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81.
82.
LIANG Hailong CHAI Baojie CHEN Guanghui CHEN Wei CHEN Sheng XIAO Hailan LIN Shujuan 《高等学校化学研究》2015,31(3):418-426
The proton-transfer between ammonia/water and HF/HBr without and with the stimulus of external electric fields(Eext) was investigated with the ab initio calculations. When external electric field is applied, the proton transfer occurs, resulting in ion-paired H4N+X- and H3O+X-(X=Br and F) from hydrogen-bonded complexes in view of the great changes of geometrical structures, dipole moments, frontier molecular orbitals and potential energy surfaces in the critical external electric fields(Ec) of 1.131×107 V/cm for H3N-HBr, 1.378×108 V/cm for H3N-HF, 9.358×107 V/cm for H2O-HBr and 2.304×108 V/cm for H2O-HF, respectively. Furthermore, one or three excess electrons can trigger the proton transfer from H3N-HBr and H3N-HF to H4N+Br- and H4N+F-, while two and four excess electrons can induce the proton transfer from H2O-HBr and H2O-HF to H3O+Br- and H3O+F-, respectively. Compared with that of the analogous NH3/H2O-HCl systems, the strength of Ec of proton transfer increases from HBr to HCl and HF for either H3N-HX or H2O-HX series, which is understandable by the fact that the acidity sequence is HBr>HCl>HF. And the larger of acidity of conjugated acid, the smaller of needed Ec. On the other hand, the Ec for the systems of NH3 with a stronger basicity is generally smaller than that of H2O systems for the same conjugated acid. 相似文献
83.
K.J. Hoffman 《Journal of Molecular Spectroscopy》2009,254(2):69-20334
Tuneable diode laser absorption spectroscopy has been used to measure the room temperature pressure broadening coefficients (γ) of rotational transitions in the v5 fundamental band of methyl bromide (12CH379Br and 12CH381Br) around 6.9 μm. Nitrogen, oxygen and self-broadening coefficients have been determined for 125 lines in the RQ1, PQ3, PQ5, PQ7 and PQ8 branches and 49 P and R branch transitions. Line profiles within Q branches were recorded at incremental pressures of nitrogen and oxygen up to 15 Torr and fitted to a Voigt profile to yield the broadening coefficients. The nitrogen broadened data for 14 lines, chosen from the five Q branches, were also fitted with Galatry profiles. The line profiles of the P and R branch transitions were recorded for total nitrogen and oxygen pressures of up to 300 Torr and fitted to both Voigt and Galatry profiles. Within individual Q branches, nitrogen broadening coefficients were found to decrease monotonically with increasing J from 0.14 cm−1 atm−1 at low J to 0.09 cm−1 atm−1 at high J. The corresponding values for oxygen were approximately 25% smaller. Self-broadening coefficients were found to vary between 0.48 and 0.16 cm−1 atm−1 with a similar J dependence to the foreign gas broadening for J > 20. However, between J = 2 and J ≈ 20 the broadening coefficient was found to increase with J. The magnitude of the pressure broadening coefficient for P and R branch transitions was found to closely follow the J dependence measured for the Q branch lines. 相似文献
84.
85.
A thorough review of 35/37Cl, 79/81Br, and 127I solid-state nuclear magnetic resonance (SSNMR) data is presented. Isotropic chemical shifts (CS), quadrupolar coupling constants, and other available information on the magnitude and orientation of the CS and electric field gradient (EFG) tensors for chlorine, bromine, and iodine in diverse chemical compounds is tabulated on the basis of over 200 references. Our coverage is through July 2005. Special emphasis is placed on the information available from the study of powdered diamagnetic solids in high magnetic fields. Our survey indicates a recent notable increase in the number of applications of solid-state quadrupolar halogen NMR, particularly 35Cl NMR, as high magnetic fields have become more widely available to solid-state NMR spectroscopists. We conclude with an assessment of possible future directions for research involving 35/37Cl, 79/81Br, and 127I solid-state NMR spectroscopy. 相似文献
86.
87.
通过溶胶凝胶法制备出LiMn2O4和LiMn1.92 Mg0.08O3.84Br0.16锤离子电池正极材料,并用XRD、SEM、XPS、充放电测试和CV对其结构、形貌、化学成份以及电化学性能进行了研究.结果表明,Mg、Br的掺杂未改变LiMn2O4的结构.在0.5C倍率下,LiMn1.92Mg0.08O3.84Br0.16的放电比容量为119 mAh/g,与LiMn2O4相比,其首次放电比容量提高了3.6;,循环100次后,LiMn1.92Mg0.08O3.84Br0.16的容量保持率高达86.9;.在5C倍率下,LiMn192Mg0.08O384Br0.16的放电比容量为91.1 mAh/g,比LiMn2O4提高了24.1;.实验表明,Mg、Br共同掺杂提高了LiMn2O4的放电比容量,并明显改善其循环稳定性和倍率性能,从而获得了较好的综合电化学性能. 相似文献
88.
采用各种固体核磁共振 (NMR) 技术详细研究了 H-MCM-22 分子筛中 Brnsted/Lewis 酸的协同效应. 二维 1H 双量子魔角旋转 (DQ-MAS) NMR 结果表明, 在脱铝 H-MCM-22 分子筛中 Brnsted 酸位 (骨架桥式羟基) 和 Lewis 酸位 (非骨架铝羟基) 之间是空间邻近的, 暗示着可能存在 B/L 酸协同效应. 二维 27Al DQ-MAS NMR 结果揭示了各种铝物种之间的空间邻近性, 表明 B/L 酸协同效应优先发生在 H-MCM-22 分子筛超笼中的骨架 T6 位铝和非骨架铝物种之间. 2-13C-丙酮探针分子实验发现, 因 B/L 酸协同效应而导致脱铝 H-MCM-22 分子筛酸性明显增强, 氘代吡啶探针分子实验也证实在 H-MCM-22 分子筛的超笼中发生了 B/L 酸协同效应. 上述结果将有助于我们理解在脱铝 H-MCM-22 分子筛上发生的多相催化机理. 相似文献
89.
《Analytical letters》2012,45(12):1999-2013
Abstract A simple, rapid, selective, and sensitive method for the derivative spectrophotometric determination of Hg(II) and its simultaneous determination in the presence of Zn(II) using 2‐(5‐bromo‐2‐pyridylazo)‐5‐diethylaminophenol in the presence of cetylpyridinium chloride, a cationic surfactant, has been developed. The molar absorption coefficient and analytical sensitivity of the 1∶1 Hg(II) complex at 558 nm (λmax) are 5.78×104 L mol?1 cm?1 and 0.67 ng mL?1, respectively. The detection limit of Hg(II) is 1.40×10?2 ng mL?1, and Beer's law is valid in the concentration range 0.05–2.40 µg mL?1. Overlapping spectral profiles of Hg(II) and Zn(II) complexes in zero‐order mode interfere in their simultaneous determination. However, 0.10–2.00 µg mL?1 of Hg(II) and 0.065–0.650 µg mL?1 of Zn(II), when present together, can be simultaneously determined at zero cross point of the derivative spectrum, without any prior separation. The relative standard deviation for six replicate measurements of solutions containing 0.134 µg mL?1 of Hg(II) and 0.620 µg mL?1 of Zn(II) is 1.72 and 1.47%, respectively. The proposed method has successfully been evaluated for trace level simultaneous determination of Hg(II) and Zn(II) in environmental samples. 相似文献
90.
In this paper,we give some interesting results concerning the entire function f(z) sharing a small function a CM with its difference operators or shifts. 相似文献