全文获取类型
收费全文 | 19968篇 |
免费 | 2695篇 |
国内免费 | 2028篇 |
专业分类
化学 | 8448篇 |
晶体学 | 252篇 |
力学 | 1303篇 |
综合类 | 299篇 |
数学 | 6618篇 |
物理学 | 7771篇 |
出版年
2024年 | 41篇 |
2023年 | 188篇 |
2022年 | 296篇 |
2021年 | 458篇 |
2020年 | 579篇 |
2019年 | 587篇 |
2018年 | 560篇 |
2017年 | 617篇 |
2016年 | 818篇 |
2015年 | 625篇 |
2014年 | 888篇 |
2013年 | 2122篇 |
2012年 | 1001篇 |
2011年 | 1252篇 |
2010年 | 1044篇 |
2009年 | 1240篇 |
2008年 | 1230篇 |
2007年 | 1216篇 |
2006年 | 1161篇 |
2005年 | 1064篇 |
2004年 | 943篇 |
2003年 | 921篇 |
2002年 | 814篇 |
2001年 | 624篇 |
2000年 | 665篇 |
1999年 | 533篇 |
1998年 | 444篇 |
1997年 | 385篇 |
1996年 | 375篇 |
1995年 | 280篇 |
1994年 | 262篇 |
1993年 | 221篇 |
1992年 | 194篇 |
1991年 | 171篇 |
1990年 | 111篇 |
1989年 | 110篇 |
1988年 | 87篇 |
1987年 | 58篇 |
1986年 | 77篇 |
1985年 | 72篇 |
1984年 | 70篇 |
1983年 | 24篇 |
1982年 | 41篇 |
1981年 | 38篇 |
1980年 | 29篇 |
1979年 | 32篇 |
1978年 | 20篇 |
1977年 | 23篇 |
1976年 | 14篇 |
1973年 | 30篇 |
排序方式: 共有10000条查询结果,搜索用时 381 毫秒
11.
Benni Du 《Molecular physics》2020,118(2)
Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH2?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (Ea= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10?12 cm3 molecule?1 s?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10?14×(T/298?K)3.4×exp(1725.7?K/T) cm3 molecule?1 s?1. 相似文献
12.
本文从理论上研究了在双色频率梳激光场驱动下多光子谐波辐射光谱中的相位突变现象。我们利用Floquet理论非微扰地模拟了频率梳激光场与原子分子等量子系统的相互作用过程。谐波辐射信号是多光子偶极跃迁相干叠加的结果,通过调节频率梳激光场间的相对相位,可以相干地控制谐波辐射信号的强度。通过对谐波信号进行傅里叶变换,可以提取不同跃迁路径的相对相位信息。我们通过改变频率梳组激光场的强度和频率组分实现多光子跃迁频率,让其跨越共振跃迁频率时,谐波相位会发生突变。从而可以观测超强激光场驱动下量子系统共振跃迁频率的斯塔克能移。 相似文献
13.
ABSTRACTQM(UB3LYP)/MM(AMBER) calculations were performed for the locations of the transition structure (TS) of the oxygen–oxygen (O–O) bond formation in the S4 state of the oxygen-evolving complex (OEC) of photosystem II (PSII). The natural orbital (NO) analysis of the broken-symmetry (BS) solutions was also performed to elucidate the nature of the chemical bonds at TS on the basis of several chemical indices defined by the occupation numbers of NO. The computational results revealed a concerted bond switching (CBS) mechanism for the oxygen–oxygen bond formation coupled with the one-electron transfer (OET) for water oxidation in OEC of PSII. The orbital interaction between the σ-HOMO of the Mn(IV)4–O(5) bond and the π*-LUMO of the Mn(V)1=O(6) bond plays an important role for the concerted O–O bond formation for water oxidation in the CaMn4O6 cluster of OEC of PSII. One electron transfer (OET) from the π-HOMO of the Mn(V)1=O(6) bond to the σ*-LUMO of the Mn(IV)4–O(5) bond occurs for the formation of electron transfer diradical, where the generated anion radical [Mn(IV)4–O(5)]-? part is relaxed to the ?Mn(III)4?…?O(5)- structure and the cation radical [O(6)=Mn(V)1]+ ? part is relaxed to the +O(6)–Mn(IV)1? structure because of the charge-spin separation for the electron-and hole-doped Mn–oxo bonds. Therefore, the local spins are responsible for the one-electron reductions of Mn(IV)4->Mn(III)4 and Mn(V)1->Mn(IV)1. On the other hand, the O(5)- and O(6)+ sites generated undergo the O–O bond formation in the CaMn4O6 cluster. The Ca(II) ion in the cubane- skeleton of the CaMn4O6 cluster assists the above orbital interactions by the lowering of the orbital energy levels of π*-LUMO of Mn(V)1=O(6) and σ*-LUMO of Mn(IV)4–O(5), indicating an important role of its Lewis acidity. Present CBS mechanism for the O–O bond formation coupled with one electron reductions of the high-valent Mn ions is different from the conventional radical coupling (RC) and acid-base (AB) mechanisms for water oxidation in artificial and native photosynthesis systems. The proton-coupled electron transfer (PC-OET) mechanism for the O–O bond formation is also touched in relation to the CBS-OET mechanism. 相似文献
15.
It is believed that there are more fundamental gauge symmetries beyond those described by the Standard Model of particle physics. The scales of these new gauge symmetries are usually too high to be reachable by particle colliders. Considering that the phase transition (PT) relating to the spontaneous breaking of new gauge symmetries to the electroweak symmetry might be strongly first order, we propose considering the stochastic gravitational waves (GW) arising from this phase transition as an indirect way of detecting these new fundamental gauge symmetries. As an illustration, we explore the possibility of detecting the stochastic GW generated from the PT of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} ![]()
![]()
in the space-based interferometer detectors. Our study demonstrates that the GW energy spectrum is reachable by the LISA, Tianqin, Taiji, BBO, and DECIGO experiments only for the case where the spontaneous breaking of \begin{document}$ {\bf{B}}-{\bf{L}}$\end{document} ![]()
![]()
is triggered by at least two electroweak singlet scalars. 相似文献
16.
In this paper, we study the existence of the uniformly minimum risk equivariant (UMRE) estimators of parameters in a class
of normal linear models, which include the normal variance components model, the growth curve model, the extended growth curve
model, and the seemingly unrelated regression equations model, and so on. The necessary and sufficient conditions are given
for the existence of UMRE estimators of the estimable linear functions of regression coefficients, the covariance matrixV and (trV)α, where α > 0 is known, in the models under an affine group of transformations for quadratic losses and matrix losses, respectively.
Under the (extended) growth curve model and the seemingly unrelated regression equations model, the conclusions given in literature
for estimating regression coefficients can be derived by applying the general results in this paper, and the sufficient conditions
for non-existence of UMRE estimators ofV and tr(V) are expanded to be necessary and sufficient conditions. In addition, the necessary and sufficient conditions that there
exist UMRE estimators of parameters in the variance components model are obtained for the first time. 相似文献
17.
施国勇 《宁波大学学报(理工版)》1998,(2)
提出了一个线性双向联想存储器的模型,一组有限个向量对由一线性算子建立起双向联想关系,此线性算于是一个网络的联结权重矩阵。该权矩阵由最小二乘法决定。由权矩阵的解导出一特殊类型的Lyapunov矩阵方程.本文提供了这种Lyapunov矩阵方程的解。 相似文献
18.
19.
The Schwinger representation of the SO(8) fermion pair algebra in terms ofd and quasispin vector (u, s, v) bosons is used in deriving a microscopic boson coherent state having both particle-hole and pair excitations. The coherent
state is the exact boson image of the HFB variational solution. We can study the shape phase transition and pairing behaviour
of the nuclear ground states using the coherent states. 相似文献
20.