全文获取类型
收费全文 | 15269篇 |
免费 | 2043篇 |
国内免费 | 1649篇 |
专业分类
化学 | 5611篇 |
晶体学 | 92篇 |
力学 | 993篇 |
综合类 | 233篇 |
数学 | 7749篇 |
物理学 | 4283篇 |
出版年
2024年 | 35篇 |
2023年 | 138篇 |
2022年 | 279篇 |
2021年 | 318篇 |
2020年 | 439篇 |
2019年 | 564篇 |
2018年 | 407篇 |
2017年 | 533篇 |
2016年 | 617篇 |
2015年 | 502篇 |
2014年 | 769篇 |
2013年 | 1220篇 |
2012年 | 840篇 |
2011年 | 925篇 |
2010年 | 801篇 |
2009年 | 1025篇 |
2008年 | 1024篇 |
2007年 | 1001篇 |
2006年 | 850篇 |
2005年 | 760篇 |
2004年 | 737篇 |
2003年 | 701篇 |
2002年 | 602篇 |
2001年 | 431篇 |
2000年 | 422篇 |
1999年 | 400篇 |
1998年 | 364篇 |
1997年 | 337篇 |
1996年 | 284篇 |
1995年 | 202篇 |
1994年 | 196篇 |
1993年 | 150篇 |
1992年 | 137篇 |
1991年 | 98篇 |
1990年 | 99篇 |
1989年 | 74篇 |
1988年 | 58篇 |
1987年 | 48篇 |
1986年 | 44篇 |
1985年 | 61篇 |
1984年 | 47篇 |
1983年 | 32篇 |
1982年 | 63篇 |
1981年 | 55篇 |
1980年 | 37篇 |
1979年 | 64篇 |
1978年 | 34篇 |
1977年 | 37篇 |
1976年 | 24篇 |
1973年 | 26篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
21.
The crystal structure of a second high-pressure copper vanadate phase, CuVO3(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (Rw = 0.051). The space group is rhombohedral, , with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [aR = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu+V5+O3 is proposed. This represents a unique example of Cu+ in an octahedral environment. 相似文献
22.
The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge
M
0
of M while the second q
2
P(r) gives the additional contributions due to the polarization of
M
0
under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M. 相似文献
23.
E. U. Franck 《Journal of solution chemistry》1973,2(2-3):339-356
A survey is given of recent experimental results obtained from high-temperature, high-pressure investigations with water, aqueous solutions, and ionic fluids. Data on the static dielectric constant of water to 550°C and 5 kbar are given and discussed with respect to their relation to water structure. Infrared and Raman spectra of HDO in pure water have been obtained to 400°C and 4 kbar, which give information on hydrogen bonding. Xe–H2O and CO2–H2O mixtures were investigated in the infrared. Ni(II) and Cu(II) complexes were investigated by absorption spectroscopy in aqueous solutions of high chloride content to 350°C and 2–6 kbar. The gas-liquid critical point of ammonium chloride was found at 880°C and 1635 bars. This fluid appears to be predominantly ionic even in the critical region. The possibility of converting pure polar fluids such as ammonia and water into concentrated ionic solutions by self-ionization at very high pressures is mentioned.This paper was presented at the symposium, The Physical Chemistry of Aqueous Systems, held at the University of Pittsburgh, Pittsburgh, Pennsylvania, June 12–14, 1972, in honor of the 70th birthday of Professor H. S. Frank. 相似文献
24.
An X-band EPR study on a Na_3(CrMo_6O_(24)H_6)·8H_2O single crystal diluted by its isomor-phic compound Na_3(AlMo_6O_(24)H_6)·8H_2O at room temperature is reported. Using the least squares-fitting method to simulate the EPR data for principal planes, the Hamiltonian parameterswere obtained. The principal values of the g tensors are g_(ZZ) = 1.904, g_(XX)= 1.973, g_(YY)=1.933. The zero field splitting tensor parameters are D = 0.275 cm~(-1), E = 0.05 cm~(-1). The fielddependence of Cr~(3+) energy levels with field at different angles from the principal axes whenthe field is along the principal planes is calculated based on these experimental parameters.The isofrequency plots of calculated field vs. angle are also shown. They agree well with theexperimental results. 相似文献
25.
The title compound, Cu(S2CNEt2)2, behaves at low temperatures (1–20 K) as a normal spin-1/2 molecule, with 〈g〉 =2.06 and the Curie-Weiss θ = +0.25 K. This result contradicts an earlier investigation that led to the suggestion that the crystallographically-occurring dimers are coupled ferromagnetically. 相似文献
26.
A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex. 相似文献
27.
Solutions of CoII salts of organic acids in primary amines absorb molecular oxygen rapidly and irreversibly forming μ-dioxygen—cobalt complexes. Thermolysis leads to a homopolar cleavage of the OO bond with subsequent radical reactions involving ligand amine. After thermolysis the capacity of oxygen uptake is reestablished (catalysis). 相似文献
28.
The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical. 相似文献
29.
MASOUMEH HASANI MOJTABA SHAMSIPUR 《Journal of inclusion phenomena and macrocyclic chemistry》1997,28(1):39-49
The formation of charge transfer complexes with 1:1 and 2:1 stoichiometries (acceptor-to-donor) between DDQ and 1,10-diaza-18-crown-6 in chloroform solution was investigated spectrophotometrically. The stepwise formation constants of the resulting complexes were evaluated from the non-linear least-squaresfitting of the absorbance-mole ratio data. The enthalpies and entropiesof the complexation reactions were determined from the temperature dependence of the stepwise formation constants. The resulting 1:1 and 2:1 complexes were isolated in crystalline form and characterized. The results are consistent with the ionic structure of the resulting charge transfer complexes. 相似文献
30.
Lorraine P. McDonnell Bushnell Eric R. Evitt Robert G. Bergman 《Journal of organometallic chemistry》1978,157(4):445-456
Reactions of η5-cyclopentadienylbis(triphenylphosphine)cobalt(I) (5) with several 2,n-alkadiynes (2) were investigated. Each of these reactions leads initially to a material in which one of the acetylene functional groups is π-coordinated to cobalt; this complex then undergoes conversion to a metallocycle. In cases where the two acetylene functions are connected by three- and four-carbon bridges (2b, 2c), metallocycles formed by intramolecular reaction of two acetylene functions in the same molecule may be isolated. In cases where the acetylene functions are joined by larger or smaller bridges, the reactions are more complex, and both inter- and intramolecular metallocycles are formed. Reactions of 5 with 1,8-bis(trimethylsilyl)-1,7-octadiyne (16) gives an isolable crystalline mono-acetylene complex (17), this material is stable in the solid state but undergoes conversion to metallocycle (18) in benzene solution. The relationship of these results to the mechanism of the CpCo(CO)2-catalyzed benzocycloalkene synthesis is discussed; it is suggested that intramolecular metallocycles are intermediates in reactions leading to benzocyclopentanes and -cyclohexenes, but intermolecular metallocycles are probably involved in reactions leading to benzocyclobutenes. 相似文献