全文获取类型
收费全文 | 1820篇 |
免费 | 29篇 |
国内免费 | 313篇 |
专业分类
化学 | 1506篇 |
晶体学 | 9篇 |
数学 | 1篇 |
物理学 | 646篇 |
出版年
2023年 | 12篇 |
2022年 | 15篇 |
2021年 | 4篇 |
2020年 | 13篇 |
2019年 | 16篇 |
2018年 | 19篇 |
2017年 | 9篇 |
2016年 | 38篇 |
2015年 | 43篇 |
2014年 | 54篇 |
2013年 | 89篇 |
2012年 | 73篇 |
2011年 | 104篇 |
2010年 | 91篇 |
2009年 | 117篇 |
2008年 | 143篇 |
2007年 | 137篇 |
2006年 | 148篇 |
2005年 | 105篇 |
2004年 | 98篇 |
2003年 | 128篇 |
2002年 | 97篇 |
2001年 | 93篇 |
2000年 | 118篇 |
1999年 | 96篇 |
1998年 | 96篇 |
1997年 | 45篇 |
1996年 | 41篇 |
1995年 | 21篇 |
1994年 | 21篇 |
1993年 | 6篇 |
1992年 | 9篇 |
1991年 | 17篇 |
1990年 | 6篇 |
1989年 | 9篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 2篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 5篇 |
1980年 | 1篇 |
1978年 | 1篇 |
1973年 | 2篇 |
排序方式: 共有2162条查询结果,搜索用时 15 毫秒
71.
《Journal of fluorine chemistry》2002,113(2):147-154
Equilibrium structures of isolated fluorolithiomethanes (1-3), chlorofluorolithiomethanes (4-6), bromofluorolithiomethanes (7-9), and bromochlorofluorolithiomethane (10) have been calculated at the HF/6-31+G(d,p) and MP2/6-31+G(d,p) levels. Depending on the number of halogens and the computational method employed, five distinct minimum structures could be recognized, viz. normal tetrahedral without coordination of halogen (T), trigonal bidentate with coordination of carbon and halogen to lithium (BCX), tetrahedral tridentate with coordination of carbon and two halogens to lithium (TCX2), quadrilateral bidentate with coordination of two halogens to lithium (BX2), and bipyramidal tridentate with coordination of three halogens to lithium (TX3). 相似文献
72.
73.
74.
K. Laihia A. Valkonen E. Kolehmainen R. Suontamo M. Nissinen V. Nikiforov S. Selivanov 《Journal of Molecular Structure》2005,754(1-3):77-84
The 1H and 13C NMR chemical shifts for six toxaphene congeners: 2-exo,3-endo,6-exo,8,9,10-hexachloro- (1), 2-exo,3-endo,5-exo,9,9,10,10-heptachloro- (2), 2-exo,3-endo,6-exo,8,9,10,10-heptachloro- (3), 2-exo,3-endo,5-exo,6-endo,8,9,10-heptachloro- (4), 2-exo,3-endo,5-exo,6-endo,8,9,9,10-octachlorobornane (5) and 2,5-endo,6-exo,8,9,9,10,10-octachloro-2-bornene (6) are reported. Their chemical shift assignments have been obtained by means of Pulsed Field Gradient (PFG) Double Quantum Filtered (DQF) 1H,1H correlation spectroscopy (COSY), PFG 1H,13C Heteronuclear Multiple Quantum Coherence (HMQC) and PFG 1H,13C Heteronuclear Multiple Bond Correlation (HMBC) experiments. A single crystal X-ray structural analysis was made for compounds 1, 3, 4 and 6. The prevalences of two octachlorobornene rotamers (6a,6b) were elucidated by ab initio MO method and single point DFT/GIAO calculations for 13C chemical shifts. Theoretical calculations proved that the single crystal structure of 6 corresponds its most stable conformer in solution. 相似文献
75.
Ab initio gradient calculations were performed on BF3 and BCl3 to evaluate the -contribution in these compounds. The influence of the basis set on the results is studied for borontrifluoride. For the chlorine compound the -contribution is smaller than for the fluorine compound. 相似文献
76.
Several Li+- and Na+-acetonitrile models were derived from ab initio calculations at the counterpoise-corrected MP2/TZV++(d,p) level for distorted ion-(MeCN)n clusters with n=1, 4 and 6. Two different many-body ion-acetonitrile models were constructed: an effective three-body potential for use with the six-site effective pair model of Böhm et al., and an effective polarizable many-body model. The polarizable acetonitrile model used in the latter model is a new empirical model which was also derived in the present paper. Mainly for comparative purposes, two ion-acetonitrile pair potentials were also constructed from the ab initio cluster calculations: one pure pair potential and one effective pair potential. Using all these potential models, MD simulations in the NPT ensemble were performed for the pure acetonitrile liquid and for Li+(MeCN) and Na+(MeCN) solutions with 1 ion in 512 solvent molecules and with a simulation time of at least 120 ps per system. Thermodynamic properties, solvation-shell structure and the self-diffusion coefficient of the ions and of the solvent molecules were calculated and compared between the different models and with experimental data, where available. The Li+ ion is found to be four-coordinated when the new many-body potentials are used, in contrast to the six-coordinated structure obtained for the pure pair and effective pair potentials. The coordination number of Na+ is close to six for all the models derived here, although the coordination number becomes slightly smaller with the many-body potentials. For both ions, the solvent molecules in the first shell point their nitrogen ends towards the cation, while in the second shell the opposite orientation is the most common. 相似文献
77.
Structures of the phenol-imine and quinoid tautomers of the titled ligand have been obtained from the ab initio and hybrid density functional methods. The phenol-imine tautomer having bifurcated NH hydrogen bonds (1.799 and 1.833 Å), has been predicted to be 14.9 kJ mol−1 more stable than the quinoid tautomer wherein OH hydrogen bonded interactions are present. Charge distributions in these tautomers have been calculated using the molecular electrostatic potential as a tool. Consequences of hydrogen bonding to the vibrational spectra are discussed. 相似文献
78.
Ralph Haist Hans-Georg Mack Alfred Waterfeld Gary L. Gard Heinz Oberhammer 《Journal of Molecular Structure》1996,380(3):213-222
The geometric structures and conformational properties of trifluoromethanesulfonic anhydride, (CF3SO2)2O, and bis(trifluoromethylsulfonyl)difluoromethane, (CF3SO2)2CF2 have been studied by gas electron diffraction (GED) and ab initio calculations (HF/3–21G*). The calculations predict for both systems two stable conformers with C2 symmetry and one with C1 symmetry. In both compounds structures with C2 symmetry and dihedral angles SOSC ≈ 100° ((CF3SO2)2O) and SCSC≈ 150° ((CF3SO2)2CF2 are lowest in energy. According to the GED analyses the dominant conformer of (CF3SO2)2O2 possesses C2 symmetry with SOSC dihedral angles of 99.1(14)°. The presence of up to 30% of the two other conformers cannot be excluded; for (CF3SO2)2CF2 only one conformer with C2 symmetry and SCSC dihedral angles of 143(2)° is observed. A complete set of geometric parameters is given. 相似文献
79.
80.
硝酸甲酯分子间相互作用的DFT和ab initio比较 总被引:5,自引:0,他引:5
用密度泛函理论(DFT)和从头算(ab initio)方法,分别在B3LYP/6 31G和HF/6 31G水平上求得硝酸甲酯三种二聚体的全优化几何构型和电子结构,并用6 311G和6 311++G基组进行总能量计算.对HF/6 31G计算结果进行MP4SDTQ电子相关校正.在各基组下均进行基组叠加误差(BSSE)和零点能(ZPE)校正求得结合能.对6 31G优化构型作振动分析并基于统计热力学求得200~600 K温度下单体和二聚体的热力学性质.详细比较两种方法的相应计算结果,发现DFT求得的分子间距离较短,分子内键长较长,所得结合能均小于相应ab initio计算值. 相似文献