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371.
PdH2、YH2分子的结构与势能函数 总被引:6,自引:0,他引:6
用密度泛函理论的B3LYP方法,对钯和钇原子采用SDD收缩价基函数,氢原子采用6-311++G**全电子基函数,对PdH2和YH2体系的结构进行优化计算,得到PdH2分子最稳态为C2v构型,电子组态为1A1,平衡核间距RPdH=0.1692 nm,键角∠HPdH=29.4°,离解能De=5.5212 eV,基态简正振动频率:ν1(b2)=1470.1 cm-1、ν2(a1)=1007.9 cm-1、ν3(a1)=2907.0 cm-1.YH2分子最稳态也为C2v构型,电子组态2A1,RYH=0.1962 nm,∠HYH=114.3°,De=5.6691 eV,基态简正振动频率:ν1(b2)=1457.9 cm-1、ν2(a1)=476.0 cm-1、ν3(a1)=1506.3 cm-1.由微观过程的可逆性原理分析了分子的可能离解极限.并用多体项展式理论方法分别导出基态PdH2和YH2分子的势能函数,其等值势能面图准确地再现了PdH2和YH2分子的结构特征和离解能,由此讨论了Pd + H2和Y + H2分子反应的势能面静态特征. 相似文献
372.
373.
Yi‐Hang Wen Xia Feng Yin‐Hua He You‐Zhao Lan Hong Sun 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(11):m504-m506
In the title complex, [Zn(C12H6O4)(H2O)]n, a ZnII polymer based on naphthalene‐1,8‐dicarboxylate (1,8‐nap), the ZnII atoms adopt an elongated octahedral coordination geometry. A zigzag chain is formed by μ2‐aqua ligands and μ2‐carboxylate groups of the 1,8‐nap ligands. Adjacent parallel chains are further linked by 1,8‐nap ligands, forming a twisted two‐dimensional layer structure along the (100) plane. 相似文献
374.
375.
氯化二氯代四苯基叶啉磷(Dichloro(5,10,15,20-tetraphenylporphinato)-phosphorus(V)chloride,[PCl2TPP]Cl)是典型的非金属卟琳配合物.据文献报导[1]该配合物能够与噻吩类化合物反应,所得单体经电解氧化,可生成具有导电性的聚合物.因此,测定[PCl2TPP]Cl的分子结构有着十分重要的意义.1标题化合物的制备及单晶生长标题化合物技文献[2]合成.用于X-射线衍射的单晶样品是将标题化合物的二氯甲烷/正庚烷混合溶液静置数周后得到的.单晶为紫色,用于X-射线衍射测定的晶粒尺寸为0.38mm×0.38mm×0.28mm.… 相似文献
376.
A new simple, rapid and sensitive spectrophotometric flow injection method for the determination of trace iodide is described
based on an ion associate of iodate (IO3
–) with 2- (3,5-dibromo-2-pyridylazo)-5-diethylamino-phenol (3,5-Br2-PADAP) and thiocyanate (SCN–). In a strongly acidic medium, this unstable violet product was formed with an absorption maximum at 605 nm. Flow injection
is an ideal method to reproducibly monitor the transient signal. Various parameters were optimized using the Super Modified
Controlled Weighted Centroid Simplex Method (SMCWC). Under the optimum experimental conditions, iodide could be determined
in the range of 1.00 × 10–6 and 2.4 × 10–5 mol l–1. The correlation coefficient of the calibration curve is 0.9991. With a sampling frequency of 80 h–1, the detection limit for iodide is 5.0 × 10–7 mol l–1. The proposed method has been applied to the determination of trace iodide after oxidizing I– in table salt or laver to IO3
–. In addition, the mechanisms of the ion association reaction was studied.
Received: 15 August 1996 / Revised: 10 October 1996 / Accepted: 16 October 1996 相似文献
377.
A method has been described for the direct determinations of trace cadmium using derivative atom trapping flame atomic absorption spectrometry with an improved water-cooled stainless steel trapping equipment. The characteristic concentration (gave a derivative absorbance of 0.0044) and detection limit (3sigma) of cadmium were 0.028 and 0.02 ng ml(-1) when collecting for a 1 min, respectively, which were 992 and 145-fold better than those of the conventional flame atomic absorption spectrometry. The detection limit and sensitivity of the proposed method for a 2 min collection time were 1 and 2 orders of magnitude higher than those of conventional flame atomic absorption spectrometry. The present method was applied to the determinations of cadmium in water samples with a recovery range of 91 approximately 111% and a relative standard deviation of 4.7 approximately 5.6%. 相似文献
378.
A novel organic/inorganic compound [Hbenzimi]4[(benzimi)2Mo8O26] · 2H2O (1) has been prepared hydrothermally and characterized by elemental analyses, i.r., x.p.s., t.g. and single crystal X-ray diffraction.
The single crystal X-ray diffraction analysis reveals that compound (1) consists of the [Mo8O26]4− cluster as the structural motif covalently linked by benzimidazole molecules and protonated benzimidazole molecules as charge
compensation cations. It is interesting that the benzimidazole molecules were synthesized from 1,2-phenylenediamine and oxalic
acid. The [Mo8O26]4− polyoxoanions and organic ligands in compound (1) interact with each other via extensive hydrogen bonds to form a three-dimensional supramolecular framework. 相似文献
379.
A detailed computational study is performed on the radical-molecule reaction between the vinyl radical (C2H3) and formaldehyde (H2CO), for which only the direct hydrogen abstraction channel has been considered by previous and very recent theoretical studies. At the Gaussian-3//B3LYP/6-31G(d) and CBS-QB3 levels, the direct H-abstraction forming C2H4 + HCO has barriers of 3.9 and 4.7 kcal/mol, respectively. The addition barrier to form H2CCHCH2O has barriers of 2.8 and 2.3 kcal/mol, respectively. Subsequently, there are two highly competitive dissociation pathways for H2CCHCH2O: One is the formation of the direct H-extrusion product H2CCHCHO + H, and the other is the formation of C2H4 + HCO via the intermediate H2CCH2CHO. Surely, the released energy is large enough to drive the secondary dissociation of HCO to H + CO. Because the involved transition states and intermediates of the H2CCHCH2O evolution all lie energetically lower than the entrance addition transition state, the addition-elimination is more competitive than the direct H-transfer for the C2H3 + H2CO reaction, in contrast to previous expectation. The present results can be useful for future experimental investigation on the title reaction. 相似文献
380.
Direct determination of brucine by square wave voltammetry on 4-amino-2-mercaptopyrimidine self-assembled monolayer gold electrode 总被引:1,自引:0,他引:1
4-Amino-2-mercaptopyrimidine self-assembled monolayer (AMP SAMs/Au) was prepared on a gold electrode. The AMP SAMs/Au was characterized by using attenuated total reflection-fourier transform infrared (ATR-FTIR) and A.C. Impedance. The electrochemical behavior of brucine on AMP SAMs/Au was studied by cyclic voltammetry (CV) and square wave adsorptive stripping voltammetry (SWASV). The modified electrode showed an excellent electrocatalytic activity for the redox of brucine. The catalytic current increased linearly with the concentration of brucine in the range of 4.0 x 10(-7) to 2.0 x 10(-4) mol l(-1) by square wave voltammetry response. The detection limit was 6.0 x 10(-8) mol l(-1). 相似文献