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1.
The kinetics of the direct synthesis reaction (Si + 2CH3Cl → (CH3)2SiCl2) were measured on a Cu3Si alloy containing 1.2 atom % Zn. Reaction was carried out in a differential reactor (520–595 K, 1 atm) attached to an ultrahigh vacuum (UHV) system. Auger spectroscopy was used to characterize the surface before and after reaction. Zinc does not significantly change the overall rate of reaction, but it changes selectivity to dimethyldichlorosilane (the desired product), surface composition, activation energies, and induction times. The rate of silicon diffusion to the surface is not limiting in the presence of zinc. Zinc is found to be a promoter for improved selectivity only in low concentrations, and only a fraction of the surface appears to be active for reaction. The kinetics appear relatively insensitive to the surface composition or the form of surface carbon. A Cu3Si surface with Zn is shown to be a good model catalyst for the direct synthesis reaction. 相似文献
2.
Summary The complexes Pd(PTH)2Cl2 · 3.5 H2O, Pd(PTH)3(PPh3), Ru(PTH)2(PPh3)Cl2, Ru(PTH)2(PPh3)Cl3, Rh(PTH)2(PPh3)Cl and Rh(PT)Cl2 · 0.5 H2O, where PTH isN-phenylcarbamoylpyrrole-2-thiocarboxamide, have been prepared and characterised by magnetic and spectral (i.r., u.v. and visible) studies. 相似文献
3.
Birendra K. Agrawal Madhup Chandra Badri V. Agarwala Arun K. Dey 《Transition Metal Chemistry》1978,3(1):243-246
Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO4], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present. 相似文献
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Summary Amperometric ascorbimetric determinations of cerium(IV) and ferric iron have been carried out at 50°C with two polarized electrodes at 200 and 100 mV respectively. The results obtained are fairly accurate and precise within ±1.0 per cent. A simple method for successive determination of cerium and iron has been developed; and conditions for such estimations have been established. At an acidity of 2.5 M with respect to sulphuric acid, it is possible to ward off the reduction of ferric iron and thereby cerium(IV) is successfully titrated with ascorbic acid in this medium. After completion of the reaction and then lowering the acid concentration to pH 1.5 with aid of ammonium hydroxide, FeIII is titrated with standard ascorbic acid yielding good results. 相似文献
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7.
Dr. Dipanwita Das Hemlata Agarwala Dr. Abhishek Dutta Chowdhury Tuhin Patra Dr. Shaikh M. Mobin Prof. Dr. Biprajit Sarkar Prof. Dr. Wolfgang Kaim Prof. Dr. Goutam Kumar Lahiri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7384-7394
The complex series [Ru(pap)(Q)2]n ([ 1 ]n–[ 4 ]n; n=+2, +1, 0, ?1, ?2) contains four redox non‐innocent entities: one ruthenium ion, 2‐phenylazopyridine (pap), and two o‐iminoquinone moieties, Q=3,5‐di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine (aryl=C6H5 ( 1+ ); m‐(Cl)2C6H3 ( 2+ ); m‐(OCH3)2C6H3 ( 3+ ); m‐(tBu)2C6H3 ( 4 +)). A crystal structure determination of the representative compound, [ 1 ]ClO4, established the crystallization of the ctt‐isomeric form, that is, cis and trans with respect to the mutual orientations of O and N donors of two Q ligands, and the coordinating azo N atom trans to the O donor of Q. The sensitive C? O (average: 1.299(3) Å), C? N (average: 1.346(4) Å) and intra‐ring C? C (meta; average: 1.373(4) Å) bond lengths of the coordinated iminoquinone moieties in corroboration with the N?N length (1.292(3) Å) of pap in 1 + establish [RuIII(pap0)(Q.?)2]+ as the most appropriate electronic structural form. The coupling of three spins from one low‐spin ruthenium(III) (t2g5) and two Q.? radicals in 1 +– 4 + gives a ground state with one unpaired electron on Q.?, as evident from g=1.995 radical‐type EPR signals for 1 +– 4 +. Accordingly, the DFT‐calculated Mulliken spin densities of 1 + (1.152 for two Q, Ru: ?0.179, pap: 0.031) confirm Q‐based spin. Complex ions 1 +– 4 + exhibit two near‐IR absorption bands at about λ=2000 and 920 nm in addition to intense multiple transitions covering the visible to UV regions; compounds [ 1 ]ClO4–[ 4 ]ClO4 undergo one oxidation and three separate reduction processes within ±2.0 V versus SCE. The crystal structure of the neutral (one‐electron reduced) state ( 2 ) was determined to show metal‐based reduction and an EPR signal at g=1.996. The electronic transitions of the complexes 1 n– 4 n (n=+2, +1, 0, ?1, ?2) in the UV, visible, and NIR regions, as determined by using spectroelectrochemistry, have been analyzed by TD‐DFT calculations and reveal significant low‐energy absorbance (λmax>1000 nm) for cations, anions, and neutral forms. The experimental studies in combination with DFT calculations suggest the dominant valence configurations of 1 n– 4 n in the accessible redox states to be [RuIII(pap0)(Q.?)(Q0)]2+ ( 1 2+– 4 2+)→[RuIII(pap0)(Q.?)2]+ ( 1 +– 4 +)→[RuII(pap0)(Q.?)2] ( 1 – 4 )→[RuII(pap.?)(Q.?)2]? ( 1 ?– 4 ?)→[RuIII(pap.?)(Q2?)2]2? ( 1 2?– 4 2?). 相似文献
8.
The salts of the linkage isomers of thiocyanatopentammineruthenium(III) [Ru(NH3)5(NCS)]2+, [Ru(NH3)5(SCN)]2+ and dithiocyanatotetrammineruthenium(III) [Ru(NH3)4(NCS)2]+ along with those of tetrathiocyanatodiammineruthenate(III) [Ru(NH3)2(SCN)4]? have been synthesized. The insoluble polymeric complex [Ru(NH3)2(SCN)2]n has also been prepared. The compounds have been characterized by chemical analyses, spectral (IR, UV and visible), magnetic susceptibility, conductivity, cyclic voltammetry and chromatography studies. 相似文献
9.
CLAUDIA L. PARKER OSCAR N. VENTURA STAN K. BURT RAÚL E. CACHAU 《Molecular physics》2013,111(17):2659-2668
We present a general purpose QM-MM-MD engine (DYNGA) designed to test alternative hybrid Hamiltonians geared towards the treatment of problems of interest in structural biology including the use of experimental data constraints. In this first presentation we use DYNGA to explore the behaviour of a traditional QM-MM approach in the treatment of the water—water interaction. We find the potential energy hypersurface for the water dimer computed with the HF 4–31G*/TIP3P hybrid Hamiltonian tends to be too flat. We also explore the effect of using traditional QM-MM techniques on proton wires and conclude there is a need for improvement, possibly addressed by using polarizable force fields. 相似文献
10.
Summary Isolation of coloured metal complexes of anisaldehyde thiosemicarbazone (HATSC) and anisaldehyde-4-phenylthiosemicarbazone (HAPTSC) of general formula [M(ATSC)2] and [M(APTSC)2]·2H2O are described. The room-temperature magnetic moment, i.r. and u.v. spectra, ligand field parameters and thermal characteristics are reported. The complexation occurs through deportonated thiol form of thiosemicarbazone and its azomethine nitrogen to yield 4- and 6-coordinate complexes. 相似文献