全文获取类型
收费全文 | 201篇 |
免费 | 27篇 |
国内免费 | 31篇 |
专业分类
化学 | 207篇 |
晶体学 | 1篇 |
力学 | 1篇 |
综合类 | 1篇 |
数学 | 25篇 |
物理学 | 24篇 |
出版年
2024年 | 1篇 |
2023年 | 1篇 |
2022年 | 8篇 |
2021年 | 8篇 |
2020年 | 9篇 |
2019年 | 6篇 |
2018年 | 13篇 |
2017年 | 9篇 |
2016年 | 11篇 |
2015年 | 10篇 |
2014年 | 14篇 |
2013年 | 12篇 |
2012年 | 10篇 |
2011年 | 17篇 |
2010年 | 10篇 |
2009年 | 11篇 |
2008年 | 10篇 |
2007年 | 12篇 |
2006年 | 15篇 |
2005年 | 10篇 |
2004年 | 6篇 |
2003年 | 10篇 |
2002年 | 8篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1998年 | 4篇 |
1996年 | 3篇 |
1995年 | 2篇 |
1994年 | 4篇 |
1993年 | 2篇 |
1992年 | 2篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 1篇 |
1987年 | 3篇 |
1984年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有259条查询结果,搜索用时 31 毫秒
51.
用QC ISD(T)/6-311 G(3DF,3PD)/MP2/6-311G(D,P)方法研究了H原子与CH3NH2的抽氢反应过程。该反应包含两个反应通道:H分别从CH3基团(R1)和NH2(R2)基团上抽氢。R1势垒比R2势垒低3.42kJ/mol,表明R1是主反应通道。在从头算的基础上,用变分过渡态理论(CVT)加小曲率隧道效应(SCT)研究了各反应温度范围为200~4000K内的速率常数,所得结果与实验值符合的很好。动力计算表明,在所研究的温度范围内,变分效应对速率常数的计算影响不大,而在低温范围内,隧道效应起了很重要的作用。 相似文献
52.
An O-methylated analog of protonated phenazine-di-N-oxide radical anion abstracts hydrogen from primary and secondary alcohols
in a slow (k
1 < 500 M−1 s−1) bimolecular reaction. No kinetic evidence has been found for the unimolecular release of free methoxyl radicals through
the homolytic N-OMe bond cleavage in these species. DFT calculations at the UB3LYP 6-31G(d) level indicate that protonated
and O-alkylated radical anions of pyrazine, quinoxaline and phenazine di-N-oxides are close analogues of aromatic nitroxyl
radicals with the highest spin density localized on the oxygen and nitrogen of the nitrone moiety. 相似文献
53.
R. G. Gasanov 《Russian Chemical Bulletin》2000,49(1):46-49
The rate constants for reactions of Cl abstraction from CCl4 by CCl3CH2·CHR radicals and Br abstraction from CCl3CH2CHBrR (R=Bun, AcO, OCNC4H8, CN) by·Re(CO)5 radicals were determined by ESR spectroscopy using spin trapping technique. Replacement of H atoms at the C(β) atom by O
or N atoms reduces the reactivity of the radicals in the reactions of Cl abstraction from CCl4 by approximately an order of magnitude. The presence of two polar groups at the C(β) atom results in appreciable decrease
in the strength of the C−Br bond in CCl3CH2CHBrR adducts.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 45–48, January, 2000. 相似文献
54.
55.
采用双水平直接动力学方法对C2H3与CH3F氢抽提反应进行了研究. 在QCISD(T)/6-311++G(d, p)//B3LYP/6-311G(d, p)水平上, 计算的三个反应通道R1、R2和R3的能垒(ΔE≠)分别为43.2、43.9和44.1 kJ·mol-1, 反应热为-38.2 kJ·mol-1. 此外, 利用传统过渡态理论(TST)、正则变分过渡态理论(CVT)和包含小曲率隧道效应(SCT)的CVT, 分别计算了200-3000 K温度范围内反应的速率常数kTST、kCVT和kCVT/SCT. 结果表明: (1) 三个氢抽提反应通道的速率常数随温度的增加而增大, 其中变分效应的影响可以忽略, 隧道效应则在低温段影响显著; (2) R1反应是主反应通道, 但随着温度的升高, R2反应的竞争力增大, 而R3反应对总速率常数的影响很小. 相似文献
56.
Debasree Raychaudhuri 《International Journal of Mathematical Education in Science & Technology》2013,44(8):1239-1256
There are numerous theories that offer cognitive processes of students of mathematics, all documenting various ways to describe knowledge acquisition leading to successful transitions from one stage to another, be it characterized by Dubinsky's encapsulation, Sfard's reification or Piaget's equilibration. We however are interested in the following question. Who succeeds at making the leap and can we describe the attributes that set them apart from the ones that do not? In this article, we offer a framework to categorize students as learners based on their individual approaches towards learning concepts in differential equations and related concepts – as demonstrated by their efforts to resolve a conflict, conserve and rebuild their cognitive structures. 相似文献
57.
金刚石(111)氢化表面脱氢势垒的量子化学研究 总被引:2,自引:0,他引:2
采用MNDO(UHF)方法,计算金刚石(111)面的脱氢势垒。在与气相有机分子脱氢活化能实验值系统比较的基础上,在一组尺度不同的金刚石表面团簇模型上进行了计算,结果收敛于42±4kJ/mol.并与MNDO(RHF)和AM1(UHF、RHF)方法给出的相应结果进行了比较。 相似文献
58.
We have used the single‐pulse shock tube technique with postshock GC/MS product analysis to investigate the mechanism and kinetics of the unimolecular decomposition of isopropanol, a potential biofuel, and of its reaction with H atoms at 918‐1212 K and 183‐484 kPa. Experiments employed dilute mixtures in argon of isopropanol, a radical scavenger, and, for H‐atom studies, two different thermal precursors of H. Without an added H source, isopropanol decomposes in our studies predominantly by molecular dehydration. Added H atoms significantly augment decomposition, mainly by abstraction of the tertiary and primary hydrogens, reactions that, respectively, lead to acetone and propene as stable organic products. Traces of acetaldehyde were observed in some experiments above ≈ 1100 K and establish branching limits for minor decomposition pathways. To quantitatively account for secondary chemistry and optimize rate constants of interest, we employed the method of uncertainty minimization using polynomial chaos expansions (MUM‐PCE) to carry out a unified analysis of all datasets using a chemical model–based originally on JetSurF 2.0. We find: k(isopropanol → propene + H2O) = 10(13.87 ± 0.69) exp(?(33 099 ± 979) K/ T) s?1 at 979‐1212 K and 286‐484 kPa, with a factor of two uncertainty (2σ), including systematic errors. For H atom reactions, optimization yields: k(H + isopropanol → H2 + p‐C3H6OH) = 10(6.25 ± 0.42) T2.54 exp(?(3993 ± 1028) K /T) cm3 mol?1 s?1 and k(H + isopropanol → H2 + t‐C3H6OH) = 10(5.83 ± 0.37) T2.40 exp(?(1507 ± 957) K /T) cm3 mol?1 s?1 at 918‐1142 K and 183‐323 kPa. We compare our measured rate constants with estimates used in current combustion models and discuss how hydrocarbon functionalization with an OH group affects H abstraction rates. 相似文献
59.
Dr. Allegra Franchino Àlex Martí Dr. Stefano Nejrotti Prof. Antonio M. Echavarren 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(46):11989-11996
A library of gold(I) chloride complexes with phosphine ligands incorporating pendant (thio)urea and squaramide H-bond donors was prepared with the aim of promoting chloride abstraction from Au(I) via H-bonding. In the absence of silver additives, complexes bearing squaramides and trifluoromethylated aromatic ureas displayed good catalytic activity in the cyclization of N-propargyl benzamides, as well as in a 1,6-enyne cycloisomerization, a tandem cyclization-indole addition reaction and the hydrohydrazination of phenylacetylene. Kinetic studies and DFT calculations indicate that the energetic span of the reaction is accounted by both the chloride abstraction step, facilitated by the bidentate H-bond donor via an associative mechanism, and the subsequent cyclization step. 相似文献
60.
Shufeng Guo 《代数通讯》2019,47(8):3170-3180