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31.
Del Bene JE Alkorta I Sanchez-Sanz G Elguero J 《The journal of physical chemistry. A》2012,116(11):3056-3060
Ab initio MP2/aug'-cc-pVTZ calculations have been carried out to determine the structures and binding energies of homodimers (PHFX)(2) for X = F, Cl, CN, CH(3), and NC. Geometric isomers of these complexes with C(i) symmetry exist, which are differentiated in terms of the nature of the atoms (F-P···P-F, H-P···P-H, or A-P···P-A, with A being the atom of X directly bonded to P), which approach a nearly linear alignment. Of these, isomers having F-P···P-F linear are the most stable. Binding energies, intermolecular distances, and EOM-CCSD spin-spin coupling constants are sensitive to both the nature of X and the atoms that assume the linear alignment. 相似文献
32.
An ab initio study has been carried out to determine the structures, relative stabilities, and spin-spin coupling constants of a set of 17 methyl-substituted 1,3-diborata-2,4-diphosphoniocyclobutanes B(2)P(2)(CH(3))(n)H(8-n), for n = 0, 1, 2, 4, with four-member B-P-B-P rings. The B-P-B-P rings are puckered in a butterfly conformation, in agreement with experimental data for related molecules. Isomers with the CH(3) group bonded to P are more stable than those with CH(3) bonded to B. If there is only one methyl group or if two methyl groups are bonded to two different P or B atoms, isomers with equatorial bonds are more stable than those with axial bonds. However, when two methyl groups are present, the gem isomers are the most stable for molecules B(2)P(2)(CH(3))(2)H(6) with P-C and B-C bonds, respectively. Transition structures present barriers to the interconversion of two equilibrium structures or to the interchange of axial and equatorial positions in the same isomer. These barriers are very low for the isomer with two methyl groups bonded to B in axial positions for the isomer with four axial bonds and for the isomer with geminal B-C bonds at both B atoms. Coupling constants (1)J(B-P), (1)J(P-C), (1)J(B-C), (2)J(P-P), and (3)J(P-C) are capable of providing structural information. They are sensitive to the number of methyl groups present and can discriminate between axial, equatorial, and geminal bonds, although not all do this to the same extent. The one-bond coupling constants (1)J(B-P), (1)J(P-C), and (1)J(B-C) are similar in equilibrium and transition structures, but (3)J(P-C) and (2)J(P-P) are not. These coupling constants and those of the corresponding fluoro-derivatives of the 1,3-diborata-2,4-diphosphoniocyclobutanes demonstrate the great sensitivity of phosphorus coupling to structural and electronic effects. 相似文献
33.
M. Trinkel W. Trettnak F. Reininger R. Beneš P. O Leary O. S. Wolfbeis 《International journal of environmental analytical chemistry》2013,93(1-4):237-251
Abstract An optical sensor for the determination of ammonia in water based on ion pairing has been investigated. A pH-sensitive dye is immobilized as an ion pair in a silicone matrix. The colour of the dye changes from yellow to blue depending on the concentration of ammonia in the sample solution. This change is reversible. The concentration of ammonia can be determined by measuring the transmittance at a given wavelength. All measurements were performed with a dual-beam optical meter. The measurement range was from 5.9 × 10?7 to 1 × 10?3 M (0.01 to 17 mg/l) in 0.1 M phosphate buffer of pH 8. The detection limit was 10 μg/l. The response times at a flow rate of 2.5 ml/min were 4 min for t90 and 10 min for t100 at a change from 41.9 to 82.5 μM ammonia and 12 min for t90 and 48 min for t100 at a change from 160 to 0 μM ammonia. The operational lifetime of the ammonia sensor was limited to a period of a few days only. A continuous decrease in baseline signal and relative signal change was observed over the whole measurement. The storage stability was more than 10 months (dry). With respect to possible application of the ammonia sensor to environmental analysis, the influence of pH, typical interferences, such as amines and various detergents on the sensor response was investigated. No interference due to pH was observed in the range from pH 5 to pH 9. With methyl- and ethylamine the response was not completely reversible. The sensor was affected by cationic detergents, but not by anionic or neutral detergents. 相似文献
34.
José Elguero Ibon Alkorta Janet E. Del Bene 《Magnetic resonance in chemistry : MRC》2020,58(8):727-732
Equation-of-motion coupled-cluster singles and doubles (EOM-CCSD) calculations have been performed to determine coupling constants 1J(X–Y) for 65 molecules HmX–YHn, with X,Y ═ 1H, 7Li, 9Be, 11B, 13C, 15N, 17O, 19F, 31P, 33S, and 35Cl. The computed 1J(X–Y) values are in good agreement with available experimental data. The reduced coupling constants 1K(X–Y) have been derived from 1J(X–Y) by removing the dependence on the magnetogyric ratios of X and Y. Patterns are found for the reduced coupling constants on a 1K(X–Y) surface that are related to the positions of X and Y in the periodic table. 相似文献
35.
The paper aims at the analysis of principal factors affecting interaction of radiocobalt with freshwater solids, important for migration of radiocobalt in surface streams. Uptake and release of radiocobalt by sediment from a small river have been studied as a function of pH and composition of aqueous phase, the cobalt concentration and contact time, using laboratory model experiments. A factor of primary importance is the contact time due to slow and two-step kinetics of radiocobalt uptake, which also strongly depends on the concentration of sediment in suspension. pH exerts the most significant effect on the interaction in the pH region of 5–7.5, where the uptake increases with pH. Ionic strength of water phase (I) and concentration of cobalt in water (c) affect the interaction only at rather high values of I or c and their variation can be neglected in the modelling of radiocobalt transport in streams under ordinary conditions. Desorption by river water of radiocobalt pre-adsorbed on the sediment passes through a maximum with desorption time, decreases with increasing adsorption time and increases upon drying of the sediment prior to desorption. Results obtained are compared with literature data and conclusions are drawn concerning the mechanism of radiocobalt uptake by the sediment. 相似文献
36.
37.
Ludvík Beneš Vítězslav Zima 《Journal of inclusion phenomena and macrocyclic chemistry》1994,20(4):381-391
The course of intercalation of water into 1-VOPO4 has been studied by thermomechanical analysis and X-ray diffraction. Neither formation of vanadyl phosphate monohydrate nor staging were observed during the intercalation. The broadening and the shift of the positions of the lines in the diffractograms have been explained by the random stacking of intercalated and nonintercalated layers in the sample. 相似文献
38.
39.
Ab initio equation-of-motion coupled cluster calculations have been carried out to evaluate one-, two-, and three-bond 13C-13C, 15N-13C, 31P-13C coupling constants in benzene, pyridine, pyridinium, phosphinine, and phosphininium. The introduction of N or P heteroatoms into the aromatic ring not only changes the magnitudes of the corresponding X-C coupling constants (J, for X = C, N, or P) but also the signs and magnitudes of corresponding reduced coupling constants (K). Protonation of the heteroatoms also produces dramatic changes in coupling constants and, by removing the lone pair of electrons from the sigma-electron framework, leads to the same signs for corresponding reduced coupling constants for benzene, pyridinium, and phosphininium. C-C coupling constants are rather insensitive to the presence of the heteroatoms and protonation. All terms that contribute to the total coupling constant (except for the diamagnetic spin-orbit (DSO) term) must be computed if good agreement with experimental data is to be obtained. 相似文献
40.
O. Beneš R. Jardin R.J.M. Konings E. Colineau F. Wastin N. Magnani 《The Journal of chemical thermodynamics》2009,41(4):560-563
The enthalpy increments of UPd3 and ThPd3 have been measured using the drop calorimetry for temperature range (480 to 1290) K. The heat capacity curves have been derived using the simultaneous linear regression of our data and the low temperature heat capacity data from previous studies. Furthermore the Schottky contributions for UPd3 were determined by comparing the ThPd3 and UPd3 heat capacity functions and correlated with the theoretical values calculated from the crystal field energy levels. 相似文献