全文获取类型
收费全文 | 510篇 |
免费 | 21篇 |
国内免费 | 3篇 |
专业分类
化学 | 323篇 |
晶体学 | 3篇 |
力学 | 15篇 |
数学 | 90篇 |
物理学 | 103篇 |
出版年
2023年 | 2篇 |
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 10篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2017年 | 9篇 |
2016年 | 19篇 |
2015年 | 18篇 |
2014年 | 19篇 |
2013年 | 25篇 |
2012年 | 49篇 |
2011年 | 39篇 |
2010年 | 25篇 |
2009年 | 15篇 |
2008年 | 28篇 |
2007年 | 27篇 |
2006年 | 27篇 |
2005年 | 26篇 |
2004年 | 23篇 |
2003年 | 27篇 |
2002年 | 17篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 7篇 |
1998年 | 5篇 |
1997年 | 5篇 |
1996年 | 7篇 |
1995年 | 4篇 |
1994年 | 4篇 |
1993年 | 6篇 |
1992年 | 8篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 1篇 |
1987年 | 2篇 |
1986年 | 3篇 |
1985年 | 11篇 |
1984年 | 5篇 |
1983年 | 6篇 |
1981年 | 1篇 |
1980年 | 8篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有534条查询结果,搜索用时 15 毫秒
1.
2.
The determination of the past and the future of a physical system are complementary aims of measurements. An optimal determination of the past of a system can be achieved by an informationally complete set of physical quantities. Such a set is always strongly noncommutative. An optimal determination of the future of a physical system can be obtained by a Boolean complete set of quantities. The two aims can be reconciled to a reasonable degree with using unsharp measurements.This work was partly supported by the Bundesministerium für Forschung und Technologie, Bonn, the Research Institute for Theoretical Physics, Helsinki, and the University of Turku Foundation, Turku. 相似文献
3.
The number-phase uncertainty relations arerevisited in view of the recent discovery of a propercovariant phase observable. The high-amplitude limits ofthe coherent-state expectations of the moment operators of the phase observable are determined and thebehavior of the number-phase uncertainty product in thatlimit is investigated. 相似文献
4.
The neutral, cationic, and anionic structures of both prototropic tautomers oftrans- andcis-urocanic acid [(E)- and (Z)-3-(1H-imidazol-4(5)-yl)propenoic acid, respectively] were studied by using semiempirical andab initio gas-phase calculations. Potential energy surfaces of the structures were calculated by using the semiempirical AM1 method, and the geometries corresponding to global minima on these surfaces were optimized up to the MP2/6-31G* level of theory. The calculated protonation forms of each urocanic acid isomer have a planar molecular structure due to a delocalized -electron system, and all of them prefer thes-trans conformation with respect to the bond between the imidazole and the propenoic acid moieties. Thecis-urocanic acid structures are stabilized by an intramolecular hydrogen bond. The chargedcis-urocanic acid isomers have a lower molecular energy than the correspondingtrans-isomers, whereas the neutral molecules have, after inclusion of thermodynamic corrections, approximately the same energy. The cationic urocanic acid structures have about 2500 kJ mol–1 lower energy than the anionic ones and about 1000 kJ mol–1 lower energy than the neutral ones. The nonzwitterionic forms of the neutral urocanic acid isomers have about 200 kJ mol–1 lower energy than the zwitterionic ones. These energy differences are explained by the proton affinities of the imidazole and the propenoic acid moieties of the urocanic acid structures. 相似文献
5.
Taylor P Lahti PM Carroll JB Rotello VM 《Chemical communications (Cambridge, England)》2005,(7):895-897
Stable radical 2-(6-uradinyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-1-oxyl (1) binds to hydrogen-bonding complement 2,6-di(propylamido)pyridine (DAP) in chloroform with Ka=220 M(-1) at 33 degrees C; ESI-MS shows not only 1:DAP complementary dyad formation, but also 1:(DAP)2 formation at higher concentrations of DAP. 相似文献
6.
Ab initio calculations are reported for the conformational potential energy surfaces of chloromethyl formate and fluoromethyl formate at minimal basis set level. The halomethyl group is shown to lie Z to the carbonyl group. A plateau on the potential energy surface demonstrates that the halomethyl group can rotate freely. The halogen atom therefore moves from an antiperiplanar (ap) to a synclinal (sp) position with respect to the carbonyl group. The effects on IR spectra and dipole moments are discussed. 相似文献
7.
Hanni M Lantto P Runeberg N Jokisaari J Vaara J 《The Journal of chemical physics》2004,121(12):5908-5919
Quantum chemical calculations of the nuclear shielding tensor, the nuclear quadrupole coupling tensor, and the spin-rotation tensor are reported for the Xe dimer using ab initio quantum chemical methods. The binary chemical shift delta, the anisotropy of the shielding tensor Delta sigma, the nuclear quadrupole coupling tensor component along the internuclear axis chi( parallel ), and the spin-rotation constant C( perpendicular ) are presented as a function of internuclear distance. The basis set superposition error is approximately corrected for by using the counterpoise correction (CP) method. Electron correlation effects are systematically studied via the Hartree-Fock, complete active space self-consistent field, second-order M?ller-Plesset many-body perturbation, and coupled-cluster singles and doubles (CCSD) theories, the last one without and with noniterative triples, at the nonrelativistic all-electron level. We also report a high-quality theoretical interatomic potential for the Xe dimer, gained using the relativistic effective potential/core polarization potential scheme. These calculations used valence basis set of cc-pVQZ quality supplemented with a set of midbond functions. The second virial coefficient of Xe nuclear shielding, which is probably the experimentally best-characterized intermolecular interaction effect in nuclear magnetic resonance spectroscopy, is computed as a function of temperature, and compared to experiment and earlier theoretical results. The best results for the second virial coefficient, obtained using the CCSD(CP) binary chemical shift curve and either our best theoretical potential or the empirical potentials from the literature, are in good agreement with experiment. Zero-point vibrational corrections of delta, Delta sigma, chi (parallel), and C (perpendicular) in the nu=0, J=0 rovibrational ground state of the xenon dimer are also reported. 相似文献
8.
Field LM Lahti PM Palacio F Paduan-Filho A 《Journal of the American Chemical Society》2003,125(33):10110-10118
Mn(hfac)(2) and Cu(hfac)(2) form coordination complexes with 5-(4-[N-tert-butyl-N-aminoxyl]phenyl)pyrimidine, PyrimPh-NIT. (Mn[PyrimPh-NIT](hfac)(2))(2) and (Cu[PyrimPh-NIT](hfac)(2))(2), 1 and 2, respectively, are cyclic M(2)L(2) dimers that exhibit strong exchange coupling between the coordinated paramagnetic dication (M) and nitroxide (NIT) unit. The M-NIT exchange is strongly antiferromagnetic (AFM) in 1 and strongly ferromagnetic (FM) in 2. Magnetic susceptibility measurements for 1 were fitted to an AFM spin pairing model with J/k = -0.25 K between Mn-NIT spin sites units. Complex 2 also exhibits AFM spin pairing between S = 1 Cu-NIT spin units that is somewhat field dependent at low temperature. The fit of corrected paramagnetic susceptibility chi(T) to an AFM spin pairing model at 200 Oe yields J/k = (-)3.8 K, quite similar to earlier measurements at 1000 Oe yielding J/k = (-)5.0 K. At 1.40 K, the magnetization of 2 does not approach saturation until somewhat above 170 kOe, giving an S-shaped curve; at 0.55 K, the magnetization curve shows steps characteristic of field-induced crossover between the S = 0 ground state and excited spin states. From the steps in the 0.55 K data, we estimate J/k = (-)3.8-4.0 K for 2, in good agreement with the analysis of chi(T). 相似文献
9.
Addition of excess R(2)NCN to an aqueous solution of K(2)[PtCl(4)] led to the precipitation of [PtCl(2)(NCNR(2))(2)] (R(2) = Me(2) 1; Et(2) 2; C(5)H(10) 3; C(4)H(8)O, 4) in a cis/trans isomeric ratio which depends on temperature. Pure isomers cis-1-3 and trans-1-3 were separated by column chromatography on SiO(2), while trans-4 was obtained by recrystallization. Complexes cis-1-3 isomerize to trans-1-3 on heating in the solid phase at 110 degrees C; trans-1 has been characterized by X-ray crystallography. Chlorination of the platinum(II) complexes cis-1-3 and trans-1-4 gives the appropriate platinum(IV) complexes [PtCl(4)(NCNR(2))(2)] (cis-5-7 and trans-5-8). The compound cis-6 was also obtained by treatment of [PtCl(4)(NCMe)(2)] with neat Et(2)NCN. The platinum(IV) complex trans-[PtCl(4)(NCNMe(2))(2)] (trans-5) in a mixture of undried Et(2)O and CH(2)Cl(2) undergoes facile hydrolysis to give trans-[PtCl(4)[(H)=C(NMe(2))OH](2)] (9; X-ray structure has been determined). The hydrolysis went to another direction with the cis-[PtCl(4)(NCNR(2))(2)] (cis-5-7) which were converted to the metallacycles [PtCl(4)[NH=C(NR(2))OC(NR(2))=NH]] (11-13) due to the unprecedented hydrolytic coupling of the two adjacent dialkylcyanamide ligands giving a novel (for both coordination and organic chemistry) diimino linkage. Compounds 11-13 and also 14 (R(2) = C(4)H(8)O) were alternatively obtained by the reaction between cis-[PtCl(4)(MeCN)(2)] and neat undried NCNR(2). The structures of complexes 11, 13, and 14 were determined by X-ray single-crystal diffraction. All the platinum compounds were additionally characterized by elemental analyses, FAB mass-spectrometry, and IR and (1)H and (13)C[(1)H] NMR spectroscopies. 相似文献
10.
Bokach NA Kuznetsova TV Simanova SA Haukka M Pombeiro AJ Kukushkin VY 《Inorganic chemistry》2005,44(14):5152-5160
Treatment of trans-[PtCl4(RCN)2] (R = Me, Et, Ph, NEt2) with 2 equiv of the amidine PhC(=NH)NHPh in a suspension of MeCN (R = Me), CHCl3 (R = Et, Ph), or in CHCl3 solution (R = NEt2) results in the formation of the imidoylamidine complexes trans-[PtCl4{NH=C(R)N=C(Ph)NHPh}2] (1-4) isolated in good yields (66-84%). The reaction of soluble complexes 3 and 4 with 2 equiv of Ph3P=CHCO2Me in CH2Cl2 (40 degrees C, 5 h) leads to dehydrochlorination resulting in a chelate ring closure to furnish the platinum(IV) chelates [PtCl2{NH=C(R)NC(Ph)=NPh}2] (R = Ph, 5; R = NEt2, 6), accordingly, and the phosphonium salt [Ph3PCH2CO2Me]Cl. Treatment of 5 with 3 equiv of Ph3P=CHCO2Me at 50 degrees C for 5 d resulted in only a 30% conversion to the corresponding Pt(II) complex [Pt{NH=C(NEt2)NC(Ph)=NPh}2] (15). The reduction can be achieved within several minutes, when Ph2PCH2CH2PPh2 in CDCl3 is used. When the platinum(II) complex trans-[PtCl2(RCN)2] is reacted with 2 equiv of the amidine, the imidoylamidinato complexes [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) and [PhC(=NH)NHPh] x HCl (7) are formed. The reaction of trans-[PtCl2(RCN)2] with 4 equiv of the amidine under a prolonged reaction time or treatment of [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) with 2 more equiv of the amidine yields the complex bearing two chelate rings [Pt{NH=C(R)NC(Ph)=NHPh}2] (12-15). The treatment of cis-[PtCl2(RCN)2] (R = Me, Et) with the amidine gives ca. 50-60% yield of [PtCl2{NH=C(R)NHC(Ph)=NHPh}] (16 and 17). All of the platinum compounds were characterized by elemental analyses; FAB mass spectrometry; IR spectroscopy; 1H, 13C{1H}, and 195Pt NMR spectroscopies, and four of them (4, 6, 8, and 15) were also characterized by X-ray crystallography. The coupling of the Pt-bound nitriles and the amidine is metal-mediated insofar as RCN and PhC(=NH)NHPh do not react in the absence of the metal centers in conditions more drastic than those of the observed reactions. The nitrile-amidine coupling reported in this work constitutes a route to the synthesis of imidoylamidine complexes, some of them exhibiting luminescent properties. 相似文献