全文获取类型
收费全文 | 321篇 |
免费 | 4篇 |
专业分类
化学 | 180篇 |
晶体学 | 1篇 |
力学 | 5篇 |
数学 | 19篇 |
物理学 | 120篇 |
出版年
2019年 | 3篇 |
2016年 | 3篇 |
2014年 | 4篇 |
2013年 | 10篇 |
2012年 | 6篇 |
2011年 | 10篇 |
2010年 | 9篇 |
2009年 | 8篇 |
2008年 | 18篇 |
2007年 | 14篇 |
2006年 | 11篇 |
2005年 | 14篇 |
2004年 | 13篇 |
2003年 | 5篇 |
2002年 | 12篇 |
2001年 | 9篇 |
2000年 | 4篇 |
1999年 | 5篇 |
1997年 | 11篇 |
1996年 | 5篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 11篇 |
1991年 | 11篇 |
1990年 | 5篇 |
1989年 | 3篇 |
1988年 | 6篇 |
1987年 | 5篇 |
1986年 | 3篇 |
1985年 | 3篇 |
1983年 | 3篇 |
1982年 | 3篇 |
1981年 | 4篇 |
1980年 | 4篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 5篇 |
1976年 | 5篇 |
1974年 | 3篇 |
1972年 | 2篇 |
1971年 | 3篇 |
1970年 | 5篇 |
1969年 | 3篇 |
1968年 | 2篇 |
1967年 | 2篇 |
1964年 | 2篇 |
1929年 | 2篇 |
1904年 | 2篇 |
1882年 | 2篇 |
排序方式: 共有325条查询结果,搜索用时 10 毫秒
31.
Devizis A Serbenta A Peckus D Thiessen A Alle R Meerholz K Hertel D Gulbinas V 《The Journal of chemical physics》2010,133(16):164904
The dynamics of charge carrier generation in poly(spirobifluorene-co-benzothiadiazole) was investigated by electric field-induced fluorescence quenching and differential absorption measurements. Three different time domains of carrier generation have been identified: an ultrafast phase, a subnanosecond phase, and an entire lifetime phase. The charge generation efficiencies during the first and second phases were found to be almost independent of temperature, being about 25% and 10%, respectively, at an applied electric field of 1.3×10(6)?V/cm, while the generation efficiency during the third phase increases from 2% at 80 K to 10% at room temperature. The results of transient spectroscopy measurements and quantum chemical calculations suggest an intramolecular charge transfer for about 1 ps from the alkoxy-substituted fluorene side group to the benzothiadiazole subunit of the main chain. The formation and evolution of the resulting charge transfer states determine the way of charge carrier generation. 相似文献
32.
Crochet JJ Hoseinkhani S Lüer L Hertel T Doorn SK Lanzani G 《Physical review letters》2011,107(25):257402
We present evidence for the generation of free carriers in aggregated single-wall carbon nanotubes by photoexcitation in the energetic range of the π→π(*) transition associated with the M saddle point of the graphene lattice. The underlying broad absorption culminating at 4.3 eV can be fit well with a Fano line shape that describes strong coupling of a saddle-point exciton to an underlying free electron-hole pair continuum. Moreover, it is demonstrated that transitions in this energetic region autoionize into the continuum by detecting features unique to the presence of free charges in the transient transmission spectra of the continuum-embedded second sub-band exciton, S(2). 相似文献
33.
Winter B Weber R Hertel IV Faubel M Jungwirth P Brown EC Bradforth SE 《Journal of the American Chemical Society》2005,127(19):7203-7214
Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties. 相似文献
34.
E. Kaiser J. de Vries H. Steger C. Menzel W. Kamke I. V. Hertel 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1991,20(1):193-196
A reflecting time of flight mass spectrometer (RETOF) is used to study unimolecular and collision induced fragmentation of ammonia cluster ions. Synchrotron radiation from the BESSY electron storage ring is used in a range of photon energies from 9.08 up to 17.7 eV for single photon ionisation of neutral clusters in a supersonic beam. The threshold photoelectron photoion coincidence technique (TPEPICO) is used to define the energy initially deposited into the cluster ions. Metastable unimolecular decay (µs range) is studied using the RETOF's capacity for energy analysis. Under collision free conditions the by far most prominent metastable process is the evaporation of one neutral NH3 monomer from protonated clusters (NH3) n ? 2NH 4 + . Abundance of homogeneous vs. protonated cluster ions and of metastable fragments are reported as a function of photon energy and cluster size up ton=10. 相似文献
35.
P. Farmanara H.-H. Ritze V. Stert W. Radloff I.V. Hertel 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2002,19(2):193-209
Neutral ammonia clusters (NH3)m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters
rearrange to form an H-transfer state (NH3)m-2NH4(3s)NH2 with the subunit NH4 in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength.
Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH3)m-2NH4(3p)NH2 states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically
upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics
of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization.
The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast
dissociation.
Received 22 September 2001 and Received in final form 31 January 2002 相似文献
36.
The photoinduced dynamics in base pairs of adenine and thymine were analyzed by femtosecond pump-probe spectroscopy. On the short-time scale up to a few picoseconds, the characteristic time constants for the dimers are quite similar to the corresponding values of the monomers. This leads to the conclusion that ultrafast intramolecular relaxation proceeds via ππ* and nπ* states of one component within the dimer. On the long-time scale, we obtained a novel time constant of roughly 40 ps for the thymine dimer and the adenine–thymine base pair. This time constant was never observed in the monomers and is tentatively assigned to an intermolecular relaxation process, possibly via a hydrogen transfer state. 相似文献
37.
Banert K Köhler F Melzer A Scharf I Rheinwald G Rüffer T Lang H Herges R Hess K Ghavtadze N Würthwein EU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):10071-10080
1,4‐Diazidobuta‐1,3‐dienes (Z,Z)‐ 10 , 17 , and 21 were photolyzed and thermolyzed to yield the pyridazines 13 , 20 , and 23 , respectively. To explain these aromatic final products, the generation of highly strained bi‐2H‐azirin‐2‐yls 12 , 19 , and 22 and their valence isomerization were postulated. In the case of meso‐ and rac‐ 22 , nearly quantitative formation from diazide 21 , isolation as stable solids, and complete characterization were possible. On the thermolysis of 22 , aromatization to 23 was only a side reaction, whereas equilibration of meso‐ and rac‐ 22 and fragmentation, which led to alkyne 24 and acetonitrile, dominated. Prolonged irradiation of 22 gave mainly the pyrimidine 25 . The change of the configuration at C‐2 of the 2H‐azirine unit was observed not only in the case of bi‐2H‐azirin‐2‐yls 22 but also for simple spirocyclic 2H‐azirines 29 at a relatively low temperature (75 °C). The fragmentation of rac‐ 22 to give alkyne 24 and two molecules of acetonitrile was also studied by high‐level quantum chemical calculations. For a related model system 30 (methyl instead of phenyl groups), two transition states TS‐ 30 – 31 of comparable energy with multiconfigurational electronic states could be localized on the energy hypersurface for this one‐step conversion. The symmetrical transition state complies with the definition of a coarctate mechanism. 相似文献
38.
Carsten Grosse-Knetter Ingolf Kuss Dieter Schildknecht 《Zeitschrift fur Physik C Particles and Fields》1993,60(2):375-388
We examine dimension-six extensions of the standard electroweak Lagrangian which are invariant under localSU(2) L ×U(1) Y -transformations. The dimensionfour trilinear and quadrilinear effective interactions of the vector bosons with one another are found to coincide with the vector boson interactions previously derived from globalSU(2) weak isospin symmetry broken by electromagnetism. Supplementing the model by a well-known dimension-six single-parameter quadrupole interaction leads to the most general vector boson self-couplings that can be obtained by addition of dimension-six terms to the standard Lagrangian. We examine in some detail anotherSU(2) L ×U(1) Y -symmetric interaction which containsW 3 B mixing and modifies both vector boson self-couplings and fermionic interactions. Independently of being strongly constrained by the LEP 1 data, the addition of this interaction to the above-mentioned non-standard ones does not change the form of the trilinear and quadrilinear non-standard self-couplings of the vector bosons. Therefore, while being interesting in itself with respect to LEP 1 physics, this term is irrelevant with respect to the phenomenology of the vector-boson self-interactions. 相似文献
39.
Ingolf Terveer 《Mathematical Methods of Operations Research》1995,41(3):359-380
Multistage Bayesian decision procedures in statistical quality control are known from attribute sampling. In this paper they are introduced in a more general framework occuring in lot-control by using the theory of Bayesian sequentially planned decision procedures. We show that under sufficiency and transitivity assumptions and monotonicity properties concerning the distribution and cost set-up these Bayes-procedures have (z, c
–,c
+)-structure which, on one hand, generalizes results of K.-H. Waldmann and, on the other hand, reduces computational effort significantly. Finally, examples taken from attribute sampling and life testing for an outgoing lot are presented.The theory presented in this paper is taken from [11]. 相似文献
40.