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11.
Roberto Cammi Caterina Ghio Jacopo Tomasi 《International journal of quantum chemistry》1986,29(3):527-539
The interaction of some neutral acids of π type, bearing appropriate unsymmetrical substitutions at the C?C group with some selected bases (H2O, NH3, OH?), is compared with that of the parent compound of a new set of neutral π acids, bearing symmetrical substitutions at the C?C group with the same bases. The analyses of the interaction energy, performed according to two decomposition schemes, with and without the counterpoise corrections, make clear the similarity of symmetrically and unsymmetrically substituted neutral organic acids. 相似文献
12.
Ingrosso F Ladanyi BM Mennucci B Elola MD Tomasi J 《The journal of physical chemistry. B》2005,109(8):3553-3564
The solvent reorganization process after electronic excitation of a polar solute in a polar solvent such as acetonitrile is related mainly to the time evolution of the solute-solvent electrostatic interaction. Modern laser-based techniques have sufficient time resolution to follow this decay in real time, providing information to be confirmed and interpreted by theories and models. We present here a study aimed at the investigation of the different steps involved in the process taking place after a vertical S(0) --> S(1) excitation of a large size chromophore, coumarin 153 (C153), in acetonitrile, from both the solute and the solvent points of view. To do this, we use accurate quantum mechanical calculations for the solute properties within the polarizable continuum model (PCM) and classical molecular dynamics (MD) simulations, both equilibrium and nonequilibrium, for C153 in the presence of the solvent. The geometry of the solute is allowed to change in order to study the role of internal motions in the time-dependent solvation process. The solvent response function has been obtained from the simulation data and compared to experiment, while the comparison between equilibrium and nonequilibrium MD results for the solvation response confirms the validity of the linear response approximation in the C153-acetonitrile system. The MD trajectories have also been used to monitor the structure of the solvation shell and to determine its change in response to the change in the solute partial charges. 相似文献
13.
The possibility is explored of calculating the time evolution of a given initial molecular state, in the presence of sufficiently strong nonadiabatic interactions, with a fully quantum-mechanical approach. Two methods are presented. The first one is based on the determination of the molecular eigenstates, with expansion of the nuclear wavefunctions on a Hermite basis. The second method is based on the Padé 1,1 approximation of the time evolution operator and on a finite difference representation of the time-dependent nuclear wavefunctions. Both methods are applied to simple models of a diatomic molecule. 相似文献
14.
Rosanna Bonaccorsi Carlo Petrongolo Eolo Scrocco Jacopo Tomasi 《Theoretical chemistry accounts》1969,15(4):332-343
The C.I. method is applied to already published double- SCF wave functions for OF2, NO
2
–
and CN–. All doubly excited configurations are considered. The second order approximation values presented for those cases are compared with the exact energy values in some minor cases. An attempt has been made to improve the rate of convergency of the process by transforming the canonical SCF occupied orbitals into localized ones and the virtual canonical orbitals into a particular type of localized orbitals. These latter show also an intuitively acceptable spatial conformation.
Work supported by the Consiglio Nazionale delie Ricerche. 相似文献
Zusammenfassung Die CI Methode wird auf bereits bekannte Doppel-Zeta-SCF-Wellenfuntionen für die Systeme OF2, NO 2 – und CN– angewandt. Dabei werden alle doppelt angeregten Konfigurationen berücksichtigt. Um die Konvergenz zu verbessern, werden versuchsweise die kanonischen und besetzten SCF-Orbitale in lokalisierte Orbitale und die virtuellen kanonischen Orbitale in einen besonderen Typ von lokalisierten Orbitalen transformiert. Die letzteren zeigen eine besonders geeignete räumliche Anpassung.
Résumé Pour un calcul de intéraction de configurations, comprenant toutes le configurations à double excitation, on a employé des fonctions d'onde SCF sur une base doublée. Pour le calcul complet on a essayé des formules d'approximation, qu'on a pu vérifier avec le calcul exact sur des cas réduits.Pour améliorer la vélocité de convergence du procés on a transformé les orbitales canoniques SCF en orbitales localisées et aprés on a construit, selon un procedé particulier, des orbitales virtuelles localisées qui montrent une conformation dans l'espace qui est intuitivement satisfaisante.
Work supported by the Consiglio Nazionale delie Ricerche. 相似文献
15.
The cathelicidin family of host defense peptides includes a group of cationic and usually amphipathic peptides that display a variety of activities related to host defense functions, among which the most acknowledged is a direct antimicrobial activity against various microbial pathogens. All members of this family are synthesized as precursors characterized by an N-terminal cathelin-like domain which is relatively well conserved also in evolutionary distant vertebrates. By contrast, the C-terminal region, which carries the active peptide, appears to be a focus for genetic mechanisms that have selectively generated a considerable sequence diversity. This process is particularly striking in Cetartiodactyls, where repeated gene duplication events and subsequent divergence have produced an array of distinct family members. The corresponding mature cathelicidin peptides are considerably diverse in length, amino acid sequence and structure, variously adopting alpha-helical, elongated or beta-hairpin conformations. The diverse nature of these peptides may account for distinct functions and for a diverse spectrum of activity and/or antimicrobial potency. 相似文献
16.
17.
Nicholas Favalli Gabriele Bassi Tania Zanetti Jrg Scheuermann Dario Neri 《Helvetica chimica acta》2019,102(4)
The construction of DNA‐encoded chemical libraries (DECLs) crucially relies on the availability of chemical reactions, which are DNA‐compatible and which exhibit high conversion rates for a large number of diverse substrates. In this work, we present our optimization and validation procedures for three copper and palladium‐catalyzed reactions (Suzuki cross‐coupling, Sonogashira cross‐coupling, and copper(I)‐catalyzed alkyne‐azide cycloaddition (CuAAC)), which have been successfully used by our group for the construction of large encoded libraries. 相似文献
18.
Dr. Joffrey Pijeat Léo Chaussy Roxanne Simoës Dr. Jacopo Isopi Prof. Dr. Jean-Sébastien Lauret Prof. Dr. Francesco Paolucci Prof. Dr. Massimo Marcaccio Dr. Stéphane Campidelli 《ChemistryOpen》2021,10(10):997-1003
The synthesis of π-extended porphyrins containing anthracenyl moieties still represents an important challenge. Here, we report on the synthesis of a series of unsubstituted naphthyl-, pyrenyl- and anthracenyl-fused zinc porphyrin derivatives. To this aim, meso-substitued porphyrins are synthesized and the fusion of the PAHs (Polycyclic Aromatic Hydrocarbon) on the β-positions are performed through thermally induced dehydro-aromatization. The fused zinc-porphyrin derivatives are fully characterized and their optical absorption and photoluminescence properties are reported. We also demonstrate that zinc can be removed from the porphyrin core, giving rise to pure C, H, N materials. This work constitutes the first step towards the synthesis of the fully-fused tetra-anthracenylporphyrin. 相似文献
19.
Flavio Sabatelli Jacopo Segato Leonardo Belpassi Alessandro Del Zotto Daniele Zuccaccia Paola Belanzoni 《Molecules (Basel, Switzerland)》2021,26(9)
The coordination ability of the [(ppy)Au(IPr)]2+ fragment [ppy = 2-phenylpyridine, IPr = 1,3-bis(2,6-di-isopropylphenyl)-imidazol-2-ylidene] towards different anionic and neutral X ligands (X = Cl−, BF4−, OTf−, H2O, 2-butyne, 3-hexyne) commonly involved in the crucial pre-equilibrium step of the alkyne hydration reaction is computationally investigated to shed light on unexpected experimental observations on its catalytic activity. Experiment reveals that BF4− and OTf− have very similar coordination ability towards [(ppy)Au(IPr)]2+ and slightly less than water, whereas the alkyne complex could not be observed in solution at least at the NMR sensitivity. Due to the steric hindrance/dispersion interaction balance between X and IPr, the [(ppy)Au(IPr)]2+ fragment is computationally found to be much less selective than a model [(ppy)Au(NHC)]2+ (NHC = 1,3-dimethylimidazol-2-ylidene) fragment towards the different ligands, in particular OTf− and BF4−, in agreement with experiment. Effect of the ancillary ligand substitution demonstrates that the coordination ability of Au(III) is quantitatively strongly affected by the nature of the ligands (even more than the net charge of the complex) and that all the investigated gold fragments coordinate to alkynes more strongly than H2O. Remarkably, a stabilization of the water-coordinating species with respect to the alkyne-coordinating one can only be achieved within a microsolvation model, which reconciles theory with experiment. All the results reported here suggest that both the Au(III) fragment coordination ability and its proper computational modelling in the experimental conditions are fundamental issues for the design of efficient catalysts. 相似文献
20.
Eapen J Williams WC Buongiorno J Hu LW Yip S Rusconi R Piazza R 《Physical review letters》2007,99(9):095901
Transient hot-wire data on thermal conductivity of suspensions of silica and perfluorinated particles show agreement with the mean-field theory of Maxwell but not with the recently postulated microconvection mechanism. The influence of interfacial thermal resistance, convective effects at microscales, and the possibility of thermal conductivity enhancements beyond the Maxwell limit are discussed. 相似文献