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21.
Andersson S Arasa C Yabushita A Yokoyama M Hama T Kawasaki M Western CM Ashfold MN 《Physical chemistry chemical physics : PCCP》2011,13(35):15810-15820
The photodesorption of H(2)O in its vibrational ground state, and of OH radicals in their ground and first excited vibrational states, following 157 nm photoexcitation of amorphous solid water has been studied using molecular dynamics simulations and detected experimentally by resonance-enhanced multiphoton ionization techniques. There is good agreement between the simulated and measured energy distributions. In addition, signals of H(+) and OH(+) were detected in the experiments. These are inferred to originate from vibrationally excited H(2)O molecules that are ejected from the surface by two distinct mechanisms: a direct desorption mechanism and desorption induced by secondary recombination of photoproducts at the ice surface. This is the first reported experimental evidence of photodesorption of vibrationally excited H(2)O molecules from water ice. 相似文献
22.
Gdanitz RJ Black GD Lansing CS Palmer BJ Schuchardt KL 《Journal of computational chemistry》2005,26(3):214-225
We describe the integration and use of the Amica software package ("Atoms & Molecules In Chemical Accuracy") within the Extensible Computational Chemistry Environment (Ecce). Amica is capable of accurately solving the electronic Schrodinger equation of small atoms and molecules using terms that are linear in the interelectronic distances, r(12), on multireference level of theory, but it requires expert knowledge to configure and execute its algorithms. Ecce is a comprehensive suite of tools that support the computational chemistry research processes of computation setup, execution, and analysis through a convenient graphical user interface. Additionally, Ecce was architected with mechanisms to integrate alternative electronic structure codes. The successful integration of Amica within Ecce validates the architecture of the latter and brings the high-accuracy capabilities of Amica to a wider audience. 相似文献
23.
Car-Parrinello molecular dynamics (CPMD) and a previously developed wave packet model are used to study ultrafast relaxation in water clusters. Water clusters of 15 water molecules are used to represent ice Ih. The relaxation is studied by exciting a symmetric or an asymmetric stretch mode of the central water molecule. The CPMD results suggest that relaxation occurs within 100 fs. This is in agreement with experimental work by Woutersen and Bakker and the earlier wave packet calculations. The CPMD results further indicate that the excitation energy is transferred both intramolecularly and intermolecularly on roughly the same time scale. The intramolecular energy transfer occurs predominantly between the symmetric and asymmetric modes while the bend mode is largely left unexcited on the short time scale studied here. 相似文献
24.
Smith CA Pope FD Cronin B Parkes CB Orr-Ewing AJ 《The journal of physical chemistry. A》2006,110(41):11645-11653
Absorption cross sections for the A1A2-X1A1 electronic transition of formaldehyde have been measured by ultraviolet (UV) laser absorption spectroscopy in the tropospherically significant wavelength range 300-340 nm, over which HCHO is photochemically active. Absorption cross sections are reported at two temperatures, 294 and 245 K and at a spectral resolution of 0.0035 nm (0.35 cm-1). At this resolution, greater peak absorption cross sections are obtained for many of the sharp spectral features than were previously reported. To simulate atmospheric conditions in the troposphere, the effects of adding a pressure of nitrogen of up to 500 Torr and of reduced sample temperature were investigated. The overall magnitudes of peak absorption cross sections are largely unaffected by the added pressure of nitrogen, but a modest degree of pressure broadening (0.2-0.3 cm-1 atm-1) is evident in the line shapes. Computer simulations of spectra have been optimized by comparison with wavelength-dependent formaldehyde absorption cross sections for each major vibronic band in the chosen wavelength range. Experimental and computer simulated spectra at 294 and 245 K are compared to test the reliability of the computer simulations for quantification of the effects of temperature on absorption cross sections. All experimental absorption cross section data and tables of input parameters for spectral simulations are available as Supporting Information. 相似文献
25.
Paulo A. R. Pires Muhammad Imran Carina Loffredo Paulo M. Donate Daniel Previdi Omar A. El Seoud 《Journal of Physical Organic Chemistry》2013,26(3):280-285
The effects of solvents on chemical phenomena (rate and equilibrium constants, spectroscopic transitions, etc.) are conveniently described by solvation free‐energy relationships that take into account solvent acidity, basicity and dipolarity/polarizability. The latter can be separated into its components by manipulating the UV–vis spectra of two solvatochromic probes, 2‐(N,N‐dimethylamino)‐7‐nitrofluorene (DMANF) and a di‐(tert‐butyl)‐tetramethyl docosanonaen probe (ttbP9) whose synthesis is laborious and expensive. Recently, we have shown that the natural dye β‐carotene can be conveniently employed instead of ttbP9 for the determination of solvent polarizability (SP) of 76 molecular solvents and four ionic liquids. In the present work, we report the polarizabilities of further 24 solvents. Based on the solvatochromism of β‐carotene and DMANF, we have calculated solvent dipolarity (SD) for 103 protic and aprotic molecular solvents, and ionic liquids. The dependence of SD and SP on the number of carbon atoms in the acyl‐ or alkyl group of several homologous series (alcohols; 2‐alkoxyethanols; carboxylic acid‐ anhydrides, and esters, ionic liquids) is calculated and briefly discussed. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
26.
Carina I. Jette Irina Geibel Shoshana Bachman Masaki Hayashi Shunya Sakurai Hideki Shimizu Jeremy B. Morgan Brian M. Stoltz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(13):4341-4345
Herein, we report the first Pd‐catalyzed enantioselective arylation of α‐substituted γ‐lactams. Two sets of conditions were developed for this transformation, allowing for the use of either aryl chlorides or bromides as electrophiles. Utilizing a highly electron‐rich dialkylphosphine ligand we have been able to construct α‐quaternary centers in good yields (up to 91 % yield) and high enantioselectivities (up to 97 % ee). 相似文献
27.
Olaya Domarco Claudia Kieler Christine Pirker Carina Dinhof Bernhard Englinger Johannes M. Reisecker Gerald Timelthaler Marcos D. García Carlos Peinador Bernhard K. Keppler Walter Berger Alessio Terenzi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(24):8091-8096
Metal‐driven self‐assembly afforded a multitude of fascinating supramolecular coordination complexes (SCCs) with applications as catalysts, host–guest, and stimuli‐responsive systems. However, the interest in the biological applications of SCCs is only starting to emerge and thorough characterization of their behavior in biological milieus is still lacking. Herein, we report on the synthesis and detailed in‐cell tracking of a Pt2L2 metallacycle. We show that our hexagonal supramolecule accumulates in cancer cell nuclei, exerting a distinctive blue fluorescence staining of chromatin resistant to UV photobleaching selectively in nucleolar G4‐rich regions. SCC co‐localizes with epitopes of the quadruplex‐specific antibody BG4 and replaces other well‐known G4 stabilizers. Moreover, the photophysical changes accompanying the metallacycle binding to G4s in solution (fluorescence quenching, absorption enhancement) also take place intracellularly, allowing its subcellular interaction tracking. 相似文献
28.
Dr. Lydia M. Peschel Carina Vidovič Dr. Ferdinand Belaj Dr. Dmytro Neshchadin Prof. Nadia C. Mösch-Zanetti 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(15):3893-3902
The synthesis and structural determination of four tungsten alkyne complexes coordinated by the bio-inspired S,N-donor ligand 2-(4′,4′-dimethyloxazoline-2′-yl)thiophenolate (S-Phoz) is presented. A previously established protocol that involved the reaction of the respective alkyne with the bis-carbonyl precursor [W(CO)2(S-Phoz)2] was used for the complexes [W(CO)(C2R2)(S-Phoz)2] (R=H, 1 a ; Me, 1 b ; Ph, 1 c ). Oxidation with pyridine-N-oxide gave the corresponding W-oxo species [WO(C2R2)(S-Phoz)2] (R=H, 2 a ; Me, 2 b ; Ph, 2 c ). All W-oxo-alkyne complexes ( 2 a , b , c ) were found to be capable of alkyne release upon light irradiation to afford five-coordinate [WO(S-Phoz)2] ( 3 ). The photoinduced release of the alkyne ligand was studied in detail by in situ 1H NMR measurements, which revealed correlation of the photodissociation rate constant ( 2 b>2 a>2 c ) with the elongation of the alkyne C≡C bond in the molecular structures. Oxidation of [WO(S-Phoz)2] ( 3 ) with pyridine-N-oxide yielded [WO2(S-Phoz)2] ( 4 ), which shows highly fluxional behavior in solution. Variable-temperature 1H NMR spectroscopy revealed three isomeric forms with respect to the ligand arrangement versus each other. Furthermore, compound 4 rearranges to tetranuclear oxo compound [W4O4(μ-O)6(S-Phoz)4] ( 5 ) and dinuclear [{WO(μ-O)(S-Phoz)}2] ( 6 ) over time. The latter two were identified by single-crystal X-ray diffraction analyses. 相似文献
29.
The so-called ‘soldering’ procedure performed by Polyakov (Int J Math Phys A5, 833–842, 1990) for a -gauge theory is geometrically explained in terms of a Cartan connection on second-order frames of the projective space P1. The relationship between a Cartan connection and the usual (Ehresmann) connection on a principal bundle allows to gain an
appropriate insight into the derivation of the genuine ‘diffeomorphisms out of gauge transformations’ given by Polyakov himself.
Unité Mixte de Recherche (UMR 6207) du CNRS et des Universités Aix-Marseille I, Aix-Marseille II et de l’Université du Sud
Toulon-Var. Unité affiliée à la FRUMAM Fédération de Recherche 2291. 相似文献