全文获取类型
收费全文 | 458篇 |
免费 | 7篇 |
国内免费 | 1篇 |
专业分类
化学 | 281篇 |
晶体学 | 7篇 |
力学 | 2篇 |
数学 | 15篇 |
物理学 | 161篇 |
出版年
2023年 | 3篇 |
2021年 | 2篇 |
2020年 | 7篇 |
2019年 | 7篇 |
2018年 | 8篇 |
2017年 | 4篇 |
2016年 | 5篇 |
2015年 | 9篇 |
2014年 | 8篇 |
2013年 | 23篇 |
2012年 | 17篇 |
2011年 | 23篇 |
2010年 | 15篇 |
2009年 | 25篇 |
2008年 | 27篇 |
2007年 | 31篇 |
2006年 | 20篇 |
2005年 | 27篇 |
2004年 | 9篇 |
2003年 | 20篇 |
2002年 | 17篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 10篇 |
1998年 | 2篇 |
1997年 | 13篇 |
1996年 | 4篇 |
1995年 | 3篇 |
1994年 | 8篇 |
1993年 | 2篇 |
1992年 | 14篇 |
1991年 | 9篇 |
1990年 | 2篇 |
1989年 | 6篇 |
1988年 | 6篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 8篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 6篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1973年 | 1篇 |
1966年 | 1篇 |
1937年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有466条查询结果,搜索用时 218 毫秒
41.
42.
43.
44.
Kenkichiro Kobayashi Masasuke Takata Shoichi Okamoto Mitsunori Sukigara 《Journal of Electroanalytical Chemistry》1985,185(1):47-60
The ac impedance theory at a semiconductor—liquid junction indicates that the addition of redox couples to an electrolyte solution makes it impossible to determine properties of the surface states from capacitance and conductance measurements. In particular, the surface-state capacitance disappears when the electron exchange between the surface states and redox couples is dominant compared with the electron exchange between the surface states and the conduction band. 相似文献
45.
Kaoru Toyoda 《International journal of quantum chemistry》1988,34(6):489-503
Here is presented a method to determine the consistent ground state (CGS ) which satisfies the so-called killer condition for the excitation operator. This method may be called an extended application of the procedure employed by Weiner and Goscinski in deriving the random phase approximation (RPA ) vacuum. The RPA vacuum is derived by solving the recurrence formula of the configuration coefficients of a multiconfigurational state vector. The role of boson approximation to the primitive p-h excitation operator is also investigated and by using the present formalism the cluster-expansion-type CGS is derived as the RPA vacuum under the boson approximation. Inclusion of the effects of a higher RPA in the CGS leads to the simultaneous equations of the configuration coefficients of the CGS . In including the effect of the second RPA , only the symmetry-broken CGS can exist. When the third RPA effect is involved instead of the second RPA , there can be a symmetry-adapted CGS , in which the picture of electron pairs acquired in the standard RPA vacuum is modified. Thus the exact CGS vectors are analytically obtained in the case of simple model systems of two or four electrons. 相似文献
46.
47.
48.
A convenient synthesis of 1,4-benzodiazepines starting from secondary-2-aminobenzhydrols, which are easily obtained from secondary anilines and benzaldehydes, is described. 7-Nitro-1-methyl-1,4-benzodiazepine 1d can be formed from 5-nitro-2-methylaminomethylacylaminobenzo-phenone 10b and c by using ammonium carbonate instead of ammonia, which gives only the Smiles-rearranged product 11 . 相似文献
49.
Kumondai K Toyoda M Ishihara M Katakuse I Takeuchi T Ikeda M Iwamoto K 《The Journal of chemical physics》2005,123(2):24314
The reaction mechanisms of silver trimer cation, Ag3+, with 12-crown-4 (12C4) were studied experimentally and theoretically. Using a cylindrical ion trap time-of-flight mass spectrometer, gas-phase ion/molecule reactions of Ag3+ with 12C4 were observed. Metal-ligand complexes of [Ag(12C4)]+, [Ag3(12C4)]+ and [Ag3(12C4)2]+, and of [Ag(12C4)2]+ and [Ag3(12C4)3]+, were observed as the reaction intermediates and terminal products, respectively. The formations of the [Ag12C4]+ and [Ag(12C4)2]+ complexes indicated that the neutral dimer (Ag2) had been eliminated from the trimer cation. From the results of ab initio calculations at the HF/LanL2DZ level of theory and the experiments, it is suggested that three 12C4 molecules can attach to Ag3+ through consecutive reactions and that neutral Ag2 can be easily eliminated from [Ag3(12C4)]+. 相似文献
50.
Umebayashi Y Mroz B Asada M Fujii K Matsumoto K Mune Y Probst M Ishiguro S 《The journal of physical chemistry. A》2005,109(21):4862-4868
Solvation structure of the zinc(II) ion in N,N-dimethylpropionamide (DMPA) was studied by Raman spectroscopy at varying temperature and by quantum mechanical calculations. No significant ion-pair formation was found for the Zn(ClO4)2 solution in the molality range m(Zn) < 1.5 mol kg(-1), and the solvation number of the zinc(II) ion was determined to be 4, indicating that 6-coordination of DMPA is sterically hindered. Interestingly, DMPA molecules are under equilibrium between planar cis and nonplanar staggered conformers, and the latter is more preferred in the coordination sphere, while the reverse is the case in the bulk. The DeltaG degrees , DeltaH degrees , and TDeltaS degrees values of conformational change from planar cis to nonplanar staggered in the coordination sphere were obtained to be -0.9, -8.5, and -7.5 kJ mol(-1), respectively. Density functional theory (DFT) calculations show that the planar cis conformer is more favorable than the nonplanar staggered one in the 1:2 cluster, as is the case for a single DMPA molecule and H(DMPA)+, indicating that there hardly occurs solvent-solvent interaction through the metal ion in the Zn2+-DMPA 1:2 cluster. On the other hand, the SCF energy of [Zn(planar cis-DMPA)4-n(nonplanar staggered DMPA)n]2+ (n = 0-4) decreases with increasing n, implying that the nonplanar staggered conformer is preferred in the solvate ion. It is thus concluded that solvent-solvent interaction through space, or solvation steric effect, plays a crucial role in the conformational equilibrium in the coordination sphere of the four-solvate metal ion. 相似文献