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31.
32.
基于尖晶石晶体结构信息,本文采用热力学三亚晶格模型,将材料热力学计算和第一性原理计算相结合,研究了Zn_xMn_(1-x) Fe_2O_4和Ni_xMn_(1-x)Fe_2O_4立方相中的Zn~(2+)、Ni~(2+)、Mn~(2+)以及Fe~(3+)在8a和16d亚晶格上的占位有序化行为。结果表明:在锰铁氧体中,室温下Mn~(2+)完全占据在8a亚晶格上,Fe~(3+)完全占据在16d亚晶格上,属于正尖晶石结构;随着热处理温度升高,在1 273 K达到热处理平衡时的占位构型为(Fe~(3+)0.09Mn~(2+)0.91)[Fe~(3+)1.91Mn~(2+)0.09]O_4,在热处理温度升至1 473 K时,达到热处理平衡时的占位构型为(Fe~(3+)0.11Mn~(2+)0.89)[Fe~(3+)1.89Mn~(2+)0.11]O_4,均与实验结果符合较好。在锌铁氧体中,室温下Zn~(2+)完全占据在8a亚晶格上,Fe~(3+)完全占据在16d亚晶格上,属于正尖晶石结构;在热处理温度较高时,Zn~(2+)和Fe~(3+)发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe~(3+)在室温下占据在8a亚晶格上,Ni~(2+)与剩下另一半的Fe~(3+)共同占据在16d亚晶格上,仅在热处理温度较高的时候发生微弱变化,亦与已有的实验结果吻合。在此基础上,本文进一步通过热力学模型研究了立方相尖晶石结构的Zn_xMn_(1-x)Fe_2O_4、Ni_xMn_(1-x)Fe_2O_4复合体系中阳离子占位行为与热处理温度对占位的影响规律。 相似文献
33.
Thatcher RJ Johnson DG Slattery JM Douthwaite RE 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(14):4329-4336
Deprotonation of the 1-isopropyl-3-(phenylamino)pyridin-1-ium iodide gives the corresponding neutral betaine, which is formalised as a pyridinium-amido ligand when coordinated to a metal. Spectroscopic, structural and theoretical methods have been used to investigate the metal-ligand bonding, ligand dynamics and electron distribution. Collectively, the data show that the ligand can be characterised as a pseudo-amide and is a strong donor akin to alkyl phosphines and N-heterocyclic carbenes. Furthermore, rotation about both N substituent C-N bonds occurs, which is in contrast to the two alternative pyridinium positional isomers that exhibit neutral resonance structures. For comparison, compounds and complexes derived from norharman were prepared, which contain an additional C-C bond supporting conjugation and the accessibility of a neutral resonance structure. Notwithstanding the formal neutral structure, norharman-derived ligands are comparably strong donors, and have the additional advantage of exhibiting stability to dioxygen and water. 相似文献
34.
Câmpian MV Perutz RN Procacci B Thatcher RJ Torres O Whitwood AC 《Journal of the American Chemical Society》2012,134(7):3480-3497
Three ruthenium complexes Λ-[cis-Ru((R,R)-Me-BPE)(2)(H)(2)] Λ-R,R-Ru1H(2), Δ-[cis-Ru((S,S)-Me-DuPHOS)(2)(H)(2)] Δ-S,S-Ru2H(2), and Λ-[cis-Ru((R,R)-Me-DuPHOS)(2)(H)(2)] Λ-R,R-Ru2H(2) (1 = (Me-BPE)(2), 2 = (Me-DuPHOS)(2)) were characterized by multinuclear NMR and CD spectroscopy in solution and by X-ray crystallography. The chiral ligands allow the full control of stereochemistry and enable mechanistic studies not otherwise available. Oxidative addition of E-H bonds (E = H, B, Si, C) was studied by steady state and laser flash photolysis in the presence of substrates. Steady state photolysis shows formation of single products with one stereoisomer. Solid state structures and circular dichroism spectra reveal a change in configuration at ruthenium for some Δ-S,S-Ru2H(2)/Λ-R,R-Ru2H(2) photoproducts from Λ to Δ (or vice versa) while the configuration for Λ-R,R-Ru1H(2) products remains unchanged as Λ. The X-ray structure of silyl hydride photoproducts suggests a residual H(1)···Si(1) interaction for Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(Et(2)SiH)(H)] and Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(PhSiH(2))(H)] but not for their Ru(R,R-BPE)(2) analogues. Molecular structures were also determined for Λ-[cis-Ru((R,R)-Me-BPE)(2)(Bpin)(H)], Λ-[Ru((S,S)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], Δ-[Ru((R,R)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], and trans-[Ru((R,R)-Me-DuPHOS)(2)(C(6)F(5))(H)]. In situ laser photolysis in the presence of p-H(2) generates hyperpolarized NMR spectra because of magnetically inequivalent hydrides; these experiments and low temperature photolysis with D(2) reveal that the loss of hydride ligands is concerted. The reaction intermediates [Ru(DuPHOS)(2)] and [Ru(BPE)(2)] were detected by laser flash photolysis and have spectra consistent with approximate square-planar Ru(0) structures. The rates of their reactions with H(2), D(2), HBpin, and PhSiH(3) were measured by transient kinetics. Rate constants are significantly faster for [Ru(BPE)(2)] than for [Ru(DuPHOS)(2)] and follow the substrate order H(2) > D(2) > PhSiH(3) > HBpin. 相似文献
35.
采用傅里叶变换红外光谱(FTIR)及其二阶导数谱对不同生长年限当归药材进行分析研究.结果表明,不同生长年限当归药材的红外图谱较为相似,仅从一维谱图上无法反映出不同生长年限当归药材的红外特征谱明显的异同,但通过二阶导数图谱中1771、1747、1712、1559、1514、1466、766、711cm-1和668cm-1处的峰型差异可发现不同生长年限当归药材之间的一些成分存在较明显的差异.由于生长时间不同,导致它们的化学成分存在差异,所以体现了各自的红外特征谱,其中第三年当归药材与第一年和第二年当归药材间差异较大. 相似文献
36.
37.
David A. Hrovat Richard Vaughan Williams Alan C. Goren Weston Thatcher Borden 《Journal of computational chemistry》2001,22(13):1565-1573
B3LYP/6‐31G* calculations on the degenerate rearrangements of substituted semibullvalenes spuriously predict the relative enthalpies of the bishomoaromatic TSs to be lower than the experimental values. However, the calculations do make the useful and experimentally testable prediction that the two cyano and two phenyl substituents in 2,6‐dicyano‐4,8‐diphenylsemibullvalene ( 9d ) are more likely than four cyano substituents in 2,4,6,8‐tetracyanosemibullvalene ( 9f ) or the four phenyl substituents in 2,4,6,8‐tetraphenylsemibullvalene ( 9g ) to produce a semibullvalene that has a bishomoaromatic equilibrium geometry in the gas phase. The major reason for the surprising finding that 9d is more likely to be bishomoaromatic than 9g is shown to be steric interactions between the phenyl groups at C‐2 and C‐8 and at C‐4 and C‐6 in bishomoaromatic structure 10g . These interactions inhibit the conjugative stabilization of 10g ; but they are absent in bishomoaromatic structure 10d , where cyano groups replace the phenyl groups at C‐2 and C‐6 in 10g . © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1565–1573, 2001 相似文献
38.
1 INTRODUCTIONWith the invention of lasers[1] and the observation of second-harmonic generation in quartz[2], nonlinear optics(NLO), as a cornerstone of photonics, has been booming since 1960's. And intense interest has been aroused to search materials exhibiting appropriate nonlinear optical properties suitable for the construction of practical optical devices for the important techniques such as frequency converting, signal processing and optical computing[3~6]. In order to determine … 相似文献
39.
SABen-Hao CAIXu TAIAn ZHOUDai-Mei 《理论物理通讯》2004,42(3):403-406
We present the simulation results of the net charge fluctuation in Au Au collisions at √Snn=130 GeV from a dynamic model, JPCIAE, and its revisions. The simulations are done for the quark-gluon matter, the directly produced pions, the pion matter, and the hadron matter. The simulated net charge fluctuation of the quark-gluon matter is close to the thermal model prediction for the quark-gluon gas. However, the discrepancy exists comparing the simulated net charge fluctuation for directly produced pions and the pion matter with the thermal model prediction for pion gas and the resonance pion gas, respectively. The net charge fluctuation of hadron matter from default JPCIAE simulations is nearly 3.5 times larger than quark-gluon matter. A discussion is given for the net charge fluctuation as an evidence of QGP phase transition. 相似文献
40.
The distributions of dynamic variables in the deep inelastic scattering (DIS) of heavy-ions are studied by a direct simulation technique based on the single-nucleon-transfer-mechanism. The relative motion of the two collision partners is described by a Lagrange equation, and the transition probability of a single nucleon during the interaction time is calculated by the statisti-cal spectroscopy method.The occurrence of the transition event and the corresponding change of the dynamic variables are both treated randomly according to the transition probability. The calculated results for the reaction of 40Ar+58Ni(EL=280MeV) are compared with experimental data. 相似文献