全文获取类型
收费全文 | 2809篇 |
免费 | 67篇 |
国内免费 | 205篇 |
专业分类
化学 | 1652篇 |
晶体学 | 24篇 |
力学 | 24篇 |
数学 | 9篇 |
物理学 | 1372篇 |
出版年
2024年 | 4篇 |
2023年 | 139篇 |
2022年 | 43篇 |
2021年 | 27篇 |
2020年 | 38篇 |
2019年 | 46篇 |
2018年 | 51篇 |
2017年 | 52篇 |
2016年 | 80篇 |
2015年 | 65篇 |
2014年 | 86篇 |
2013年 | 273篇 |
2012年 | 168篇 |
2011年 | 158篇 |
2010年 | 134篇 |
2009年 | 185篇 |
2008年 | 180篇 |
2007年 | 218篇 |
2006年 | 165篇 |
2005年 | 125篇 |
2004年 | 93篇 |
2003年 | 93篇 |
2002年 | 91篇 |
2001年 | 67篇 |
2000年 | 95篇 |
1999年 | 70篇 |
1998年 | 50篇 |
1997年 | 44篇 |
1996年 | 54篇 |
1995年 | 30篇 |
1994年 | 20篇 |
1993年 | 17篇 |
1992年 | 27篇 |
1991年 | 12篇 |
1990年 | 8篇 |
1989年 | 4篇 |
1988年 | 14篇 |
1987年 | 8篇 |
1985年 | 4篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 2篇 |
1976年 | 3篇 |
1972年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有3081条查询结果,搜索用时 31 毫秒
11.
V. V. AntiĆ M. P. AntiĆ M. N. Govedarica P. R. DvorniĆ 《Journal of polymer science. Part A, Polymer chemistry》2007,45(11):2246-2258
The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10−6 to 3.1 × 10−5 mol Pt/mol CHCH2. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10−6 mol of Pt per mol of CHCH2, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH2 groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007 相似文献
12.
Orotic acid (vitamin B13) is a key intermediate in biosynthesis of the pyrimidine nucleotides in living organisms, moreover, it may serve as the biological carrier for some metal ions. cis-Diammine(orotato)platinum(II), cis-[Pt(C5H2N2O4)(NH3)2] can be considered as a new potential cisplatin analogue. The FT-Raman and FT-IR spectra of the title complex are reported, for the first time. The molecular structure, vibrational frequencies, and the theoretical infrared and Raman intensities have been calculated by the density functional mPW1PW91 method. The detailed vibrational assignment has been made on the basis of the calculated potential energy distribution. The theoretically predicted IR and Raman spectra show very good agreement with experiment. Natural bond orbital (NBO) analyses were performed for cisplatin, carboplatin and the title complex. The results provided new data on the nature of platinum–ligand bonding in these compounds. Strong intramolecular hydrogen bond between the orotate ligand and the coordinated ammonia group stabilizes the structure of the platinum(II) complex. Thus, it is suggested that the orotate ligand in the title complex is more inert to the substitution reactions than the chloride ligands in cisplatin. 相似文献
13.
David Loffreda 《Surface science》2006,600(10):2103-2112
Adsorption thermodynamics based on density functional theory (DFT) calculations are exposed for the interaction of several multifunctional molecules with Pt and Au(1 1 0)-(1 × 2) surfaces. The Gibbs free adsorption energy explicitly depends on the adsorption internal energy, which is derived from DFT adsorption energy, and the vibrational entropy change during the chemisorption process. Zero-point energy (ZPE) corrections have been systematically applied to the adsorption energy. Moreover the vibrational entropy change has been computed on the basis of DFT harmonic frequencies (gas and adsorbed phases, clean surfaces), which have been extended to all the adsorbate vibrations and the metallic surface phonons. The phase diagrams plotted in realistic conditions of temperature (from 100 to 400 K) and pressure (0.15 atm) show that the ZPE corrected adsorption energy is the main contribution. When strong chemisorption is considered on the Pt surface, the multifunctional molecules are adsorbed on the surface in the considered temperature range. In contrast for weak chemisorption on the Au surface, the thermodynamic results should be held cautiously. The systematic errors of the model (choice of the functional, configurational entropy and vibrational entropy) make difficult the prediction of the adsorption-desorption phase boundaries. 相似文献
14.
熔制了掺铒碲铌玻璃样品(100-X)TeO2-XNb2O5(X=5,10,15,20mol%),测试了其密度、折射率、转变温度、析晶温度、维氏机械强度、吸收光谱、荧光光谱、荧光寿命等参量。利用Judd-Ofelt和McCumber理论分别计算了铒离子强度参量Ωt(t=2,4,6)和受激发射截面σemi的大小,研究了掺铒碲铌玻璃样品光谱参量对Nb2O5成分的依赖性,并与典型的碲锌钠玻璃(75TeO2-20ZnO-5Na2O)在热学、机械强度、光谱性质和放大品行四个方面进行了比较. 相似文献
15.
Schiff碱水杨醛苯甲酰腙的特性 总被引:3,自引:1,他引:2
研究了 Schiff碱水杨醛苯甲酰腙 (简称 SBH)晶体在 DMSO及其 DMSO- H2 O的混合溶剂中的红外光谱 ,通过 SBH氘代前后的 IR对比发现 ,羟基氢质子与混合溶剂 DMSO- H2 O(3∶ 1 ,V/ V)产生较大的相互作用。向溶有 SBH的 75 % DMSO- 2 5 % H2 O的溶液滴加 KOH发现 ,SBH分子上的 C O羰基基团先与 KOH作用 ,其后与 O H 羟基基团作用 相似文献
16.
17.
18.
19.
The subject of spectral distribution methods where one derives and applies the locally smoothed forms of observables in nuclei
is briefly reviewed. It is well understood that the local forms (with respect to energy) of the level density function, expectation
values and strength densities are Gaussian, linear (or ratio of Gaussians) and a bivariate Gaussian respectively. To accomodate
symmetries in the above forms, one has to deal with multivariate distributions in general; for example the angular-momentum
(J) decomposition leads to a bivariate Gaussian form for the level density. These results extend to indefinitely large spaces
by method of partitioning and they generate convolution forms. The origin of these remarkable spectral properties is discussed
and shell model examples are given to substantiate their applicability to nuclear systems. Spectral distribution theory is
a practical, usable theory because the smoothed forms are defined in terms of traces of low particle-rank operators, and the
trace information propagates. Finally we discuss the application of the spectral methods for a wide range of nuclear problems;
these include binding energies, orbit occupancies, electromagnetic andβ-decay sum rule quantities, analysis of operators, symmetry breaking, numerical level densities, and determination of bounds
on time-reversal non-invariant part of nucleon-nucleon interaction. 相似文献
20.