全文获取类型
收费全文 | 147134篇 |
免费 | 11521篇 |
国内免费 | 8416篇 |
专业分类
化学 | 72830篇 |
晶体学 | 1538篇 |
力学 | 10856篇 |
综合类 | 628篇 |
数学 | 39343篇 |
物理学 | 41876篇 |
出版年
2024年 | 255篇 |
2023年 | 1344篇 |
2022年 | 2347篇 |
2021年 | 2634篇 |
2020年 | 2735篇 |
2019年 | 2787篇 |
2018年 | 12250篇 |
2017年 | 11929篇 |
2016年 | 9074篇 |
2015年 | 4136篇 |
2014年 | 4434篇 |
2013年 | 5571篇 |
2012年 | 9907篇 |
2011年 | 16576篇 |
2010年 | 9777篇 |
2009年 | 10088篇 |
2008年 | 11088篇 |
2007年 | 12722篇 |
2006年 | 4172篇 |
2005年 | 4535篇 |
2004年 | 4022篇 |
2003年 | 3969篇 |
2002年 | 3116篇 |
2001年 | 1855篇 |
2000年 | 1703篇 |
1999年 | 1648篇 |
1998年 | 1441篇 |
1997年 | 1324篇 |
1996年 | 1440篇 |
1995年 | 1099篇 |
1994年 | 932篇 |
1993年 | 804篇 |
1992年 | 744篇 |
1991年 | 643篇 |
1990年 | 535篇 |
1989年 | 439篇 |
1988年 | 333篇 |
1987年 | 291篇 |
1986年 | 300篇 |
1985年 | 248篇 |
1984年 | 172篇 |
1983年 | 146篇 |
1982年 | 111篇 |
1981年 | 98篇 |
1980年 | 79篇 |
1979年 | 70篇 |
1978年 | 67篇 |
1977年 | 44篇 |
1975年 | 46篇 |
1914年 | 45篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
221.
UB3LYP/6-31G(d) and ROMP2/6-311++G(d,2p) methods were used to calculate the Si-X bond dissociation energies (BDEs) of a number of para-substituted aromatic silanes (4-Y-C(6)H(4)-SiH(2)X, where X = H, F, Cl, or Li). It was found that the substituent effect on the Si-H BDE of 4-Y-C(6)H(4)-SiH(3) was small, as the slope (rho(+)()) of the BDE- regression was only 0.09 kJ/mol. In comparison, the substituent effect on the Si-F BDE of 4-Y-C(6)H(4)-SiH(2)F was much stronger, whose rho(+ )()value was -2.34 kJ/mol. The substituent effect on the Si-Cl BDE of 4-Y-C(6)H(4)-SiH(2)Cl was also found to be strong with a rho(+)() value of -1.70 kJ/mol. However, the substituent effect on the Si-Li BDE of 4-Y-C(6)H(4)-SiH(2)Li was found to have a large and positive slope (+9.12 kJ/mol) against. The origin of the above remarkably different substituent effects on the Si-X BDEs was found to be associated with the ability of the substituent to stabilize or destabilize the starting material (4-Y-C(6)H(4)-SiH(2)X) as well as the product (4-Y-C(6)H(4)-SiH(2)* radical) of the homolysis. Therefore, the direction and magnitude of the effects of Y-substituents on the Z-X BDEs in compounds such as 4-YC(6)H(4)Z-X should have some important dependence on the polarity of the Z-X bond undergoing homolysis. This conclusion was in agreement with that from earlier studies (for example, J. Am. Chem. Soc. 1991, 113, 9363). However, it indicated that the proposal from a recent work (J. Am. Chem. Soc. 2001, 123, 5518) was unfortunately not justified. 相似文献
222.
Friedrichs G Colberg M Fikri M Huang Z Neumann J Temps F 《The journal of physical chemistry. A》2005,109(21):4785-4795
The determination of rate constants for fast chemical reactions from nonexponential cavity ringdown profiles requires a consideration of the interfering laser bandwidth effect that arises if the line width of the ringdown probe laser exceeds the absorption line width of the detected species. The deconvolution of the kinetics and the bandwidth effect can be accomplished with the extended simultaneous kinetics and ringdown (eSKaR) model presented by Guo et al. (Guo, et al. Phys. Chem. Chem. Phys. 2003, 5, 4622). We present a detailed validation of this eSKaR model by a corresponding investigation of the well-known rate constant for the reaction NH2 + NO. Line profiles of the pulsed ringdown probe laser and the NH2 absorption line were determined from forward modeling of experimental ringdown profiles and verified by narrow-bandwidth laser absorption measurements. In addition, the rate constant for the title reaction was evaluated using the eSKaR model and also by means of a conventional pump-probe approach with variable time delays between the photolysis (pump) and ringdown (probe) laser pulses. The resulting room temperature rate constant for the NH2 + NO reaction, k1= (8.5 +/- 1.0) x 10(12) cm(3) mol(-1) s(-1), and the room temperature pressure broadening coefficient of NH2, = 2.27 GHz/bar, measured on the A2A1<-- X2B1 transition at wavelengths around lambda = 597 nm, were found to be in excellent agreement with the available literature data. 相似文献
223.
A theoretical comparative study of complexes of porphyrin (P), porphyrazine (Pz), phthalocyanine (Pc), porphycene (Pn), dibenzoporphycene (DBPn), and hemiporphyrazine (HPz) with iron (Fe) has been carried out using a density functional theory (DFT) method. The difference in the core size and shape of the macrocycle has a substantial effect on the electronic structure and properties of the overall system. The ground states of FeP and FePc were identified to be the 3A2g [(d(xy))2(d(z)2)2(d(pi))2] state, followed by 3E(g) [(d(xy))2(d(z)2)1(d(pi))3]. For FePz, however, the 3E(g)-3A2g energy gap of 0.02 eV may be too small to distinguish between the ground and excited states. When the symmetry of the macrocycle is reduced from D4h to D2h, the degeneracy of the d(pi) (d(xz), d(yz)) orbitals is removed, and the ground state becomes 3B2g [(d(xy))2(d(z)2)1(d(yz))2(d(xz))1] or 3B3g [...(d(yz))1(d(xz))2] for FePn, FeDBPn, and FeHPz. The calculations also show how the change of the macrocycle can influence the axial ligand coordination of pyridine (Py) and CO to the Fe(II) complexes. Finally, the electronic structures of the mono- and dipositive and -negative ions for all the unligated and ligated iron macrocycles were elucidated, which is important for understanding the redox properties of these compounds. The differences in the observed electrochemical (oxidation and reduction) properties between metal porphycenes (MPn) and metal porphyrins (MP) can be accounted for by the calculated results (orbital energy level diagrams, ionization potentials, and electron affinities). 相似文献
224.
Zhao J Zhang Y Kan Y Zhu L 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(3):679-688
The vibrational spectra of Group IIB elements halides MX2 and their dimers M2X4 (M=Zn(II), Cd(II) and Hg(II); X=F, Cl, Br and I) have been systematically investigated by ab initio RHF and B3LYP methods with LanL2MB, LanL2DZ and SDD basis sets. The optimized geometries, calculated vibrational frequencies are evaluated via comparison with the experimental data. The vibrational frequencies, calculated by these methods with different basis sets, are compared to each other too. The best results can be obtained by RHF/SDD method, with this method, the deviations for MX2 and Hg2X4 are <7%. Some vibrational frequencies of M2X4 that have not been experimentally reported are also predicted. 相似文献
225.
Alpha-fluorosulfonamides were prepared by electrophilic fluorination of tertiary sulfonamides using N-fluorobenzenesulfonimide as fluorinating agent and utilizing the dimethoxybenzyl group (DMB) as a new sulfonamide protecting group. Removal of the DMB group with TFA/CH(2)Cl(2) gave primary and secondary alpha-fluorosulfonamides. 相似文献
226.
Wengang Huang 《应用数学学报(英文版)》1991,7(3):279-283
In this paper, the author considered the stability of zero solution of linear RDDE $$\begin{gathered} \ddot x(t) + p_1 (t)\dot x(t) + q_1 (t)x(t) + p_2 (t)\dot x(t - r(t)) + q_2 (t)x(t - r(t)) = O, \hfill \\ \ddot x(t) + p_1 (t)\dot x(t) + q_1 (t)x(t) + p_2 (t)\dot x(t - r(t)) = O \hfill \\ \end{gathered} $$ using Liapunov-Razumikhin functional and transformations and obtained some sufficient conditions for the stability of Eqs.(1) and (2). These results are suitable both for boundedp i (t),q i (t) andr(t).i=1,2. 相似文献
227.
228.
229.
230.