real-world attractor and after initialisation the model drifts towards its own attractor, giving rise to model bias. The anomaly initialisation aims to initialise the model close to its own attractor, by initialising only the anomalies. The flux correction strategy aims to keep the model trajectory close to the real-world attractor by adding empirical corrections. These three strategies have been implemented in the ECMWF coupled model, and are evaluated at seasonal and decadal time-scales. The practical implications of the different strategies are also discussed. Results show that full initialisation results in a clear model drift towards a colder climate. The anomaly initialisation is able to reduce the drift, by initialising around the model mean state. However, the erroneous model mean state results in degraded seasonal forecast skill. The best results on the seasonal time-scale are obtained using momentum-flux correction, mainly because it avoids the positive feedback responsible for a strong cold bias in the tropical Pacific. It is likely that these results are model dependent: the coupled model used here shows a strong cold bias in the Central Pacific, resulting from a positive coupled feedback between winds and SST. At decadal time-scales it is difficult to determine whether any of the strategies is superior to the others. 相似文献