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951.
Benedito J. Costa Cabral Lidia M. P. C. Albuquerque Fernando M. S. Silva Fernandes 《Theoretical chemistry accounts》1991,78(4):271-280
Summary The conformational equilibrium of ethylene glycol (CH2OHCH2OH) has been examined by performing geometry optimizations at the 6-31G*, MP2/6-31G* and 6-31G** levels. Final energies have been calculated at the MP3 level with the optimized geometries. The two most stable conformers are atGg andgGg but it is verified that the inclusion of electronic correlations reduces their energy difference of 0.6 kcal/mol at the HF level to less than 0.2 kcal/mol. The possible coexistence of the two most stable conformers is in agreement with some previous studies of Frei et al. For thetXg conformer a detailed analysis of the intramolecular potential as a function of rotation around the C-C bond is also reported. 相似文献
952.
953.
The standard gas-phase enthalpies of formation, at T = 298.15 K, of the complete series of fluorobenzene and their corresponding dewar isomers have been determined by means of the CBS-QB3 and G3MP2B3 composite approaches. These values have been estimated by using appropriate supporting reactions, such as, reactions of atomization or of atom substitution. The results show that there is a linear dependence between the enthalpy of the most stable n-fluorobenzene and the corresponding n-fluorodewar benzene (n = 0, 1, …, 6). Further, the estimates are always more negative than the experimental results and so, suggested enthalpies of formation for 1,2,3-, 1,2,4- and 1,3,5-trifluorobenzenes and for 1,2,3,4- and 1,2,3,5-tetrafluorobenzenes are those retrieved from G3MP2B3 calculations added by 8 kJ/mol. The interaction of four different M+ ions with fluorobenzene and the three difluorobenzenes shows that the σ-interaction with 1,2-difluorobenzene is stronger than π-interaction on these fluorobenzenes. 相似文献
954.
Soo Gyeong Cho 《Journal of organometallic chemistry》1996,510(1-2)
The unimolecular rearrangements of hydrogen, methyl and phenyl groups at the Si atom in α-silylcarbenium ions have been investigated using an ab initio molecular orbital method. MP2/6–31 + G*//HF/6–31G* calculations predict that all three groups migrate from the Si to an adjacent Cα with no energy barrier. Thus, the silicenium ion is the only stable species in each potential energy surface. The conformation of the benzylsilicenium ion, (C6H5)CH2−SiH2+, indicates that the phenyl ring is significantly bent toward the silyl cationic center in order to interact with the vacant 3p(Si+) orbital. In contrast to MP2 results, Hartree-Fuck calculations (both HF/3–21G* and HF/6–31G* levels) predict small energy barriers for 1,2-migrations of H and Me (1.4 kcal mol−1 for H migration, and 1.5 kcal mol−1 for Me migration, respectively, at the HF/6–31G* level). This difference provides convincing evidence that the incorporation of electron correlation is of particular importance in describing the potential energy surface for the rearrangement of α-silylcarbenium ions to silicenium ions. The results of the calculations have also been applied to the possible rearrangement mechanism of α-chlorosilanes to chlorosilanes, assuming that the experimental conditions are favorable toward the generation of ionic species. Various factors which may govern the migratory aptitudes of various R groups, i.e. (1) activation energies, (2) overall reaction energies and (3) the conformational preference of reactants have been investigated. The calculated activation energy obtained, namely the energy for the generation of the silicenium ion and the C−1 ion from an α-chlorosilane, is consistent with the experimental migratory aptitude in the gas phase observed in mass spectrometers. 相似文献
955.
B2C3簇的结构和振动光谱的理论研究 总被引:1,自引:1,他引:1
用量子化学从头计算方法研究了B2C3簇各种可能的空间结构,计算了相应的振动光谱和结合能。对B2C3最稳定构型的电子结构进行了深入的分析和讨论。 相似文献
956.
957.
Ab initio molecular orbital calculations of nuclear spin-spin coupling constants in PH−2, PH3, PH+4 and P2H4 have been carried out employing SCF perturbation theory. Basis set dependence of all the four contributing terms has been studied in order to find the criterion for the selection of basis sets to be employed for computing this property. The dependence of the coupling constants of PH−2 on its geometry has also been found. This study also discusses the requirement for satisfactory computation of couplings in cases where none of the coupling nuclei is a proton. It is found that bond-centred functions along with at least double zeta basis sets reproduce coupling constants quite satisfactorily. In all the cases studied, uncontracted core basis functions yield couplings which are in better agreement with experimental couplings than those obtained with contracted core functions. 相似文献
958.
959.
Excited-State Proton Transfer and Decay in Hydrogen-Bonded Oxazole System:MS-CASPT2//CASSCF Study
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Herein we have employed high-level multi-reference CASSCF and MS-CASPT2 electronic structure methods to systematically study the photochemical mechanism of intramolecularly hydrogen-bonded 2-(2'-hydroxyphenyl)-4-methyloxazole. At the CASSCF level, we have optimized minima, conical intersections, minimum-energy reaction paths relevant to the excited-state intramolecular proton transfer (ESIPT), rotation, photoisomerization, and the excited-state deactivation pathways. The energies of all structures and paths are refined by the MS-CASPT2 method. On the basis of the present results, we found that the ESIPT process in a conformer with the OH…N hydrogen bond is essentially barrierless process; whereas, the ESIPT process is inhibited in the other conformer with the OH…O hydrogen bond. The central single-bond rotation of the S1 enol species is energetically unfavorable due to a large barrier. In addition, the excited-state deactivation of the S1 keto species, as a result of the ultrafast ESIPT, is very efficient because of the existence of two easily-approached keto S1/S0 conical intersections. In stark contrast to the S1 keto species, the decay of the S1 enol species is almostly blocked. The present theoretical study contributes valuable knowledge to the understanding of photochemistry of similar intramolecularly hydrogen-bonded molecular and biological systems. 相似文献
960.
EuAlO3 (EAO) is synthesized by the sol–gel process. The Rietveld refinement of the X-ray diffraction data shows that the material has orthorhombic structure with Pbnm space group. The density functional theory calculations are initiated with the experimental lattice parameters. The full potential linearized augmented plane wave method and projector augmented wave method are used to investigate the ground state properties of EAO. An indirect band gap of 1.8 eV is observed with the valence band maximum at the Γ point and the conduction band minimum at the R point. The X-ray photoemission spectroscopy (XPS) spectra of EAO are obtained in the energy window of 0–1000 eV. Using the electronic density of states, the valence band (VB) spectrum of EAO is generated and compared with the observed VB-XPS spectrum. The optical dielectric constant and the refractive index of the material are calculated for the photon energy radiation. The optical properties show a considerable anisotropy in the material. The Born effective charge of various elements and the dielectric tensor of EAO have been calculated. 相似文献