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71.
Lehnig R Slipchenko M Kuma S Momose T Sartakov B Vilesov A 《The Journal of chemical physics》2004,121(19):9396-9405
The laser-induced fluorescence (LIF) excitation spectra of free base phthalocyanine (Pc), Mg-Pc, and Zn-Pc molecules in superfluid helium droplets at T=0.38 K have been studied. The spectra reveal the rich vibronic structure of the S(1)<--S(0) electronic transitions. The band origins of the transitions consist of zero phonon lines accompanied by phonon wings, which originate from simultaneous electronic excitation of the molecule and excitation of the collective modes of the helium surrounding it. The phonon wings have discrete structures suggesting localization of some helium atoms in the neighborhood of the molecules. Zero phonon lines of Mg-Pc and Zn-Pc molecules are split into three components, which are separated by 0.2-0.4 cm(-1). Possible mechanism of splitting involves static or dynamic Jahn-Teller interaction of metal-phthalocyanine molecules in the twofold degenerate S(1)((1)E(u)) state with the helium shell. 相似文献
72.
Andrés R Galakhov MV Gómez-Sal MP Martín A Mena M del Carmen Morales-Varela M Santamaría C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(4):805-811
The photochemical treatment of mu(3)-alkylidyne complexes [[TiCp*(mu-O)](3)(mu(3)-CR)] (R=H (1), Me (2), Cp*=eta(5)-C(5)Me(5)) with the amines (2,6-Me(2)C(6)H(3))NH(2), Et(2)NH, and Ph(2)NH and the imine Ph(2)C=NH leads to the partial hydrogenation of the alkylidyne moiety that is supported on the organometallic oxide, [Ti(3)Cp*O(3)], and the formation of new oxoderivatives [[TiCp*(3)(mu-CHR)(R'NR")] (R"=2,6-Me(2)C(6)H(3), R'=H, R=H (3), Me (4); R'=R"=Et, R=H (5), Me (6); R'=R"=Ph, R=H (7), Me (8)) and [[TiCp*(mu-O)](3)(mu-CHR)(N=CPh(2))] (R=H (9), R=Me (10)), respectively. A sequential transfer hydrogenation process occurs when complex 1 is treated with tBuNH(2), which initially gives the mu-methylene [[TiCp*(mu-O)](3)(mu-CH(2))(HNtBu)] (11) complex and finally, the alkyl derivative [[TiCp*(mu-O)](3)(mu-NtBu)Me] (12). Furthermore, irradiation of solutions of the mu(3)-alkylidyne complexes 1 or 2 in the presence of diamines o-C(6)H(4)(NH(2))(2) and H(2)NCH(2)CH(2)NH(2) (en) affords [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(6)H(4)NH)] (13) and [[TiCp*(mu-O)](3)(mu(3)-eta(2)-NC(2)H(4)NH)] (14) by either methane or ethane elimination, respectively. In the reaction of 1 with en, an intermediate complex [[TiCp*(mu-O)](3)(mu-CH(2))(NHCH(2)CH(2)NH(2))] (15) is detected by (1)H NMR spectroscopy. Thermal treatment of the complexes 4-10 quantitatively regenerates the starting mu(3)-alkylidyne compounds and the amine R'(2)NH or the imine Ph(2)C=NH; however, heating of solutions of 3 or 4 in [D(6)]benzene or a equimolecular mixture of both at 170 degrees C produces methane, ethane, or both, and the complex [[TiCp*(mu-O)](3)[mu(3)-eta(2)-NC(6)H(3)(Me)CH(2)]] (16). The molecular structure of 8 has been established by single-crystal X-ray analysis. 相似文献
73.
Mikhail I. Kodess Marina A. Ezhikova Galina L. Levit Victor P. Krasnov Valery N. Charushin 《Journal of organometallic chemistry》2005,690(11):2766-2768
Experimental conditions for determination of enantiomeric composition of 1-substituted 3-aminocarboranes by 1H and 13C NMR spectroscopy using chiral shift reagent Eu(hfc)3 have been found. 相似文献
74.
E. N. Yurchenko L. G. Matvienko L. I. Kuznetsova Yu. D. Pankratiev K. I. Matveev 《Reaction Kinetics and Catalysis Letters》1976,4(3):405-411
The heats of interaction of VO
2
+
and of heteropolyacids H3+nPMo12−nVnO40 (n=1,2,3,6) with N2H4 have been measured.
Измерены теплоты взаимодействия VO 2 + и гетерополикислот H3+nPMo12−nVnO40 (n=1,2,3,6) с N2H4.相似文献
75.
Igarashi RY Laryukhin M Dos Santos PC Lee HI Dean DR Seefeldt LC Hoffman BM 《Journal of the American Chemical Society》2005,127(17):6231-6241
We here show that the iron-molybdenum (FeMo)-cofactor of the nitrogenase alpha-70(Ile) molybdenum-iron (MoFe) protein variant accumulates a novel S = (1)/(2) state that can be trapped during the reduction of protons to H(2). (1,2)H-ENDOR measurements disclose the presence of two protons/hydrides (H(+/)(-)) whose hyperfine tensors have been determined from two-dimensional field-frequency (1)H ENDOR plots. The two H(+/)(-) have large isotropic hyperfine couplings, A(iso)( )() approximately 23 MHz, which shows they are bound to the cofactor. The favored analysis for these plots indicates that the two H(+/)(-) have the same principal values, which indicates that they are chemically equivalent. The tensors are further related to each other by a permutation of the tensor components, which indicates an underlying symmetry of binding relative to the cofactor. At present, no model for the structure of the iron-molybdenum (FeMo)-cofactor in the S = (1)/(2) state trapped during the reduction of H(+) can be shown unequivocally to satisfy all of the constraints generated by the ENDOR analysis. The data disfavors any model that involves protonation of sulfides, and thus suggests that the intermediate instead contains two chemically equivalent bound hydrides; it appears unlikely that these are terminal monohydrides. 相似文献
76.
M. A. Khilla H. Mikhail A. Abu-El Soud Z. M. Hanafi 《Czechoslovak Journal of Physics》1980,30(9):1039-1045
Magnetic susceptibility measurements were done on MoO3, MoO2 and some suboxides in between. The mass susceptibilities ×106 for MoO3, Mo13O38, Mo9O26, Mo8O23, Mo17O47, Mo4O11 and MoO2 were as follows 0·02, 0·055, 0·11, 0·160, 0·0937, 0·123 and 0·20 respectively. They were all feebly paramagnetic and attempts were made to interpret these data. The effect of temperature on the specific susceptibility was also studied. 相似文献
77.
Structural and magnetic properties of iron(II) complexes with 1,4,5,8,9,12-hexaazatriphenylene (HAT)
Shatruk M Chouai A Prosvirin AV Dunbar KR 《Dalton transactions (Cambridge, England : 2003)》2005,(11):1897-1902
Reactions of Fe(II) salts with the ligand 1,4,5,8,9,12-hexaazatriphenylene (HAT) led to the isolation and characterization of four new compounds: [Fe3(HAT)(H2O)12](SO4)3.3.3H2O (1), [Fe2(HAT)(SO4)(H2O)5](SO4).2H2O.CH3OH (2), [Fe2(HAT)(SO4)(H2O)5](SO4).3H2O (3), and [Fe3Cl5(HAT)(CH3OH)4(H2O)]Cl (4). Compound 1 crystallizes as a trinuclear cluster in which HAT acts as a tris-chelating ligand. Compounds 2 and 3 are two polymorphs of an infinite one-dimensional structure in which the Fe atoms are coordinated to HAT and then connected into the chain through bridging sulfate anions. Compound 4 exhibits a similar chain structure, but with bridging chloride ligands. The magnetic behavior of the new compounds is indicative of weak antiferromagnetic coupling between the Fe(II) centers through the HAT ligand. 相似文献
78.
Investigation of the LaI2/H2 System: Phase Relations and Stacking Disorder Heating of LaI2 under 1 bar hydrogen pressure to 650 °C leads to light gray LaI2H0.95(3), accompanied by a structural change from tetragonal to hexagonal. Sharp reflections in the XRD pattern can be indexed in P63/mmc with a = 4.2158(7)Å and c = 15.508(3)Å, however, diffuse reflections indicate the presence of stacking faults in the structure, which correspond to a polytypic intergrowth of MoS2 and NbS2 type structural fragments. Increasing the reaction temperature to 730 °C results in a better defined diffraction pattern with the peak positions close to those of the 2H‐NbS2 structure type. An X‐ray powder study of the samples LaI2Hn proved the miscibility gap between LaI2 and LaI2Hn (0 ≤ n ≤ 0.5) in agreement with previous results. With decreasing H‐content of the homogeneous phase the lattice parameters change in opposite direction, a increasing to 4.236(1)Å and c decreasing to 15.39(2)Å for the lower limit. 相似文献
79.
Palladium(II) bromide reacts with gallium(III) bromide in the presence of arenes yielding binuclear palladium(I) complexes [Pd2(GaBr4)2(arene)2], where arene=benzene (1), toluene (2) and p-xylene (3). Reaction of palladium(II) chloride with gallium(III) chloride in p-xylene leads to the analogous palladium(I) compound [Pd2(GaCl4)2(p-xylene)2] (4); the X-ray structures of 1-4 were determined. 相似文献
80.
Yu. V. Maksimov V. V. Matveev V. D. Tyurin A. N. Muratov A. I. Nekhaev I. P. Suzdalev 《Russian Chemical Bulletin》1991,40(4):674-680
Thermal decomposition of the [FeCp(SPh)CO]2 complex and its reaction with the surface of activated silica gel were investigated by Mössbauer spectroscopy. A small amount of a complex with properties similar to ferrocene is separated in the first stage of thermal decomposition (120–130°C). The starting carbonyl complex totally disappears in the second stage (165–210°C), and two compounds are present among the products: a derivative of ferrocene and the final product, an x-ray amorphous, iron-containing structure with an ionic-covalent type of chemical bond (CB) and a 25 and 5 wt. % concentration of oxygen and sulfur, respectively. The Mössbauer parameters of this product and the compound formed in the reaction of [FeCp(SPh)CO]2 with the surface of activated silica gel at 4.2–300 K are identical. The analysis of the data suggested that both structures are highly disperse clusters of iron oxide with the structure of an inverted spinel with superparamagnetic properties.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 771–778, April, 1991.We would like to thank Yu. B. Kopylovskii for assistance in processing the spectra with the MESLIN program. 相似文献