全文获取类型
收费全文 | 49088篇 |
免费 | 4089篇 |
国内免费 | 4873篇 |
专业分类
化学 | 10042篇 |
晶体学 | 109篇 |
力学 | 2282篇 |
综合类 | 339篇 |
数学 | 10792篇 |
物理学 | 11313篇 |
综合类 | 23173篇 |
出版年
2024年 | 144篇 |
2023年 | 422篇 |
2022年 | 817篇 |
2021年 | 953篇 |
2020年 | 1108篇 |
2019年 | 1011篇 |
2018年 | 988篇 |
2017年 | 1252篇 |
2016年 | 1448篇 |
2015年 | 1436篇 |
2014年 | 2385篇 |
2013年 | 2999篇 |
2012年 | 2655篇 |
2011年 | 3096篇 |
2010年 | 2446篇 |
2009年 | 2910篇 |
2008年 | 3056篇 |
2007年 | 3554篇 |
2006年 | 3137篇 |
2005年 | 2732篇 |
2004年 | 2346篇 |
2003年 | 2213篇 |
2002年 | 2009篇 |
2001年 | 1653篇 |
2000年 | 1540篇 |
1999年 | 1250篇 |
1998年 | 1123篇 |
1997年 | 938篇 |
1996年 | 778篇 |
1995年 | 674篇 |
1994年 | 532篇 |
1993年 | 551篇 |
1992年 | 519篇 |
1991年 | 418篇 |
1990年 | 433篇 |
1989年 | 408篇 |
1988年 | 328篇 |
1987年 | 278篇 |
1986年 | 193篇 |
1985年 | 184篇 |
1984年 | 158篇 |
1983年 | 91篇 |
1982年 | 122篇 |
1981年 | 114篇 |
1980年 | 98篇 |
1979年 | 103篇 |
1978年 | 78篇 |
1977年 | 76篇 |
1976年 | 71篇 |
1973年 | 62篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
21.
Jiatian Chen Le Yang Ying Li Qinghua Hou Lanlan Li Peng Jin 《International journal of quantum chemistry》2019,119(16):e25961
Inorganic planar ring-shape molecules with 4n + 2 π electrons are always the focus of experimental synthesis and theoretical research due to their potential aromaticity and stability. In this work, the whole series of five-membered heterocycle monoanions X nY5-n− (X, Y = group 15 elements; n = 1-4) were thoroughly investigated by means of density functional theory calculations. They all have large formation energies and HOMO-LUMO gap energies, suggesting the potential thermodynamic and kinetic stability. Their aromaticities are comparable to that of typical aromatic hydrocarbons. Their thermal stabilities were firmly established by the ab initio molecular dynamics simulations. As most of them are predicted for the first time, their various spectra were simulated for experimental characterization. Furthermore, we demonstrate that these five-membered cyclic anions can be employed as η5-ligand to construct novel all-inorganic metallocenes, which may serve as the building blocks of low-dimensional nanomaterials. 相似文献
22.
23.
Greg Orosi 《商业与工业应用随机模型》2015,31(4):515-527
In this work, we suggest a novel quadratic programming‐based algorithm to generate an arbitrage‐free call option surface. The empirical performance of the proposed method is evaluated using S&P 500 Index call options. Our results indicate that the proposed method provides a more precise fit to observed option prices than other alternative methodologies. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
24.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
25.
Umie F.M. Haziz Rosenani A. Haque Shun-Ze Zhan Hassan H. Abdallah Mohd R. Razali 《应用有机金属化学》2020,34(10):e5818
The synthesis and characterizations for a series of dinuclear gold (I)-di-NHC complexes, 1–8 through the trans-metalation method of their respective silver (I)-di-NHC complexes, i–viii are reported (where NHC = N-heterocyclic carbene). The successful complexation of a series of unusual non-symmetrical and symmetrical di-NHC ligands, 3,3'-(ethane-1,2-diyl)-1-alkylbenzimidazolium-1'-butylbenzimidazolium (with alkyl = methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, benzyl) with the gold (I) ions are suggested by elemental analysis, Fourier transform-infrared, 1H- and 13C-NMR data. The 13C-NMR spectra of 1–8 show a singlet sharp peak in the range of 190.00–192.00 ppm, indicating the presence of a carbene carbon that bonded to the gold (I) ion. From single crystal X-ray diffraction data, the structure of complex 6 with the formula of [di-NHC-Au (I)]2·2PF6 is obtained [where NHC = 3,3'-(ethane-1,2-diyl)-1-hexylbenzimidazolium-1'-butylbenzimidazolium]. The photophysical study in solid state of 6 displays an intense photoluminescence with a strong emission maxima, λem = 480 nm, upon excitation at 340 nm at room temperature. Interestingly, the emission maximum at 77 K shows a structural character with a strong peak at 410 nm, a medium at 433 nm and a weak at 387 nm, accompanied by a tail band to about 500 nm. 相似文献
26.
采用密度泛函理论B3LYP方法,研究了锡苯和铅苯的[2+2],[4+2]及[4+4]二聚反应的微观机理和势能剖面,考察了Sn(Pb)原子上的2,4,6-三甲基苯基(Mes)取代基对反应势能剖面的影响.研究结果表明,所有反应均为协同过程,且大多数情况下,2个C—Sn(Pb)键同步形成.[2+2]和[4+2]反应在热力学和动力学上均比相应的[4+4]反应容易进行,而[4+2]反应在动力学上比相应的[2+2]反应有利.Sn(Pb)原子上的Mes取代基在热力学和动力学上均不利于反应的进行.铅苯的动力学稳定性与锡苯相当,但其热力学稳定性高于锡苯. 相似文献
27.
Muhammad Usman Khan Muhammad Yasir Mehboob Riaz Hussain Zainab Afzal Muhammad Khalid Muhammad Adnan 《International journal of quantum chemistry》2020,120(22):e26377
The development of organic electron acceptor materials is one of the key factors for realizing high-performance organic solar cells (OSCs). Nonfullerene electron acceptors, compared to traditional fullerene acceptor materials, have gained much impetus owing to their better optoelectronic tunabilities and lower cost, as well as higher stability. Therefore, 5 three-dimensional (3D) cross-shaped acceptor materials having a spirobifullerene core flanked with 2,1,3-benzothiadiazole are designed from a recently synthesized highly efficient acceptor molecule SF(BR) 4 and are investigated in detail with regard to their use as acceptor molecules in OSCs. The density functional theory (DFT) and time-dependent DFT (TDDFT) calculations have been performed for the estimation of frontier molecular orbital (FMO) analysis, density of states analysis, reorganization energies of electron and hole, dipole moment, open-circuit voltage, photo-physical characteristics, and transition density matrix analysis. In addition, the structure-property relationship is studied, and the influence of end-capped acceptor modifications on photovoltaic, photo-physical, and electronic properties of newly selected molecules ( H1-H5 ) is calculated and compared with reference ( R ) acceptor molecule SF(BR) 4 . The structural tailoring at terminals was found to effectively tune the FMO band gap, energy levels, absorption spectra, open-circuit voltage, reorganization energy, and binding energy value in selected molecules H1 to H5 . The 3D cross-shaped molecules H1 to H5 suppress the intermolecular aggregation in PTB7-Th blend, which leads to high efficiency of acceptor material H1 to H5 in OSCs. Consequently, better optoelectronic properties are achieved from designed molecules H1 to H5 . It is proposed that the conceptualized molecules are superior than highly efficient spirobifullerene core-based SF(BR) 4 acceptor molecules and, thus, are recommended to experiments for future developments of highly efficient solar cells. 相似文献
28.
29.
自然事物的情感表现性产生于人类与大自然事物生命情调上的相似,自然事物的形式美因素以及人类情感形式与自然物在“力的图式”上同形同构。 相似文献
30.
基于模糊控制的公路隧道通风控制系统 总被引:6,自引:0,他引:6
提出了一种新型的基于模糊控制的公路隧道通风控制系统,将CO浓度值和烟雾浓度值作为系统输入,风机数值作为系统输出。仿真结果显示,这种模糊通风控制系统用在隧道通风控制系统中可以缓解传统的分级式控制的风机频繁启停的问题。 相似文献