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101.
We consider the class of unicyclic graphs on n vertices with girth g, and over that class, we attempt to determine which graph maximizes the algebraic connectivity. When g is fixed, we show that there is an N such that for each n>N, the maximizing graph consists of a g cycle with n?g pendant vertices adjacent to a common vertex on the cycle. We also provide a bound on N. On the other hand, when g is large relative to n, we show that this graph does not maximize the algebraic connectivity, and we give a partial discussion of the nature of the maximizing graph in that situation. 相似文献
102.
Rodriguez KR Williams SM Young MA Teeters-Kennedy S Heer JM Coe JV 《The Journal of chemical physics》2006,125(19):194716
Reliable thermochemistry is computed for infinite stretches of pure-carbon materials including acetylenic and cumulenic carbon chains, graphene sheet, and single-walled carbon nanotubes (SWCNTs) by connection to the properties of finite size molecules that grow into the infinitely long systems. Using ab initio G3 theory, the infinite cumulenic chain (:C[double bond]C[double bond]C[double bond]C:) is found to be 1.9+/-0.4 kcal/mol per carbon less stable in free energy at room temperature than the acetylenic chain (.C[triple bond]C-C[triple bond]C.) which is 24.0 kcal/mol less stable than graphite. The difference between carbon-carbon triple, double, and single bond lengths (1.257, 1.279, and 1.333 A, respectively) in infinite chains is evident but much less than with small hydrocarbon molecules. These results are used to evaluate the efficacy of similar calculations with the less rigorous PM3 semiempirical method on the (5,5) SWCNT, which is too large to be studied with high-level ab initio methods. The equilibrium electronic energy change for C(g)-->C[infinite (5,5) SWCNT] is -166.7 kcal/mol, while the corresponding free energy change at room temperature is -153.3 kcal/mol (6.7 kcal/mol less stable than graphite). A threefold alternation (6.866, 6.866, and 6.823 A) in the ring diameter of the equilibrium structure of infinitely long (5,5) SWCNT is apparent, although the stability of this structure over the constant diameter structure is small compared to the zero point energy of the nanotube. In general, different (n,m) SWCNTs have different infinite tube energetics, as well as very different energetic trends that vary significantly with length, diameter, and capping. 相似文献
103.
Khamaganov VG Bui VX Carl SA Peeters J 《The journal of physical chemistry. A》2006,110(47):12852-12859
The rate constants for the reaction OH + CH3C(O)OH --> products (1) were determined over the temperature range 287-802 K at 50 and 100 Torr of Ar or N2 bath gas using pulsed laser photolysis generation of OH by CH3C(O)OH photolysis at 193 nm coupled with OH detection by pulsed laser-induced fluorescence. The rate coefficient displays a complex temperature dependence with a sharp minimum at 530 K, indicating the competition between a reaction proceeding through a pre-reactive H-bonded complex to form CH3C(O)O + H2O, expected to prevail at low temperatures, and a direct methyl-H abstraction channel leading to CH2C(O)OH + H2O, which should dominate at high temperatures. The temperature dependence of the rate constant can be described adequately by k1(287-802 K) = 2.9 x 10(-9) exp{-6030 K/T} + 1.50 x 10(-13) exp{515 K/T} cm3 molecule(-1)(s-1), with a value of (8.5 +/- 0.9) x 10-13 cm3 molecule(-1)(s-1) at 298 K. The steep increase in rate constant in the range 550-800 K, which is reported for the first time, implies that direct abstraction of a methyl-H becomes the dominant pathway at temperatures greater than 550 K. However, the data indicates that up to about 800 K direct methyl-H abstraction remains adversely affected by the long-range H-bonding attraction between the approaching OH radical and the carboxyl -C(O)OH functionality. 相似文献
104.
Guirgis GA Panikar SS Klaassen JJ Purohit SS Johnston MD Durig JR 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(5):858-866
Infrared and Raman spectra (3500-60 cm(-1)) of gas and/or liquid and solid 1-bromo-1-silacyclopentane (c-C4H8SiBrH) have been recorded and the vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twisted form. Ab initio calculations with a variety of basis sets up to MP2(full)/6-311+G(2df,2pd) predict the envelope-axial and envelope-equatorial conformers to be saddle points with nearly the same energies but approximately 900 cm(-1) (5.98 kJ/mol) lower in energy than the planar conformer. Density functional theory calculations by the B3LYP method predict slightly lower energies for the two envelope forms and considerably lower energy for the planar form compared to the MP2 predictions. By utilizing the MP2(full)/6-31G(d) calculations the force constants, frequencies, infrared intensities, band contours, Raman activities, and depolarization values have been obtained to support the vibrational assignment. Estimated r0 structural parameters have been obtained from adjusted MP2(full)/6-311+G(d,p) calculations. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings. 相似文献
105.
A series of complexes between recently developed four-membered group 13 metal(I) heterocycles and group 10 metal(0) fragments have been prepared and structurally characterized. One prepared complex, [Pt{Ga[N(Ar)]2CNCy2}3] (Ar = C6H3Pri2-2,6; Cy = cyclohexyl), possesses the shortest Pt-Ga bonds yet reported, the covalent components of which are suggested by theoretical studies to have significant pi character. 相似文献
106.
S. Ramanujan gave fourteen families of series in his Second Notebook in Chap. 17, Entries 13–17. In each case he gave only
the first few examples, giving us the motivation to find and prove a general formula for each family of series. The aim of
this paper is to develop a powerful tool (four versatile functions f
0,f
1,f
2, and f
3) to collect all of Ramanujan’s examples together.
相似文献
107.
Damiano Rossetti StefaanJ.R. Simons Paolo Pagliai Rob Ward Shaun Fitzpatrick 《Particle & Particle Systems Characterization》2004,21(4):284-292
The selection of an appropriate polymeric binder to be used to agglomerate drug with excipients is a critical issue for the development of high shear wet granulation processes for pharmaceutical tablet systems. The aim of the study reported here is to determine the potential for successful granulation through measurement of the interactions of two polymer binder solutions, hydroxypropyl methylcellulose (HPMC) and polyvinyl‐pyrrolidone (PVP), with individual paracetamol drug crystals. A novel micro‐force balance (MFB) has been used to measure different parameters of the crystal‐to‐binder interaction, including the forces exerted by axially strained liquid bridges formed between either two paracetamol crystals or between a reservoir of binder solution and a single paracetamol crystal, the paracetamol‐to‐binder wettability, the post rupture volume distribution and the residue deposited on each crystal. Video images of the separation sequences were obtained simultaneously for analysis of bridge geometry, contact angles, volume distribution and binder residues. It was found that the formation of liquid bridges and their ability to bond particles together depends on the amount of binder left on a crystal after contacting a reservoir of binder (for example, large binder drop). Crystals in contact with HPMC were able to retain more liquid from a binder reservoir than those contacted with PVP solutions. This behaviour is seen to be more important to the final granule strength than the liquid binding force holding particles together in the wet agglomerate. 相似文献
108.
Timothy L. Fletcher Shaun M. Kandathil Paul L. A. Popelier 《Theoretical chemistry accounts》2014,133(7):1-10
A novel design of a next-generation force field considers not only the electronic inter-atomic energy but also intra-atomic energy. This strategy promises a faithful mapping between the force field and the quantum mechanics that underpins it. Quantum chemical topology provides an energy partitioning in which atoms have well-defined electronic kinetic energies, and we are interested in capturing how they respond to changes in the positions of surrounding atoms. A machine learning method called kriging successfully creates models from a training set of molecular configurations that can then be used to predict the atomic kinetic energies occurring in previously unseen molecular configurations. We present a proof-of-concept based on four molecules of increasing complexity (methanol, N-methylacetamide, glycine and triglycine). We test how well the atomic kinetic energies can be modelled with respect to training set size, molecule size and elemental composition. For all atoms tested, the mean atomic kinetic energy errors fall below 1.5 kJ mol?1, and far below this in most cases. This represents errors all under 0.5 % and thus the kinetic energies are well modelled using the kriging method, even when using modest-to-small training set sizes. 相似文献
109.
Michael E. Kitto Traci A. Menia Douglas K. Haines Shaun E. Beach Clayton J. Bradt Eileen M. Fielman Umme-Farzana Syed Thomas M. Semkow Abdul Bari A. J. Khan 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):49-56
An air-sampling network that operates continuously as part of New York State’s environmental surveillance program collected radionuclides emitted as a result of the Fukushima nuclear accident. Samples were collected, typically for 7 days each, by drawing ~600 m3 of air through a particulate-collecting filter followed in series by a canister containing activated charcoal. Additional air sampling was implemented at ~3-day intervals at two locations. Gamma-ray spectroscopy was used to confirm the detection of 131I, 137Cs, 134Cs, and 7Be in the particulate phase at all sites, with maximum concentrations near 1,260, 160, 160, and 5,200 μBq/m3, respectively. Gas-phase 131I, collected on activated charcoal, exhibited a maximum concentration of 3,400 μBq/m3 at the sites. Assessment of radionuclide levels in the air samples suggests that there were minimal health impacts from the airborne radionuclides as the activities contributed an insignificant amount to the annual human dose. 相似文献
110.
Detailed chemical analysis of the solid phase fermentation of an Australian Penicillium citrinum isolate has returned the known compounds citrinin (1), phenol A acid (6), dihydrocitrinone (7) and dihydrocitrinin (8), together with a novel cytotoxic dimer, dicitrinin A (5). Dicitrinin A (5) was determined to be a dimerised artefact of the major co-metabolite citrinin, and its structure solved by spectroscopic analysis and chemical modification. Analysis of the products encountered during the controlled decomposition of citrinin led to the discovery of additional citrinin dimers and delineated a plausible mechanistic pathway linking all monomeric and dimeric citrinin degradation products. 相似文献