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最小一乘稳健多元分析校正 总被引:1,自引:3,他引:1
本文论述最小一乘求解的多元分析校正算法,探讨了最小一乘较常规最小二乘法及其他隐健算法的优点。用计算机数值模拟及实际多组分光谱体系对方法进行了检验,展示了最小一乘法在分析化学计量学中实际应用的可行性。 相似文献
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Ohsuna T Slater B Gao F Yu J Sakamoto Y Zhu G Terasaki O Vaughan DE Qiu S Catlow CR 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(20):5031-5040
High-resolution electron microscopy (HREM) has been used to image the surface structure of nano- and micrometer-sized synthetic crystals of zeolite-Linde-L (LTL). Columnar holes and rotational, nano-sized, wheel-like defects were observed within the crystals, where the hole has a minimum size equal to that of the rotational defect. Predictions of surface structure from atomistic computer simulation concur with the observations from HREM and provide insight into the crystal growth mechanism of perfect and defective LTL. Analysis of the energetics of the formation of rotational defect structures reveals that the driving force for defect creation is thermodynamic and furthermore, the rotational defects could be created in high concentrations. Formation of a columnar hole is found to be slightly energetically unfavourable and therefore we speculate that the incidence of both rotational and nano-sized vacancy defects is strongly dependent on kinetic factors and reaction conditions. The morphology of nano- and microcrystalline LTL is contradistinct and we use insights from simulation to propose an explanation of the disparity in crystal shape. 相似文献
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The Sixth-Generation (6G) standard for wireless communications is expected to realize ubiquitous coverage for massive Internet of Things (IoT) networks by 2030. Satellite-based communications are recognized as a highly promising technical enabler to satisfy IoT service requirements in the 6G era. This study analyzes multiple access technologies, which are essential for the effective deployment of satellite-based IoT. First, we thoroughly investigate the existing research related to massive access, including information-theory considerations as well as Non-Orthogonal Multiple Access (NOMA) and Random Access (RA) technologies.Then, we explore the influence of the satellite transmission environment on multiple access technologies. Based on this study, a Non-orthogonal Massive Grant-Free Access (NoMaGFA) scheme, which reaps the joint benefits of RA and NOMA, is proposed for asynchronous transmissions in satellite-based IoT to achieve improved system throughput and enhance the system robustness under varying traffics. Finally, we identify some important and interesting future developments for satellite-based IoT, including waveform design, transceiver design, resource allocation, and artificial intelligence-enhanced design. 相似文献
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Using ethylenediamine as a template, two one-dimensional (1-D) aluminophosphate compounds [AlP(2)O(8)H][NH(3)CH(2)CH(2)NH(3)] (1) and [AlP(2)O(8)][NH(3)CH(2)CH(2)NH(3)][NH(4)] (2) have been prepared from a gel system: 1.0:x:y:44 Al(i-PrO)(3)-H(3)PO(4)-en-EG (x = 3.0-9.0, y = 1.0-11.0). Compound 1 consists of edge-sharing four-membered ring (MR) chains, denoted as AlPO-ESC, and compound 2 consists of corner-sharing 4-MR chains, denoted as AlPO-CSC. The molar ratio of en:H(3)PO(4) in the starting gel has an important influence on the final product. If en:H(3)PO(4) > or = 1, AlPO-CSC is obtained, while if en:H(3)PO(4) < 1, AlPO-ESC is formed. These two chains can transform to each other upon addition of some extra amount of en or H(3)PO(4) to the reaction mixture in which AlPO-ESC or AlPO-CSC is crystallized. On the basis of XRD and (27)Al and (31)P MAS NMR analyses, a possible chain-to-chain transformation mechanism is proposed. The corner-sharing 4-MR chains of AlPO-CSC, as well as the edge-sharing 4-MR chains of AlPO-ESC can be assembled to 3-D open-framework compound NiAlP(2)O(8).C(2)N(2)H(9) through Ni(2+) cations. It is noted that AlPO-CSC remains in the structure of NiAlP(2)O(8).C(2)N(2)H(9). It is believed that AlPO-ESC might be first transformed to AlPO-CSC followed by the assembly to 3-D open-framework of NiAlP(2)O(8).C(2)N(2)H(9) through Ni(2+) cations. 相似文献
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The photodissociation dynamics of nitromethane (CH(3)NO(2)) starting at the S(3) excited state has been studied at the complete active space self-consistent field level of theory in conjunction with atomic natural orbital type basis sets. In addition, the energies of all the critical points and the energy profiles connecting them have been recomputed with the multiconfigurational second-order perturbation method. It is found that the key step in the reaction mechanism is a radiationless decay through an S(3)S(2) conical intersection. The branching space spanned by the gradient difference and nonadiabatic coupling vectors of this crossing point comprises dissociation into excited nitromethane plus singlet atomic oxygen [CH(3)NO(1A")+O((1)D)] and S(3)-->S(2) deactivation, respectively. Furthermore, deactivated nitromethane S(n (n<3)) can decompose in subsequent steps into CH(3)+NO(2), where NO(2) is generated at least in two different electronic states (1 (2)B(2) and 1 (2)A(1)). It is shown that formation of excited nitric oxide NO(A (2)Sigma) arises from CH(3)NO(1A") generated in the previous step. In addition, four crossings between singlet and triplet states are localized; however, no evidence is found for a relevant role of such crossings in the photochemistry of CH(3)NO(2) initiated at S(3) state in the gas phase. 相似文献
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Systematic Study of Ti‐Distribution in Titanosilicate *BEA Zeolites via Symmetry‐Adapted Enumeration
The high performance of titanosilicate zeolites in various industrial oxidation reactions is highly affected by the distribution of Ti atoms in their frameworks. Because of their structural complexity, previous theoretical studies mainly focus on the preferential location of single Ti atoms within the unit cells of titanosilicate zeolites. When multiple Ti atoms are required, conventional approaches consider only symmetrically related T sites to reduce the computation complexity. Such symmetry‐constrained approaches obviously overlooked many possible configurations. Herein, we conduct a systematic study on the distribution of two Ti atoms in the unit cell of titanosilicate zeolite *BEA . Different from conventional symmetry‐constrained approaches, we introduce two Ti atoms simultaneously without any constraint and adopt a symmetry‐adapted algorithm to enumerate all possible configurations for double‐Ti introduction. We generate a total of 273 distinct configurations and analyze the Ti‐distribution via Boltzmann statistics. We find that many of the configurations overlooked by conventional symmetry‐constrained approaches indeed exhibit more feasible energies, which may lead to different Ti‐distributions. Our study indicates the necessity of unconstrained introduction of Ti atoms when multiple‐Ti atoms are considered for calculations. 相似文献
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The structure elucidation of a new zinc phosphate [Co(II)(en)(3)][Zn(4)(H(2)PO(4))(3)(HPO(4))(2)(PO(4))(2 H(2)O)(2)] (1) reveals that the racemic cobalt complex templates the zinc phosphate framework in such a way that the local C(2) point symmetry of the structural motif of the inorganic framework conforms with that of the cobalt complex pairing with it, in essence transferring its chirality to the inorganic host. An analysis of hydrogen bonding between the guest molecules and the inorganic host framework reveals that hydrogen bonding is responsible for the stereospecific structural arrangement. Upon examining previously reported chiral metal-complex-templated structures of metal phosphates, it is revealed that such hydrogen bonding is the common origin for inducing chirality transfer in metal-phosphate frameworks templated with chiral metal complexes. Crystal data of 1: orthorhombic, Pbcn (no. 60), a=10.4787(8) A, b=20.0091(14) A, c=14.9594(10) A, and Z=2. 相似文献