全文获取类型
收费全文 | 6533篇 |
免费 | 274篇 |
国内免费 | 161篇 |
专业分类
化学 | 4404篇 |
晶体学 | 23篇 |
力学 | 184篇 |
综合类 | 8篇 |
数学 | 889篇 |
物理学 | 1460篇 |
出版年
2023年 | 33篇 |
2022年 | 50篇 |
2021年 | 66篇 |
2020年 | 80篇 |
2019年 | 87篇 |
2018年 | 101篇 |
2017年 | 88篇 |
2016年 | 163篇 |
2015年 | 150篇 |
2014年 | 160篇 |
2013年 | 268篇 |
2012年 | 313篇 |
2011年 | 348篇 |
2010年 | 176篇 |
2009年 | 145篇 |
2008年 | 261篇 |
2007年 | 248篇 |
2006年 | 225篇 |
2005年 | 214篇 |
2004年 | 200篇 |
2003年 | 155篇 |
2002年 | 136篇 |
2001年 | 103篇 |
2000年 | 84篇 |
1999年 | 54篇 |
1998年 | 40篇 |
1997年 | 40篇 |
1996年 | 38篇 |
1995年 | 39篇 |
1994年 | 37篇 |
1993年 | 42篇 |
1991年 | 37篇 |
1990年 | 44篇 |
1983年 | 37篇 |
1982年 | 50篇 |
1981年 | 43篇 |
1980年 | 39篇 |
1979年 | 39篇 |
1978年 | 43篇 |
1976年 | 35篇 |
1959年 | 90篇 |
1958年 | 151篇 |
1957年 | 187篇 |
1956年 | 47篇 |
1936年 | 32篇 |
1932年 | 33篇 |
1930年 | 53篇 |
1929年 | 56篇 |
1928年 | 74篇 |
1927年 | 48篇 |
排序方式: 共有6968条查询结果,搜索用时 15 毫秒
91.
P. Révész 《Probability Theory and Related Fields》1992,93(1):21-37
Summary We say that the discD()R
2, of radius , located around the origin isp-covered in timeT by a Wiener processW(·) if for anyzD() there exists a 0tT such thatW(t) is a point of the disc of radiusp, located aroundz. The supremum of those 's (0) is studied for which,D() isp-covered inT. 相似文献
92.
C-H hydroxylation is a fundamental process. In Nature it is catalyzed by the enzyme cytochrome P450, in a still-debated mechanism that poses a major intellectual challenge for both experiment and theory; currently, the opinions keep swaying between the original single-state rebound mechanism, a two-oxidant mechanism (where ferric peroxide participates as a second oxidant, in addition to the primary active species, the high-valent iron-oxo species), and two-state reactivity (TSR) mechanism (where two spin states are involved). Recent product isotope effect (PIE) measurements for the trans-2-phenyl-methyl cyclopropane probe (1), led Newcomb and co-workers (Newcomb, M.; Aebisher, D.; Shen, R.; Esala, R.; Chandrasena, P.; Hollenberg, P.; Coon, M. J. J. Am. Chem. Soc. 2003, 125, 6064-6065) to rule out TSR in favor of the two-oxidant scenario, since the direction of the PIE was at odds with the one predicted from calculations on methane hydroxylation. The present report describes a density functional theoretical study of C-H hydroxylation of the Newcomb probe, 1, leading to rearranged (3) and unrearranged (2) products. Our study shows that the reaction occurs via TSR in which the high-spin pathway gives dominant rearranged products, whereas the low-spin pathway favors unrearranged products. The calculated PIE(2/3) values based on TSR are found to be in excellent agreement with the experimental data of Newcomb and co-workers. This match between experiment and theory makes a strong case that the reaction occurs via TSR mechanism. 相似文献
93.
Anthony Poë 《Journal of organometallic chemistry》1976,120(1):C20-C21
The palladium(I) and platinum(I) complexes [(CH3NC)6M2]2+ undergo substitution reactions with isocyanides, phosphines and halide or pseudohalide ions. With triphenylphosphine, axial substitution is preferred. The product [(CH3NC)5(Ph3P)Pd2]2+ is fluxional. 相似文献
94.
Richard Combes Marie-Noëlle Levelut Bernard Trémillon 《Journal of Electroanalytical Chemistry》1978,91(1):125-131
Reactions between cerium trichloride and oxide ions were studied in NaCl+KCl (1/1) at 1000°K, by potentiometry with a calcia-stabilized zirconia membrane electrode. Titration curves clearly demonstrated the existence of soluble cerium oxychloride (CeO+) and precipitated cerium oxide (Ce2O3), with respective dissociation constants 10?11 and 10?30 (molality scale). The corresponding conditional solubility diagram {log S (CeIII)=f(pO2?)} is presented and discussed. 相似文献
95.
B. Lesiak A. Kosiński R. Nowakowski L. Kövér J. Tóth D. Varga I. Cserny A. Sulyok G. Gergely 《Surface and interface analysis : SIA》2007,39(10):798-804
In elastic peak electron spectroscopy (EPES), the nearest vicinity of elastic peak in the low kinetic energy region reflects electron inelastic and quasielastic processes. Incident electrons produce surface excitations, inducing surface plasmons, with the corresponding loss peaks separated by 1–20 eV energy from the elastic peak. In this work, X‐ray photoelectron spectroscopy (XPS) and helium pycnometry are applied for determining surface atomic composition and bulk density, whereas atomic force microscopy (AFM) is applied for determining surface morphology and roughness. The component due to electron recoil on hydrogen atoms can be observed in EPES spectra for selected primary electron energies. Simulations of EPES predict a larger contribution of the hydrogen component than observed experimentally, where hydrogen deficiency is observed. Elastic peak intensity is influenced more strongly by surface morphology (roughness and porosity) than by surface excitations and quasielastic scattering of electrons by hydrogen atoms. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
96.
A. S. Aynacioglu A. -H. Meißner F. Walachowicz G. v. Oppen 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,18(1):85-91
The magnetic depolarization of the impact radiation at λ(41 D?21 P)=492 nm and λ(31 D?21 P) = 668 nm as well as the splitting of the magnetic depolarisation signals in electric fields were investigated for 10–25 keV H 2 + (D 2 + )-He collisions (only 492 nm line) and for 5-22.5 keV He-He collisions (both lines). The results are compared with analogous measurements for He+- He and Ne+ - He collisions and the dynamics of the excitation process are qualitatively discussed. In particular, we emphasize the importance of inertia for the evolution of the electron cloud during the final phase of the collision process. 相似文献
97.
The complexes of 4-chloro-2-methoxybenzoic acid anion with Mn2+,
Co2+, Ni2+, Cu2+
and Zn2+ were obtained as polycrystalline solids
with general formula M(C8H6ClO3)2·nH2O and colours typical for M(II) ions (Mn – slightly pink, Co –
pink, Ni – slightly green, Cu – turquoise and Zn – white).
The results of elemental, thermal and spectral analyses suggest that compounds
of Mn(II), Cu(II) and Zn(II) are tetrahydrates whereas those of Co(II) and
Ni(II) are pentahydrates. The carboxylate groups in these complexes are monodentate.
The hydrates of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II)
and Zn(II) heated in air to 1273 K are dehydrated in one step in the range
of 323–411 K and form anhydrous salts which next in the range of 433–1212
K are decomposed to the following oxides: Mn3O4,
CoO, NiO and ZnO. The final products of decomposition of Cu(II) complex are
CuO and Cu. The solubility value in water at 293 K for all complexes is in
the order of 10–3 mol dm–3.
The plots of χM
vs.
temperature of 4-chloro-2-methoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II)
follow the Curie–Weiss law. The magnetic moment values of Mn2+,
Co2+, Ni2+ and Cu2+
ions in these complexes were determined in the range of 76−303 K and
they change from: 5.88–6.04 μB for Mn(C8H6ClO3)2·4H2O, 3.96–4.75
μB for Co(C8H6ClO3)2·5H2O, 2.32–3.02 μB for Ni(C8H6ClO3)2·5H2O and 1.77–1.94
μB for Cu(C8H6ClO3)2·4H2O. 相似文献
98.
Aresta M Tommasi I Quaranta E Fragale C Mascetti J Tranquille M Galan F Fouassier M 《Inorganic chemistry》1996,35(14):4254-4260
Extended labeling experiments have shown that formation of rhodium peroxocarbonate from CO(2) and [RhCl(eta(2)-O(2))(P)(3)] (P is PEt(2)Ph or PEtPh(2)) proceeds through O-O bond cleavage and CO(2) insertion. O-transfer to ancillary phosphine ligand to give R(3)P=O selectively (>85%) involves the Rh-linked O atom of the peroxo group of RhCl(CO(4))(P)(3). 相似文献
99.
Noëlle Ehlinger Monique Perrin 《Journal of inclusion phenomena and macrocyclic chemistry》1995,22(1):33-40
The structure of thep-tetrakis-(4-nitrophenylazo)calix[4]arene-4-picoline (14) complex has been determined by X-ray crystallography. Crystals are monoclinic, space groupC2/c,a=24.9097) Å,b=8.425(6) Å,c=33.81(1) Å, =101.13(2)°,D
c
=1.330 g/cm3,Z=4, finalR value =0.067. The cone conformation adopted by this azocalixarene is disturbed by the positions of the picoline molecules. Two of them are inside the macorocycle cavity and the two others are outside.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. Sup. 82190 (32 pages). 相似文献
100.
在MOCVD设备中采用改进的射频辅助生长装置,通过裂解N2及N-Al共掺杂的方法进行ZnO的p型掺杂研究。通过二次离子质谱(SIMS)、X射线衍射(XRD)、原子力显微镜(AFM)、光致发光(PL)谱等方法分析了薄膜中N杂质的浓度,以及射频功率与晶体质量、表面形貌以及光学特性之间的关系,并与Al掺杂和N掺杂的ZnO薄膜进行对比。实验结果表明,N掺杂的浓度高达1020cm-3;N-Al共掺杂极大地增加了ZnO的成核速率,其主要原因是N离化所起的作用;N-Al共掺的ZnO薄膜显示出p型性质,而N掺杂的ZnO薄膜由于N原子处于非激活状态而呈现高阻,这说明N-Al共掺杂对ZnO中N原子的活化起到一定作用。 相似文献