全文获取类型
收费全文 | 426篇 |
免费 | 76篇 |
国内免费 | 169篇 |
专业分类
化学 | 498篇 |
晶体学 | 7篇 |
力学 | 5篇 |
综合类 | 3篇 |
数学 | 10篇 |
物理学 | 148篇 |
出版年
2023年 | 8篇 |
2022年 | 14篇 |
2021年 | 13篇 |
2020年 | 30篇 |
2019年 | 16篇 |
2018年 | 15篇 |
2017年 | 18篇 |
2016年 | 27篇 |
2015年 | 20篇 |
2014年 | 23篇 |
2013年 | 31篇 |
2012年 | 35篇 |
2011年 | 25篇 |
2010年 | 16篇 |
2009年 | 27篇 |
2008年 | 32篇 |
2007年 | 36篇 |
2006年 | 31篇 |
2005年 | 29篇 |
2004年 | 37篇 |
2003年 | 14篇 |
2002年 | 41篇 |
2001年 | 21篇 |
2000年 | 9篇 |
1999年 | 20篇 |
1998年 | 18篇 |
1997年 | 15篇 |
1996年 | 10篇 |
1995年 | 5篇 |
1994年 | 8篇 |
1993年 | 4篇 |
1992年 | 6篇 |
1991年 | 3篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有671条查询结果,搜索用时 15 毫秒
31.
Novel vibrational circular dichroism (VCD) studies in the CH region of a series of methyl glycosidic carbohydrates were examined. The specific CH stretching VCD band predicts absolute stereochemistries of their anomeric positions. The C-1 chiral information was extracted to the methoxy substituent as a probe. The concept of the vibrational chirality probe from a single chiral center in the presence of numerous such centers might be useful in determining the absolute configuration, when a multiplicity of chiral centers is present in a molecule such as a carbohydrate. 相似文献
32.
添加剂铜和银离子对MnO2催化燃烧CH4的影响 总被引:2,自引:1,他引:2
催化燃烧法,由于起燃温度低、去除率高、适用氧浓度范围大、无二次污染、燃烧缓和等,是国内外治理有机废气时,回收利用能量最有效的方法之一[1].但目前用于该过程的催化剂中均含有来源有限、价格昂贵的贵金属铂或钯[2].因此,寻找来源丰富、价格低廉、性能相当... 相似文献
33.
Yi‐Zhen Tang Hao Sun Ya‐Ru Pan Xiu‐Mei Pan Rong‐Shun Wang 《International journal of quantum chemistry》2007,107(6):1495-1501
The mechanisms for the reaction of CH3S with NO2 are investigated at the QCISD(T)/6‐311++G(d,p)//B3LYP/6‐311++G(d,p) on both single and triple potential energy surfaces (PESs). The geometries, vibrational frequencies, and zero‐point energy (ZPE) correction of all stationary points involved in the title reaction are calculated at the B3LYP/6‐311++G(d,p) level. More accurate energies are obtained at the QCISD(T)/6‐311++G(d,p). The results show that 5 intermediates and 14 transition states are found. The reaction is more predominant on the single PES, while it is negligible on the triple PES. Without any barrier height for the whole process, the main channel of the reaction is to form CH3SONO and then dissociate to CH3SO+NO. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
34.
Addition reaction of two geometrical isomers of 1-chlorovinyl p-tolyl sulfoxides, derived from unsymmetrical ketones and chloromethyl p-tolyl sulfoxide, with lithium enolate of tert-butyl acetate gave single isomers of the adduct, respectively. Treatment of each diastereomer with i-PrMgCl resulted in the formation of magnesium carbenoids. Highly regiospecific 1,3-CH insertion reaction was found to take place from the magnesium carbenoids to afford cyclopropanes in high yields. Stereochemistry of the adducts, reaction mechanism, and origin of the regiospecificity are discussed. 相似文献
35.
Laura Masgrau Àngels González-Lafont José M. Lluch 《Theoretical chemistry accounts》2002,108(1):38-40
Variational transition state theory including tunneling corrections (as implemented in Polyrate 8.7) and using multilevel
energy calculations at the MCCM-CCSD(T)-1sc level for the CH4 + OH reaction and at the MCCM-CCSD(T)-2m level for the CD4 + OH process, reproduces very well the experimental rate constants. However, no single methodology was found that reproduces
equally well the experimental rate constants for both title reactions.
Received: 24 March 2002 / Accepted: 11 April 2002 / Published online: 4 July 2002 相似文献
36.
The iterative difference-dedicated CI method (IDDCI) has been applied to determine excitation energies in small systems for
which benchmark FCI and other high-level calculations exist. Transitions to excited singlet and triplet states in Be and vertical
transitions in CH+, BH and CH2 are reported. The deviations from FCI results are lower than 0.1 eV and compare advantageously with SDCI including size-consistency
corrections, (SC)2SDCI, and with coupled cluster calculations including the effect of triples, especially for the states which have a predominant
double excitation character. The IDDCI procedure has been speeded up by using smaller subspaces for optimizing the molecular
orbitals.
Received: 17 January 1997 / Accepted: 31 July 1997 相似文献
37.
The photodissociation of methyl iodide in various matrices at low temperature was studied. The observed Raman spectra excited by 514.5 nm laser radiation showed that there were two different photolytically produced iodine species isolated in the matrices after illumination by a medium pressure mercury lamp. One species which was dominant at lower iodine concentrations and exhibited a progression with an ωe of 201 cm?1, belonged to the matrix isolated iodine monomer (I2). The other species, which was dominant at higher iodine concentrations with an ωe of approximately 180 cm?1, belonged to the iodine aggregate ((I2)n). Five progressions of resonance Raman or resonance fluorescence of these two species were also observed in the other matrices. The iodine aggregate in the methyl iodide matrix at 77 K was formed in a crystalline structure, while the photolytically generated iodine aggregate from CH3I/Ar (2/3) matrix at 10 K, after illumination with a mercury lamp, was in amorphous form. The rearrangement of photolytically produced iodine aggregate in methyl iodide matrix was observed as a function of the duration of illumination. Local heating effects of the laser radiation might induce the iodine monomer to aggregate in matrices. The photodissociation mechanism of methyl iodide in matrices is also proposed. 相似文献
38.
CH_3自由基和O(~3P)反应机理的量子化学研究 总被引:4,自引:0,他引:4
用分子轨道从头计算MP2(full)方法和密度泛函理论(DFT)中的B3LYP方法 研究了CH_3自由基和三线态O原子反应的微观机理,优化得到了反应途径上的反应 物、过渡态、中间体和产物的几何构型,通过振动分析对过渡态和中间体构型进行 了确认,在G3不平上计算了能量,同时用经典过渡态理论对该反应的绝对速率常数 进行了理论计算。研究结果表明:CH_3自由基与O(~3P)反应有四条不同的放热反 应通道,主反应通道为IM1→TS1→CH_2O + H,同时反应可彻底裂解生成CO, H_2 及H。 相似文献
39.
40.
Dr. Alexia Ville Dr. Julien Annibaletto Dr. Sébastien Coufourier Prof. Christophe Hoarau Dr. Rodolphe Tamion Dr. Guillaume Journot Dr. Cédric Schneider Dr. Jean-François Brière 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(56):13961-13965
An efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA. 相似文献