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41.
Kinetics of radical‐molecule reactions in aqueous solution: A benchmark study of the performance of density functional methods 下载免费PDF全文
The performance of 18 density functional approximations has been tested for a very challenging task, the calculations of rate constants for radical‐molecule reactions in aqueous solution. Despite of the many difficulties involved in such an enterprise, six of them provide high quality results, and are recommended to that purpose. They are LC‐ωPBE, M06‐2X, BMK, B2PLYP, M05‐2X, and MN12SX, in that order. This trend was obtained using experimental data as reference. The other relevant aspects used in this benchmark are: (i) the SMD model for mimicking the solvent; (ii) the conventional transition state, the zero‐curvature tunneling correction, and the limit imposed by diffusion for the calculation of the rate constants. Even though changing any of these aspects might alter the trend in performance, at least, when using them, the aforementioned functionals can be successfully used to obtain high quality kinetic data for the kind of reactions investigated in this work. © 2014 Wiley Periodicals, Inc. 相似文献
42.
Kazuaki Z. Takahashi 《Journal of computational chemistry》2014,35(11):865-875
In our previous study (Takahashi et al., J. Chem. Theory Comput. 2012, 8, 4503), we developed the linear‐combination‐based isotropic periodic sum (LIPS) method. The LIPS method is based on the extended isotropic periodic sum theory that produces a ubiquitous interaction potential function to estimate homogeneous and heterogeneous systems. The LIPS theory also provides the procedure to design a periodic reaction field. To demonstrate this, in the present work, a novel reaction field of the LIPS method was developed. The novel reaction field was labeled LIPS‐SW, because it provides an interaction potential function with a shape that resembles that of the switch function method. To evaluate the ability of the LIPS‐SW method to describe in homogeneous and heterogeneous systems, we carried out molecular dynamics (MD) simulations of bulk water and water–vapor interfacial systems using the LIPS‐SW method. The results of these simulations show that the LIPS‐SW method gives higher accuracy than the conventional interaction potential function of the LIPS method. The accuracy of simulating water–vapor interfacial systems was greatly improved, while that of bulk water systems was maintained using the LIPS‐SW method. We conclude that the LIPS‐SW method shows great potential for high‐accuracy, high‐performance computing to allow large scale MD simulations. © 2014 Wiley Periodicals, Inc. 相似文献
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Dr. Kirill V. Kovtunov Dr. Milton L. Truong Danila A. Barskiy Prof. Igor V. Koptyug Dr. Aaron M. Coffey Prof. Kevin W. Waddell Prof. Eduard Y. Chekmenev 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14629-14632
Parahydrogen induced polarization was employed to prepare a relatively long‐lived correlated nuclear spin state between methylene and methyl protons in propane gas. Conventionally, such states are converted into a strong NMR signal enhancement by transferring the reaction product to a high magnetic field in an adiabatic longitudinal transport after dissociation engenders net alignment (ALTADENA) experiment. However, the relaxation time T1 of ~0.6 s of the resulting hyperpolarized propane is too short for potential biomedical applications. The presented alternative approach employs low‐field MRI to preserve the initial correlated state with a much longer decay time TLLSS=(4.7±0.5) s. While the direct detection at low‐magnetic fields (e.g. 0.0475 T) is challenging, we demonstrate here that spin‐lock induced crossing (SLIC) at this low magnetic field transforms the long‐lived correlated state into an observable nuclear magnetization suitable for MRI with sub‐millimeter and sub‐second spatial and temporal resolution, respectively. Propane is a non‐toxic gas, and therefore, these results potentially enable low‐cost high‐resolution high‐speed MRI of gases for functional imaging of lungs and other applications. 相似文献
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Xianghua Zhang Haoliang Chen Weiling Liu Ni Xiao Qi Zhang Xianhong Rui Shaoming Huang 《化学:亚洲杂志》2020,15(9):1430-1435
Aqueous zinc‐ion batteries (ZIBs) have become the highest potential energy storage system for large‐scale applications owing to the high specific capacity, good safety and low cost. In this work, a NASICON‐type Na3V2(PO4)3 cathode modified by a uniform carbon layer (NVP/C) has been synthesized via a facile solid‐state method and exhibited significantly improved electrochemical performance when working in an aqueous ZIB. Specifically, the NVP/C cathode shows an excellent rate capacity (e. g., 48 mAh g?1 at 1.0 A g?1). Good cycle stability is also achieved (e. g., showing a capacity retention of 88% after 2000 cycles at 1.0 A g?1). Furthermore, the Zn2+ (de)intercalation mechanism in the NVP cathode has been determined by various ex‐situ techniques. In addition, a Zn||NVP/C pouch cell has been assembled, delivering a high capacity of 89 mAhg?1 at 0.2 A g?1 and exhibiting a superior long cycling stability. 相似文献
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利用长光程比色池 流动注射系统快速测定水样中的微量挥发酚.该方法的检出限为0.232 μg·L-1,相对标准偏差小于0.553%,相对误差小于0.185%,样品加标回收率在91.0%~99.8%,且标准曲线具有良好线性(r =0.999 9).与传统国标方法(《水质挥发酚的测定4-氨基安替比林分光光度法》,HJ503-2009)相比,样品浓度测定偏差为2.59%~8.25%,在分析速率上,传统的国标方法约为5个·h-1,而该方法分析速率达24个·h-1,能满足大批量样品连续准确测定的要求,特别适合事故性的应急监测. 相似文献
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This study focuses on the full-form model-free adaptive controller (FFMFAC) for SISO discrete-time nonlinear systems, and proposes enhanced FFMFAC. The proposed technique design incorporates long short-term memory neural networks (LSTMs) and fuzzy neural networks (FNNs). To be more precise, LSTMs are utilized to adjust vital parameters of the FFMFAC online. Additionally, due to the high nonlinear approximation capabilities of FNNs, pseudo gradient (PG) values of the controller are estimated online. EFFMFAC is characterized by utilizing the measured I/O data for the online training of all introduced neural networks and does not involve offline training and specific models of the controlled system. Finally, the rationality and superiority are verified by two simulations and a supporting ablation analysis. Five individual performance indices are given, and the experimental findings show that EFFMFAC outperforms all other methods. Especially compared with the FFMFAC, EFFMFAC reduces the by 21.69% and 11.21%, respectively, proving it to be applicable for SISO discrete-time nonlinear systems. 相似文献
49.
用高温固相法合成了红色长余辉发光材料LiAl5O8:Mn4+,Li5AlO4:Mn4+,LiAlO2:Mn4+,发现前两种材料有红色余辉,这方面并没有报道过,并对这两种材料的发光性能作了研究,指明了不同基质中发光强弱不同原因。对不同Mn4+掺杂浓度的材料做了浓度依赖关系研究,确认Mn4+的发光是2E→4A2的跃迁。Mn4+的发光是个宽带谱,材料在紫外区有强的吸收,发射谱范围可达620~770nm,峰值在675nm。对长余辉机制进行了探讨。 相似文献
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