全文获取类型
收费全文 | 477篇 |
免费 | 40篇 |
专业分类
化学 | 411篇 |
晶体学 | 7篇 |
力学 | 1篇 |
数学 | 3篇 |
物理学 | 95篇 |
出版年
2022年 | 3篇 |
2021年 | 2篇 |
2020年 | 6篇 |
2019年 | 5篇 |
2018年 | 6篇 |
2017年 | 3篇 |
2016年 | 10篇 |
2015年 | 16篇 |
2014年 | 14篇 |
2013年 | 21篇 |
2012年 | 19篇 |
2011年 | 41篇 |
2010年 | 23篇 |
2009年 | 15篇 |
2008年 | 36篇 |
2007年 | 35篇 |
2006年 | 30篇 |
2005年 | 31篇 |
2004年 | 31篇 |
2003年 | 20篇 |
2002年 | 24篇 |
2001年 | 14篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 7篇 |
1997年 | 3篇 |
1996年 | 1篇 |
1995年 | 2篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 4篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 6篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 8篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 8篇 |
1976年 | 2篇 |
1975年 | 1篇 |
1974年 | 4篇 |
1973年 | 1篇 |
1967年 | 3篇 |
排序方式: 共有517条查询结果,搜索用时 15 毫秒
1.
Femtosecond laser is a perfect laser source for materials processing when high accuracy and small structure size are required. Due to the ultra short interaction time and the high peak power, the process is generally characterized by the absence of heat diffusion and, consequently molten layers. Various induced structures have been observed in materials after the femtosecond laser irradiation. Here, we report on fabrication of micro-optical devices by the femtosecond laser. 1) formation of optical waveguide with internal loss less than 0.5dB/cm in the wavelength region from 1.2 to 1.6 mm, by translating a silica glass perpendicular to the axis of the focused femtosecond laser beam; 2) nano-scale valence state manipulation of active ions inside transparent materials; 3) space-selective precipitation and control of metal nanoparticles inside transparent materials; The mechanisms and applications of the femtosecond laser induced phenomena were also discussed. 相似文献
2.
Shigeru Katayama Mika Horiike Kazuyuki Hirao Naoto Tsutsumi 《Journal of Polymer Science.Polymer Physics》2002,40(24):2800-2806
We investigated the structures induced by an irradiation of a near‐infrared (NIR) femtosecond laser pulse in dye‐doped polymeric materials {poly(methyl methacrylate) (PMMA), thermoplastic epoxy resin (Epoxy), and a block copolymer of methyl methacrylate and ethyl acrylate‐butyl acrylate [p(MMA/EA‐BA) block copolymer]}. Dyes used were classified into two types—type 1 with absorption at 400 nm and type 2 with no absorption at 400 nm. The 400‐nm wavelength corresponds to the two‐photon absorption region by the irradiated NIR laser pulse at 800 nm. Type 1 dye‐doped PMMA and p(MMA/EA‐BA) block copolymer showed a peculiar dye additive effect for the structures induced by the line irradiation of a NIR femtosecond laser pulse. On the contrary, dye‐doped Epoxy did not exhibit a dye additive effect. The different results among PMMA, p(MMA/EA‐BA) block copolymer, and Epoxy matrix polymers are supposed to be related to the difference of electron‐acceptor properties. The mechanism of this type 1 dye‐additive‐effect phenomenon for PMMA and p(MMA/EA‐BA) block copolymer is discussed on the basis of two‐photon absorption of type 1 dye at 400 nm by the irradiation of a femtosecond laser pulse with 800 nm wavelength and the dissipation of the absorbed energy to the polymer matrix among various transition processes. Dyes with a low‐fluorescence quantum yield favored the formation of thicker grating structures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2800–2806, 2002 相似文献
3.
Panagiota G. Fragouli Hermis Iatrou Nikos Hadjichristidis Takuro Sakurai Akira Hirao 《Journal of polymer science. Part A, Polymer chemistry》2006,44(1):614-619
3‐Miktoarm star copolymers, 3μ‐D2V, with two poly(dimethylsiloxane) (PDMS) and one poly(2‐vinylpyridine) (P2VP) arm, were synthesized by using anionic polymerization–high vacuum techniques and (chloromethylphenylethyl)methyl dichlorosilane, heterofunctional linking agent, with two SiCl groups and one CH2Cl group. The synthetic strategy involves the selective reaction of the two ? SiCl groups with PDMSOLi living chains, followed by reaction of the remaining chloromethyl group with P2VPLi. Combined molecular characterization results (size exclusion chromatography, membrane osmometry, and 1H NMR spectroscopy) revealed a high degree of structural and compositional homogeneity. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 614–619, 2006 相似文献
4.
The electrostatic calculation for molecules using approximated variational wave functions leads to well known difficulties connected with the application of the Hellmann-Feynman (H? F) theorem. This is due to the basis set inadequacies in the underlying calculations. This defect can easily be remedied by floating functions, whose centers are optimized in space. We can keep almost everything of the traditional wave function with a nuclear-fixed basis set, but we apply single floating to ensure the H? F theorem. Then, one can obtain a wave function obeying the H? F theorem. This provides a great conceptual simplification and may lead to practical advantages. The single floating scheme, which retains one expansion center per nucleus, is successfully applied to a series of small molecules using SCF and CASSCF wave functions with sufficiently polarized basis sets. 相似文献
5.
The photo-reaction of phenol (1) with chloroform in the presence of diethylamine gave salicylaldehyde (2) and 4-hydroxybenzaldehyde (3) in fair yield. Dihydroxybenzenes, sensitive to alkali, under similar conditions without the base gave corresponding aldehydes and a cyclohexa-2,5-dienone (15). The photo-reaction was also applied to diethylaniline (18), indoline (21) and N-methylindoline (24). In carbon tetrachloride instead of chloroform in an alcohol solution the same type of reaction took place to give esters. The mechanism involving the coupling of a phenoxy radical or a radical cation with dichloromethyl radical and not involving dichlorocarbene is proposed. 相似文献
6.
The INDO calculations were performed on the three azines: pyridazine, pyrimidine, and pyrazine. The cannonical molecular orbitais obtained by these calculations were then transformed into the localized molecular orbitals. With the use of the localized molecular orbitals, the variation in the lone-pair orbital energies of these molecules were pursued in the light of the through-space and/or the through-bond interactions between the specified localized molecular orbitals in a molecule selectively. The interactions were expressed by the summation of several terms: through-space, through-bond, through-virtuals and coupling terms. 相似文献
7.
Kumar D Hirao H de Visser SP Zheng J Wang D Thiel W Shaik S 《The journal of physical chemistry. B》2005,109(42):19946-19951
Density functional theory (DFT) is applied to the dark section of the catalytic cycle of the enzyme cytochrome P450, namely, the formation of the active species, Compound I (Cpd I), from the ferric-hydroperoxide species (Cpd 0) by a protonation-assisted mechanism. The chosen 96-atom model includes the key functionalities deduced from experiment: Asp(251), Thr(252), Glu(366), and the water channels that relay the protons. The DFT model calculations show that (a) Cpd I is not formed spontaneously from Cpd 0 by direct protonation, nor is the process very exothermic. The process is virtually thermoneutral and involves a significant barrier such that formation of Cpd I is not facile on this route. (b) Along the protonation pathway, there exists an intermediate, a protonated Cpd 0, which is a potent oxidant since it is a ferric complex of water oxide. Preliminary quantum mechanical/molecular mechanical calculations confirm that Cpd 0 and Cpd I are of similar energy for the chosen model and that protonated Cpd 0 may exist as an unstable intermediate. The paper also addresses the essential role of Thr(252) as a hydrogen-bond acceptor (in accord with mutation studies of the OH group to OMe). 相似文献
8.
The long-range correction (LC) scheme for the exchange functional of density-functional theory (DFT) was combined with the coupled-perturbed Kohn-Sham (CPKS) method to calculate nonlinear optical response properties. By using this LC-CPKS method, we calculated the hyperpolarizabilities of typical molecules and the dipole moments, polarizabilities, and hyperpolarizabilities of push-pull pi-conjugated systems: p-nitroaniline, 4-amino-4'-nitrostilbene, and alpha,omega-nitroaminopolyenes. It was found that the LC scheme clearly improved the calculation of these optical properties for all of these systems, which have been significantly overestimated by conventional DFTs. We therefore concluded that the long-range exchange interaction played an important role in calculating the optical properties using the DFT formalism. 相似文献
9.
A new tridentate cyclometalated platinum(II) complex derived from N,2-diphenyl-8-quinolinamine, which consists of two crystallographic independent molecules with two intermolecular N-H-Cl-Pt hydrogen bonds forming a dimer, exhibited a low-energy luminescence at ca. 740 nm in a 1 × 10−3 M dichloromethane solution and a strong emission centered at 670 nm in a solid state, but the analogous palladium(II) complex was nonemissive at room temperature. 相似文献
10.
Kazuki Nakanishi Yosuke Sato Yayat Ruyat Kazuyuki Hirao 《Journal of Sol-Gel Science and Technology》2003,26(1-3):567-570
Silica gels with hierarchical macropores and mesopores have been prepared by inducing phase separation in the alkoxide-based sol-gel system with an addition of alkyltrimethylammonium salt. Narrowly distributed mesopores were observed in the heat-treated gel samples possibly as a result of supramolecular templating of silica oligomers in the reacting solution. The ionic attractive interaction and hydrophobicity of the attached alkyl group cooperatively determined the phase separation tendency. No indication of long-range order of the mesopores was obtained. 相似文献