全文获取类型
收费全文 | 5075篇 |
免费 | 905篇 |
国内免费 | 446篇 |
专业分类
化学 | 1717篇 |
晶体学 | 31篇 |
力学 | 76篇 |
综合类 | 20篇 |
数学 | 378篇 |
物理学 | 4204篇 |
出版年
2024年 | 15篇 |
2023年 | 53篇 |
2022年 | 102篇 |
2021年 | 121篇 |
2020年 | 178篇 |
2019年 | 143篇 |
2018年 | 138篇 |
2017年 | 133篇 |
2016年 | 212篇 |
2015年 | 170篇 |
2014年 | 195篇 |
2013年 | 332篇 |
2012年 | 245篇 |
2011年 | 301篇 |
2010年 | 237篇 |
2009年 | 314篇 |
2008年 | 351篇 |
2007年 | 398篇 |
2006年 | 341篇 |
2005年 | 262篇 |
2004年 | 236篇 |
2003年 | 280篇 |
2002年 | 249篇 |
2001年 | 191篇 |
2000年 | 205篇 |
1999年 | 146篇 |
1998年 | 140篇 |
1997年 | 83篇 |
1996年 | 89篇 |
1995年 | 60篇 |
1994年 | 54篇 |
1993年 | 49篇 |
1992年 | 44篇 |
1991年 | 29篇 |
1990年 | 36篇 |
1989年 | 31篇 |
1988年 | 22篇 |
1987年 | 23篇 |
1986年 | 32篇 |
1985年 | 24篇 |
1984年 | 26篇 |
1983年 | 7篇 |
1982年 | 10篇 |
1981年 | 21篇 |
1980年 | 18篇 |
1979年 | 12篇 |
1978年 | 14篇 |
1977年 | 16篇 |
1976年 | 12篇 |
1974年 | 8篇 |
排序方式: 共有6426条查询结果,搜索用时 15 毫秒
71.
G. A. Mezincescu 《Journal of statistical physics》1987,49(5-6):1181-1190
UsingX-bounding (lower bounds by Laplacians with mixed boundary conditions and discrete analogs), we obtain the Lifschitz exponent at the bottom of the spectrum for random operators of typeH
=T+V
, withT a (periodic) generator of a positivity-preserving semigroup, extending results by Kirsch and Simon. 相似文献
72.
Kenzo Sato 《International Journal of Infrared and Millimeter Waves》1986,7(6):927-947
Under the influence of perpendicularly applied positive electro-static field less than 103V/cm to silk fibron textiles, at the high frequency side of the C2–O bending reflection band (450350 cm–1), effect of step creation and step annihilation of the C2–O pseudo dending bands was induced in three stages at 600450 cm–1 region IR spectroscopically relating to the stepnized statistical transfer of the unbonded 2P2, electrons in carbon which present with density of 4.0×1014/cm2 in the surface mono-layer of silk fibroin from the states formed in (–C1–C2–N–)m spiral chains upto the pseudo-bending states formed in C2–O bondings. Fine 90 steps measured overlapping on these four types of C2–O reflection bands were analysed as to consist four step series and they were shown as,y = A·Jm + B cm–1 with A=20, B=521, m=0.55 and J=1, 2...18 for the B-series.And with A=39, B=283, m=0.63 and J=1, 2 ...17 for the C-series.y
J = A·J + B cm–1 with A=11.42, B=201 and J=1, 2...13, for the D-series. And, stepnized C2–O bending bands including that of permanent oscillators and pseudo-bending oscillators induced by the effect of transfer of the unbonded 2P2 electrons in carbon atoms were shown as, EN=A·N2+B·N+C (eV) with A=–1.50×10–3, B=1.65×10–2 and C=2.4×10–2. 相似文献
73.
Gostev F. E. Petrukhin A. N. Titov A. A. Shienok A. I. Marevtsev V. S. Sarkisov O. M. 《Russian Chemical Bulletin》2003,52(3):557-561
Intramolecular processes in electronic-excited states of 2,4,5-triarylimidazole molecules were studied by femtosecond laser spectroscopy. Experiments were carried out with two types of compounds, namely, those experiencing intramolecular proton transfer and two model compounds in which it is impossible. Schemes of the processes studied were proposed and the characteristic rate constants were determined. The excited-state intramolecular proton transfer (ESIPT) in the molecules with planar structure of the reaction center is a very fast process (100 fs). If the reaction center has a nonplanar structure and, hence, the intramolecular hydrogen bond is weakened, the ESIPT time is determined by the time of conformational rearrangement of the molecule. 相似文献
74.
Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB-like expansions. 相似文献
75.
NH_2基态和激发态的SAC-CI和量子拓扑方法研究郑世钧,蔡新华,宋天乐,孟令鹏,中迁博,波田雅彦(河北师范学院化学系,石家庄,050091)(京都大学工程学院京都,日本)关键词SAC-CI方法,激发态,电子密度,拓扑分析用量子拓扑学方法研究激发态... 相似文献
76.
Linear scaling local correlation approach for solving the coupled cluster equations of large systems
A linear scaling local correlation approach is proposed for approximately solving the coupled cluster doubles (CCD) equations of large systems in a basis of orthogonal localized molecular orbitals (LMOs). By restricting double excitations from spatially close occupied LMOs into their associated virtual LMOs, the number of significant excitation amplitudes scales only linearly with molecular size in large molecules. Significant amplitudes are obtained to a very good approximation by solving the CCD equations of various subsystems, each of which is made up of a cluster associated with the orbital indices of a subset of significant amplitudes and the local environmental domain of the cluster. The combined effect of these two approximations leads to a linear scaling algorithm for large systems. By using typical thresholds, which are designed to target an energy accuracy, our numerical calculations for a wide range of molecules using the 6-31G or 6-31G* basis set demonstrate that the present local correlation approach recovers more than 98.5% of the conventional CCD correlation energy. 相似文献
77.
Extremely localized molecular orbitals are rigorously localized on only a preselected set of atoms and do not have any tails outside the localization region. The importance of these orbitals lies in their ability to be transferred from one molecule to another one. A new algorithm to determine extremely localized molecular orbitals in the framework of the density functional theory method is presented. This could also be a valuable tool in the quantum mechanics/molecular mechanics methodology where localized molecular orbitals are used to describe covalent bonds across the frontier region. The present approach is used to build up the electron density of thymopentin, a polypeptide constituted by five residues, starting from extremely localized molecular orbitals determined on a set of model molecules. The results obtained confirm good transferability properties for these orbitals.Proceedings of the 11th International Congress of Quantum Chemistry satellite meeting in honor of Jean-Louis Rivail 相似文献
78.
The localized molecular orbitals and their energy levels for the clusters [Fe3S4(SH)3]2–, [(HS)3Fe3S4·Ni(PH3)]2–, [Mo3S4(OH2)9]4+, and [Mo3S4·Ni]4+ have been calculated by mean of the Edmiston-Ruedenberg energy localization technique under the CNDO/2 approximation in order to reveal the resemblance between [Fe3S4]+ and [Mo3S4]4+ in the geometrical configurations and the addition reactivities with heterometal atoms. It is shown that in these two cluster species with core {M
3(3-S)(-S)3} of similar structure (M = Mo, Fe) there exist three synergically connected three-centered two-electron (M-S-M) -bonds around the puckered six-membered {M3S3} rings on account of delocalization of a lone electron pair on each bridging S atom; these (M-S-M) -bonds are thus capable of forming cubane-like heterometal clusters with intruder metal atoms through the ( M) bonding. It is therefore seen that unlike the [Mo3S4]4+ with appreciable bonding between the Mo atoms, the extra d-electrons on the metal atoms in the [Fe3S4]+ cluster are localized on the Fe atoms, exhibiting an electronic structure significantly different from that of the [Mo3S4]4+ cluster. 相似文献
79.
We present a theoretical study of dissociative photoionization of H2 via the 1Πu symmetry in the photon energy range 30–43 eV. Our results explain the various peaks observed in the experiments below 40 eV and illustrate, in particular, the important role of the 2Πu(2pπu) ionization threshold. At higher photon energies, they suggest the existence of new resonance structures that may be associated with doubly excited states of H2 lying above the third and fourth ionization thresholds (the Q3 and Q4 resonance series). From the calculated resonance parameters, we conclude that the dominant mechanism at high photon energies should involve the Q4 (and probably higher) doubly excited states of H2. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 相似文献
80.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献