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131.
Guang-Ming Yang Peng Cheng Dai-Zheng Liao Zong-Hui Jiang Shi-Ping Yan Geng-Lin Wang Xin-Kan Yao Hong-Gen Wang 《Journal of Cluster Science》1998,9(4):465-471
The preparation, magnetic properties, and crystal structure of [(salen)Cu]4[(salen)Fe(H2O)2]2(ClO4)2 via hydrogen bonding are described [salen=N,N-ethylenebis (salicylideneiminate)]. Crystals are triclinic, of space group
, with cell constants a=12.853(3), b=13.921(3), c=14.251(3) Å, =68.68(3)°, =87.86(3)°, =86.82(3)°, and Z=1. The structure was solved and refined to R=0.064 and R=0.068. The structure comprises the hexanuclear units which result from the linking of four mononuclear fragments [(salen)Cu] and two mononuclear fragment [(salen)Fe(H2O)]+, through Cu -O H -O -Fe -O -H O -Cu hydrogen bonds of coordinating H2O. In this complex, FeIII ions are in almost square-planar surroundings. The temperature dependences of the magnetic susceptibilities of the complex have been studied in the 4.2–300 K range, indicating the presence of an antiferromagnetic interactions between metal ions. 相似文献
132.
应用INDO/S半经验量子化学方法,对簇合物离子Mo3S和Mo3S4Mn+(M=Fe、Ni,n=4;M=Cu,n=5)分别进行分子轨道计算。根据计算得到的簇离子中的原子表观电荷和成键指标,说明Fe、Ni、Cu+与Mo3S成键作用的相对强度依次是Fe-Mo>Ni-Mo>Cu+-Mo。比较了用含组态作用的INDO/S方法计算得到的电子跃迁能与实验得到的电子吸收光谱值,并讨论了吸收峰归属情况。对于M为Fe、Ni的簇离子Mo3S4M4+,最低能量的电子跃迁吸收峰起源于异金属间电荷转移跃迁(MM’CT);而Mo3S4Cu(5+)簇离子观察到的吸收峰主要是Mo3S芯的局域内电荷转移跃迁。根据理论计算结果,由Cu+离子到Mo3S的电荷转移跃迁谱线,大约在46000cm-1以上才能观察到吸收峰。从Mo3S4Fe4+次低能量吸收峰的实验值16600cm-1和理论值16500cm-1与Mo3S的最低能量吸收峰的实验值16600cm-1和理论值16900cm-1比较,表明无论从理论上或实验上都能证实簇离子Mo3S4Fe4+在能量为16600cm-1处的吸收峰是起因于Mo3S芯的局域内电荷转移跃迁。 相似文献
133.
Riccò M Shiroka T Carretta S Bolzoni F Femoni C Iapalucci MC Longoni G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(9):2856-2861
The magnetic behaviour of the even-electron [Ni16Pd16(CO)40]4- cluster, in its [NnBu4]+ salt, has been investigated by magnetometry and muon spin rotation/relaxation (muSR) spectroscopy. The susceptibility measurements show an exceptionally high magnetic moment corresponding to a total spin value J=2. This suggests a Hund filling of a quadruplet ground state, quite unique in carbonyl-metal clusters. SQUID magnetometry shows a departure from the Curie-Weiss law, for T>150 K, and strong deviation from a Brillouin behaviour of the magnetisation curves. muSR spectroscopy in zero applied field shows a temperature independent decay of the muon spin polarisation, similar to that of a purely paramagnetic system. The observed muon spin repolarisation in a moderate external longitudinal field, however, invalidates this simple picture and suggests the presence of a local anisotropy field acting on the cluster's magnetic moment. A consistent interpretation of magnetometry and muSR results implies the occurrence of an additional interaction of the cluster spin with an effective crystalline field. The inclusion of this interaction in a model Hamiltonian allows us to successfully reproduce both the susceptibility and magnetisation data. 相似文献
134.
135.
A regular polyhedron is isomorphic to a cluster on which every face has same number of bonds and every atom has an equal number of coordinating atoms. A general strategy for generating the eigenvectors and the eigenvalues of regular polyhedra is given. Not sign analyses are also performed on the eigenvectors of regular polyhedra. The results provide us a quick way to grasp the topological feature of the electronic structure of clusters having interesting topology. 相似文献
136.
The reaction of Os3(CO)10(NCMe)[Si(OMe)3](-H),1, with PMe2Ph yielded the new complex Os3(CO)10(PMe2Ph)[Si(OMe)3](-H),2 by substitution of the MeCn ligand with the phosphine ligand. When heated to 125°C compound2 was decarbonylated and transformed into the new unsaturated cluster complex Os3(CO)8[-PMe2(C6H4)][Si(OMe)3](-H)2,3 in 54% yield. Compound3 was characterized by a single crystal X-ray diffraction analysis, osmium bonds. The phenyl ring of the phosphine ligand has undergoneortho-metallation by a neighboring metal atom. A terminally coordinated Si(OMe)3 ligand is coordinated to the third osmium atom. The cluster is unsaturated by the amount of 2 electrons, and there is an open coordination site on the siloxyl substituted osmium atom that is partially filled by a weak interaction with one of the -bonds of theortho-metalled phenyl ring. Complex3 reacts with CO at 1 atm to reform compound2 in 85% yield in 5 h at 40°C. Crystal Data: for3: space group = P21/n,a = 9.911(2) Å,b = 18.451(6) Å,c = 14.872(2) Å, = 95.64(2)°,Z = 4, 1994 reflections,R = 0.028. 相似文献
137.
The polyoxo rare-earth core
(Ln = Y, Gd, and Yb) has been synthesized from the appropriate rare-earth chloride hydrate and K2Se and Se in dmf (dimethylformamide). The cluster core is ligated with a variety of polyselenido chains in addition to a number of dmf molecules. The structure of the Gd8(dmf)13(4-O)(3-OH)12(Se3)(Se4)2(Se5)2 cluster, 1, was determined by X-ray diffraction methods. It is similar to an Eu cluster previously characterized. Two new clusters, Yb8(dmf)11(4-O)(3-OH)12(Se4)2(Se5)2Cl2·dmf, 2, and Y8(dmf)12(4-O)(3-OH)12(Se4)4Cl2·6 dmf, 3, have also been synthesized and characterized. Clusters 2 and 3 have the same octanuclear core of rare-earth atoms as the Gd cluster but contain two chloro ligands in two isomeric conformations in place of the Se
3
2-
ring in the Gd cluster. The geometry of the Ln
8 core is described as a triangulated dodecahedron with 3-OH groups capping the 12 faces. A 4-O atom centers the cluster with close contacts to four Ln atoms in an approximate tetrahedral arrangement. Pertinent crystallographic data are: Compound 1, monoclinic,
, a= 14.410(3) Å, b = 24.439(5) Å, c = 28.927(6) Å, = 101.05(3)°, V = 9998(3) Å3, T = 106(2) K, Z = 4; Compound 2, orthorhombic,
, a = 17.049(9) Å, b = 24.68(1) Å, c = 45.03(2)Å, V = 18,945(16) Å3, T = 153(2) K, Z = 8; Compound 3, monoclinic, C
2h
5
-P21/c, a =18.728(l) Å, b = 29.263( 1) Å, c = 20.548(1) Å, = 90.144(1)°, V = 11,261(1) Å3, T = 153(2) K, Z = 4. 相似文献
138.
Lieve A. De Bock Boris Treiger Ludo Van der Auwera René E. Van Grieken 《Mikrochimica acta》1998,128(3-4):191-200
To reveal useful environmental information which is contained in large analytical data sets, an approach, based on the successive application of hierarchical cluster analysis and factor analysis, is proposed. Estimation criteria to determine the most suitable number of clusters and/or factors, are discussed and the interpretation of the cluster and factor analyses results is performed using visual techniques. The data sets were obtained by scanning electron microscope-energy-dispersive X-ray analysis of individual North Sea aerosol particles. 相似文献
139.
Marx T Mosel B Pantenburg I Hagen S Schulze H Wesemann L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(18):4472-4478
The tetrasubstituted polyanions of platinum, palladium, and gold [M(SnB(11)H(11))(4)](x-) (x=6, M=Pd, Pt; x=5, M=Au) have been prepared and characterized by single-crystal X-ray diffraction, elemental analysis, IR, Raman, (11)B, and (119)Sn heteronuclear NMR spectroscopy. In the case of the platinum derivative [Bu(3)MeN](6)[Pt(SnB(11)H(11))(4)] (2) (119)Sn M?ssbauer spectroscopy has been carried out. The isolated salts are stable towards moisture and air and the complexes 2 and 3 were treated with 1,3-bis(diphenylphosphino)propane (dppp) to give the respective substitution products [Bu(3)MeN](2)[(dppp)M(SnB(11)H(11))(2)] (M=Pd, Pt). 相似文献
140.
Syntheses, Structure Determination and Reactions of Phosphine Substituted Derivatives of Fe3(CO)9(μ3-CF)2 Photolysis of Fe3(CO)9(μ3-CF)2 1 in the presence of acetonitrile 2a or benzoenitrile 2b results in the substitution of a single carbonyl ligand by a nitrile ligand yielding Fe3(CO)8(CH3CN)(μ3-CF)2 3a and Fe3(CO)8(C6H5CN)(μ3-CF)2 3b, respectively. The acetonitrile ligand in 3a can be easily replaced by trimethyl-phosphine 4a or triphenylphosphine 4b . The monosubstituted compounds Fe3(CO)8(PR3)(μ3-CF)25, R = CH3 a, R = C6H5, b are obtained as major products besides a small amount of the disubsituted products Fe3(CO)7(PR3)2(μ3-CF)2 6. The structure of 5a has been elucidated by a single crystal X-ray structure determination. Thermal ligand substitution in 1, however, results in the formation of a mixture of mono-, disubstituted, and trisubstituted products, in which 6b is the major product for diphenylphosphine. 5a reacts with ethyne 7 forming a phosphine substituted diferra-allyl-cluster Fe3(CO)7(PR3)(μ3-CF)(μ3? CF? CH? CH) 8. The structure of one isomere of 8 has been determinated by X-ray crystallography. 相似文献