全文获取类型
收费全文 | 1020篇 |
免费 | 43篇 |
国内免费 | 5篇 |
专业分类
化学 | 781篇 |
晶体学 | 9篇 |
力学 | 21篇 |
数学 | 41篇 |
物理学 | 216篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 15篇 |
2020年 | 22篇 |
2019年 | 22篇 |
2018年 | 13篇 |
2017年 | 6篇 |
2016年 | 27篇 |
2015年 | 23篇 |
2014年 | 17篇 |
2013年 | 61篇 |
2012年 | 79篇 |
2011年 | 81篇 |
2010年 | 34篇 |
2009年 | 62篇 |
2008年 | 67篇 |
2007年 | 64篇 |
2006年 | 51篇 |
2005年 | 72篇 |
2004年 | 51篇 |
2003年 | 48篇 |
2002年 | 40篇 |
2001年 | 13篇 |
2000年 | 19篇 |
1999年 | 14篇 |
1998年 | 8篇 |
1997年 | 3篇 |
1996年 | 11篇 |
1995年 | 7篇 |
1994年 | 2篇 |
1993年 | 2篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 9篇 |
1989年 | 2篇 |
1988年 | 6篇 |
1987年 | 10篇 |
1986年 | 5篇 |
1985年 | 9篇 |
1984年 | 12篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1980年 | 4篇 |
1979年 | 5篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 5篇 |
1973年 | 4篇 |
排序方式: 共有1068条查询结果,搜索用时 46 毫秒
151.
Ito F Ishibashi Y Khan SR Miyasaka H Kameyama K Morisue M Satake A Ogawa K Kobuke Y 《The journal of physical chemistry. A》2006,110(47):12734-12742
Photoinduced electron transfer (ET) and excitation energy transfer (ENT) reactions in monomer and slipped-cofacial dimer systems of a directly linked Zn porphyrin (Por)-Zn phthalocyanine (Pc) heterodyad, ZnPc-ZnPor, were investigated by means of the picosecond and femtosecond transient absorption spectroscopies. In the dimer dyad system of two heterodyads connected through the coordination bond between two imidazolyl-substituted ZnPor bearing ZnPc, ZnPc-ZnPor(D), the rapid ENT from the ZnPor to ZnPc in the subpicosecond time region was followed by photoinduced charge separation (CS) and charge recombination (CR) with time constants of 47 and 510 ps, respectively. On the other hand in the monomer dyad system, no clear charge-separated state was observed although the CS with a time constant of 200 ps and CR with < or =70 ps were estimated. These results indicated that the dimer slipped-cofacial arrangement of pair porphyrins is advantageous for the effective production of the CS state. This advantage was discussed from the viewpoint of a decrease in the reorganization energy of the dimer relative to that of the monomer system. In addition, the electrochemical measurements indicated that the strong interaction between ZnPc and ZnPor moieties also contributed to the fast CS process despite the marginal driving force for the CS process. The dimer dyad of ZnPc-ZnPor provides full advantages in efficiencies of the light harvesting and the CS state production. 相似文献
152.
Uchiyama M Ozawa H Takuma K Matsumoto Y Yonehara M Hiroya K Sakamoto T 《Organic letters》2006,8(24):5517-5520
We systematically investigated, for the first time, the relationship between regioselectivity and acid/base effects in the cyclization reactions between carboxylic acids and carbon-carbon triple bonds. We found novel acid- and base-promoted cyclizations to selectively give isocoumarin or pyran-2(2H)-one and phthalide or furan-2(5H)-one skeletons, respectively, and established a catalytic version of regioselective heterocyclic ring synthesis. Density functional theory calculations and application to a short route to thunberginol A were also described. [reaction: see text]. 相似文献
153.
Kazuto Koike Gen-you Takada Kazuya Fujimoto Shigehiko Sasa Masataka Inoue Mitsuaki Yano 《Physica E: Low-dimensional Systems and Nanostructures》2006,32(1-2):191
Thermal stability of single-crystalline [ZnO]m[Zn0.7Mg0.3O]n multiple quantum wells (MQWs) grown on a-plane sapphire substrates by plasma-assisted molecular beam epitaxy is reported. X-ray diffraction analysis revealed that these MQWs were grown as designed with a fixed Zn0.7Mg0.3O barrier width of and a series of ZnO well widths of . Cathodoluminescence spectra from these MQWs consisted of two major peaks; one was the emission from the bound excitons in Zn0.7Mg0.3O barrier layers, and the other was that from the confined excitons in ZnO well layers. These structural and optical properties were found to be dramatically changed by the ex situ annealing treatments over 700 °C. These changes were presumably due to the onset of phase separation of the Zn0.7Mg0.3O barrier layers with pronounced Mg diffusion toward the ZnO wells. 相似文献
154.
155.
INTRODUCTION The tensor associated with a Raman band plays an important role in determining the band intensity and its structural significance. Each Raman tensor interrelates two electric vectors, that of the exciting radiation (i.e. laser photon) and that of the Raman scattered radiation (i.e. the inelastically scattered photon which results from the exchange of a vibrational quantum between the exciting photon and the molecule). The Raman tensor is obtained formally as the first derivative of the molecular polarizability tensor, the derivative being taken with respect to the vibrational normal coordinate. In other words, the Raman tensor associated with a vibrational Raman band is an indicator of how the polarizability of the molecule oscillates with the molecular normal mode of vibration. 相似文献
156.
157.
Kazuya Tachibana 《辐射效应与固体损伤》2013,168(2):135-137
Abstract Redistribution of phosphorus dopant in 1N2175 phototransistors damaged by a pulsed neodynium laser has been investigated using the electron microprobe technique. Four different effects observed in the concentration profdes were explained by the action of diffusion and segregation, in the presence of temperature and compositional gradients. One specific effect was analyzed using a simplified model consisting of diffusion in the melt followed by the segregation upon refreezing. It was estimated that certain areas of the phototransistor surface remained above the melting point for times of the order of 10?4 sec. Correlation was made between the results of these microprobe measurements and previously observed laser-damage effects in the electrical characteristics. It is suggested that impurity migration may be an important mechanism for damage to junction devices by pulsed lasers in an intermediate energy range. 相似文献
158.
Transverse wave generation mechanism in rotating detonation 总被引:2,自引:0,他引:2
Yuho Uemura A. Koichi Hayashi Makoto Asahara Nobuyuki Tsuboi Eisuke Yamada 《Proceedings of the Combustion Institute》2013,34(2):1981-1989
Detonation engines are expected to be included in a number of aerospace thrusters in the future. Several types of detonation engines are currently under examination, including the rotating detonation engine (RDE). Although the RDE has been explored experimentally, its rotating detonation propagation mechanism is not well understood. This paper clarifies the detonation mechanism and dynamics of the RDE by 2D and 3D simulation using compressible Euler equations with a full chemical reaction mechanism of H2/O2 and H2/Air, especially from the triple-point and transverse detonation points of view. A total variation diminishing (TVD) scheme is used for the mixture of H2/Air, and an advection upwind splitting method difference vector (AUSMDV) scheme is used for the mixture of H2/O2. The use of an AUSMDV scheme provides a much clearer detonation structure than does the TVD scheme. We focus on the complex interaction mechanism of the detonation front and burned mixture gases. We found out that at this interaction point, an unreacted gas pocket appears and ignites periodically to generate transverse waves at the detonation front and maintain detonation propagation. 相似文献
159.
T. Tsuboi 《Phase Transitions》2013,86(1-2):119-124
Two anomalous behaviors are observed in the Raman spectra of BaMnF4 at room temperature. One is that the number of Raman lines is smaller than that expected for the orthorhombic crystal structure with C 2ν 12 symmetry, the other is that, of the b(aa)c, a(bb)c, and b(cc)a scattering geometries giving the same A1-symmetry spectrum, the number of Raman lines in the b(aa)c spectrum is considerably smaller than those in the other two spectra. It is suggested that rotation of MnF6 octahedra about c-axis occurring in the orthorhombic phase is responsible for the former behavior, and Ba2+-ion displacement along a-axis for the latter one. 相似文献
160.
Keiichi Murai Lukas Lauterbach Kazuya Teramoto Zhiyang Quan Lena Barra Tsuyoshi Yamamoto Kenichi Nonaka Kazuro Shiomi Makoto Nishiyama Tomohisa Kuzuyama Jeroen S. Dickschat 《Angewandte Chemie (International ed. in English)》2019,58(42):15046-15050
The skeletons of some classes of terpenoids are unusual in that they contain a larger number of Me groups (or their biosynthetic equivalents such as olefinic methylene groups, hydroxymethyl groups, aldehydes, or carboxylic acids and their derivatives) than provided by their oligoprenyl diphosphate precursor. This is sometimes the result of an oxidative ring‐opening reaction at a terpene‐cyclase‐derived molecule containing the regular number of Me group equivalents, as observed for picrotoxan sesquiterpenes. In this study a sesquiterpene cyclase from Trichoderma spp. is described that can convert farnesyl diphosphate (FPP) directly via a remarkable skeletal rearrangement into trichobrasilenol, a new brasilane sesquiterpene with one additional Me group equivalent compared to FPP. A mechanistic hypothesis for the formation of the brasilane skeleton is supported by extensive isotopic labelling studies. 相似文献