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排序方式: 共有354条查询结果,搜索用时 125 毫秒
61.
62.
Xiao‐Ping Wang Panagiotis Angaridis Carlos A. Murillo F. Albert Cotton 《Acta Crystallographica. Section C, Structural Chemistry》2005,61(2):m109-m111
The title compound, [Ru2(C2H3O2)4(C15H16N2O2)2], lies on a crystallographic inversion center and exhibits an Ru—Ru bond length of 2.2847 (8) Å. There are weak intramolecular hydrogen‐bonding interactions between the N1,N2‐di‐p‐anisylformamidine (HDAniF) ligands and the bridging acetate ligands. The molecule is one of the few examples of a crystallographically characterized axial bis‐adduct of a {Ru2}4+ complex with two N‐donor ligands. 相似文献
63.
Carlos A. Murillo Prof. 《Angewandte Chemie (International ed. in English)》2009,48(28):5076-5077
Full metal bonding : The reduction of a six‐coordinate, mononuclear Werner‐type iron(II) complex (see scheme) resulted in the isolation of a compound with an extraordinarily rare, unsupported Fe–Fe bond having an experimental Fe–Fe distance of 2.6869(6) Å and a calculated bond order of 0.5.
64.
Cotton FA Donahue JP Gruhn NE Lichtenberger DL Murillo CA Timmons DJ Van Dorn LO Villagrán D Wang X 《Inorganic chemistry》2006,45(1):201-213
A far superior synthesis is reported for W(2)(hpp)(4)Cl(2), a key intermediate in the synthesis of the most easily ionized closed-shell molecule W(2)(hpp)(4) (hpp = the anion of the bicyclic guanidine compound 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidine). At 200 degrees C, the one-pot reaction of the air-stable and commercially available compounds W(CO)(6) and Hhpp in o-dichlorobenzene produces W(2)(hpp)(4)Cl(2) in multigram quantities with isolated yields of over 90%. At lower temperatures, the reaction can lead to other compounds such as W(Hhpp)(2)(CO)(4) or W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2), which are isolable in good purity depending upon the specific conditions employed. These compounds provide insight into the reaction pathway to W(2)(hpp)(4)Cl(2) and W(2)(hpp)(4). Two additional derivatives, W(2)(hpp)(4)X(2) where X is PF(6)(-) or the anion tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB), have also been synthesized and structurally characterized. A comparison of the electrode potentials of W(2)(mu-CO)(2)(mu-hpp)(2)(eta(2)-hpp)(2) and the di-p-anisylformamidinate analogue shows that oxidation of the hpp compound is significantly displaced (1.12 V) and shows that the bicyclic guanidinate ligand is considerably better than the formamidinate anion at stabilizing high oxidation states. A differential pulse voltammogram of W(2)(hpp)(4)(TFPB)(2) in THF shows two reduction processes with an E(1/2) of -0.97 V for the first and -1.81 V (vs Ag/AgCl) for the second. DFT calculations on the W(2)(hpp)(4)(2+) units in W(2)(hpp)(4)X(2) compounds show that the metal-metal bonding orbitals are destabilized by the axial ligands, which accounts for significant variations in the W-W distances. The low-energy gas-phase ionizations of W(2)(hpp)(4) are also reported and discussed. 相似文献
65.
Tetranuclear Mo4 clusters with two quadruply bonded Mo2(4+) units, [Mo2(cis-DAniF)2] (DAniF = N,N'-di-p-anisylformamidinate), linked by alkoxides (OCH3 for 1 and OC2H5 for 4) have been prepared. The nonbonding separation between the midpoints of the quadruply bonded units, ca. 3.24 A, is the shortest among compounds having two linked Mo2(4+) units. Electrochemical measurements show two redox waves for each compound with large DeltaE(1/2) values (554 and 587 mV for 1 and 4, respectively) that correspond to K(C) values on the order of 10(9). The large electronic communication is attributed to the short separation between dinuclear units that favor direct delta-to-delta orbital interactions between the two dimetal centers. Compound 1 was chemically oxidized using stoichiometric amounts of ferrocenium salts to a one-electron oxidation product 2 (in which the counteranion is PF6-) and a two-electron oxidation product 3 (which contains two BF4- anions). Upon oxidation there are significant decreases in the distance between the two [Mo2] units to 3.100 A and then to 2.945 A. The mixed-valence species 2 shows two broad absorption bands at 5900 and 7900 cm(-1) in the NIR region which are assigned to the HOMO-1 --> SOMO and HOMO-2 --> SOMO transitions. Compound 3 is fluxional in solution, as shown by variable-temperature 1H NMR spectra. The sharp signals in the NMR spectrum at -50 degrees C and the lack of an EPR signal suggest that this species is diamagnetic and that a four-center, two-electron bond is formed in the cyclometallic Mo4 cluster. To a first-order approximation, an average bond order of 0.25 is assigned to the bonding interaction between the two Mo atoms along the long edges of the rectangle defined by the four Mo atoms. 相似文献
66.
García F Moreno E Solano J Barragán M Sotomayor A Fuentes M Acevedo P 《Ultrasonics》2006,44(Z1):e307-e312
This paper describes the design of a continuous wave blood flow bi-directional Doppler system based on an open, high-resolution architecture that is portable and low cost. The system incorporates the advantages of expensive systems with dedicated hardware. The system is composed of a flow detector probe, a signal conditioning stage, a direction detection module, a signal processing stage and a graphic user interface. The direction detection of the signal is achieved using a fast digital phasing filter. The Doppler signal is processed using a short-time Fourier transform-based algorithm. This is commonly used as a reference. Nevertheless, the system allows us to incorporate alternative high-resolution spectral estimation methods that might offer more precise information to the specialist. 相似文献
67.
Peter Grassl David Grégoire Laura Rojas Solano Gilles Pijaudier-Cabot 《International Journal of Solids and Structures》2012,49(13):1818-1827
The size effect on the fracture process zone in notched and unnotched three point bending tests of concrete beams is analysed by a meso-scale approach. Concrete is modelled at the meso-scale as stiff aggregates embedded in a soft matrix separated by weak interfaces. The mechanical response of the three phases is modelled by a discrete lattice approach. The model parameters were chosen so that the global model response in the form of load-crack mouth opening displacement curves were in agreement with experimental results reported in the literature. The fracture process zone of concrete is determined numerically by evaluating the average of spatial distribution of dissipated energy densities of random meso-scale analyses. The influence of size and boundary conditions on the fracture process zone in concrete is investigated by comparing the results for beams of different sizes and boundary conditions. 相似文献
68.
PM De Biase CJ Solano S Markosyan L Czapla SY Noskov 《Journal of chemical theory and computation》2012,8(7):2540-2551
A theoretical framework is presented to model ion and DNA translocation across a nanopore confinement under an applied electric field. A combined Grand Canonical Monte Carlo Brownian Dynamics (GCMC/BD) algorithm offers a general approach to study ion permeation through wide molecular pores with a direct account of ion-ion and ion-DNA correlations. This work extends previously developed theory by incorporating the recently developed coarse-grain polymer model of DNA by de Pablo and colleagues [Knotts, T. A.; Rathore, N.; Schwartz, D. C.; de Pablo, J. J. J. Chem. Phys. 2007, 126] with explicit ions for simulations of polymer dynamics. Atomistic MD simulations were used to guide model developments. The power of the developed scheme is illustrated with studies of single-stranded DNA (ss-DNA) oligomer translocation in two model cases: a cylindrical pore with a varying radius and a well-studied experimental system, the staphylococcal α-hemolysin channel. The developed model shows good agreement with experimental data for model studies of two homopolymers: ss-poly(dA)(n) and ss-poly(dC)(n). The developed protocol allows for direct evaluation of different factors (charge distribution and pore shape and size) controlling DNA translocation in a variety of nanopores. 相似文献
69.
We present a method to implement ultrafast two-qubit gates valid for the ultrastrong coupling and deep strong coupling regimes of light-matter interaction, considering state-of-the-art circuit quantum electrodynamics technology. Our proposal includes a suitable qubit architecture and is based on a four-step sequential displacement of the intracavity field, operating at a time proportional to the inverse of the resonator frequency. Through ab?initio calculations, we show that these quantum gates can be performed at subnanosecond time scales while keeping a fidelity above 99%. 相似文献
70.
M. Morales-Hernandez P. García-Navarro J. Murillo 《Journal of computational physics》2012,231(19):6532-6557
It is possible to relax the Courant–Friedrichs–Lewy condition over the time step when using explicit schemes. This method, proposed by Leveque, provides accurate and correct solutions of non-sonic shocks. Rarefactions need some adjustments which are explored in the present work with scalar equation and systems of equations. The non-conservative terms that appear in systems of conservation laws introduce an extra difficulty in practical application. The way to deal with source terms is incorporated into the proposed procedure. The boundary treatment is analysed and a reflection wave technique is considered. In presence of strong discontinuities or important source terms, a strategy is proposed to control the stability of the method allowing the largest time step possible. The performance of the above scheme is evaluated to solve the homogeneous shallow water equations and the shallow water equations with source terms. 相似文献