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41.
Harro Lentz Ernst Ulrich Franck 《Angewandte Chemie (International ed. in English)》1978,17(10):728-730
Liquid or dense supercritical ammonia has been suggested as an extraction fluid. It is indeed good solvent for very different classes of compounds, as can be seen from phase diagrams. Such diagrams for binary systems of ammonia and hydrocarbons are presented and discussed on the basis of their critical curves. Apparatus and methods for the measurement of phase equilibria and equation of state data of fluid mixtures at high pressure are described. 相似文献
42.
Peter Scharfenberg 《Theoretical chemistry accounts》1980,58(1):73-79
A simple classification scheme is proposed for critical points, based only on rankr and signatures of the (n,n)-matrixG of harmonic force constants. The determination ofr ands, e.g. by the well-known factorizationG=L
T
gL (L: triangular matrix,g: diagonal matrix), has several theoretical as well as practical (computational) advantages over the inspection of eigenvalues ofG, so far used in quantum chemistry. The eigenvalues are sufficient butnot necessary for a classification whereas rank and signature are the only necessary and sufficient prerequisites for solving the task. For the purpose of presenting a working example, by calculating only a 2×2 torque constant matrix, it is shown that the coplanar ethylbenzene is unstable in the CNDO/2 picture. 相似文献
43.
The selectivity of a column system, S, defined by equation 28, includes a variation coefficient (β) of plate number with capacity ratio which has a large influence on the peak capacity, as shown in Fig. 18. Some typical chromatograms are given. In order to predict S for a column system from Kovat's Index, equations 40 and 41 are given to calculate the constant of the carbon number rule for squalane at different temperatures or for different stationary phases. The specific retention value of heptane on squalane at different temperatures can be calculated from equation 42. The nonpolarity index, defined by equation 43, was used to calculate the retention value of heptane on various stationary phases. In liquid chromatography, the order of elution may be reversed by changing the composition of the eluent on the same chemically bonded silica (manufactured in China). The linear relations between the log retention values of different kinds of solutes or of a single solute on the silicas of different surface areas when using the same eluent are given. 相似文献
44.
Ahmed M. Mkadmh 《International journal of quantum chemistry》2020,120(23):e26393
Different isomers of N5+ were modeled at DFT(PBE0)/aug-cc-pV(Q + d)Z, and their ground(transition) state characteristics were assessed through frequency calculations. Single-point energies were accomplished at PBE0/aug-cc-pV(5 + d)Z. Nonlinear optical susceptibilities (NLO) of isomers were accomplished using Firefly, while the linear optical invariant was examined using the finite-field method, Firefly, and modified dipole field tensor in the presence of two different screening factors. The excited states, singlets and triplets, of were modeled at the CIS and CIS(D) and then their optical parameters were estimated at TDFT(PBE0)/aug-cc-pV(Q + d)Z using Firefly. The singlet is found the most stable isomer, with the inversional rate constant larger than that of the Cs isomer and high energy barrier with the triplet counterpart. Isomers 2 , 3 , and 4 are found local minima, while 5 and 6 are saddle points: transition states between equivalent invertomers. Energy calculations of the singlet and triplet isomers were in excellent agreement with the literature. An excellent correlation is found between the average polarizability and the impulse factor. Substantial variations were found between the singlet and triplet excited states in terms of energy, geometry, and optical properties from one side and with from the other side. Reactivity indices showed that N1 and N5 are the optimum nucleophilic and electrophilic reactivity sites. 相似文献
45.
D. Fennell Evans Martin Allen B. W. Ninham Abdel Fouda 《Journal of solution chemistry》1984,13(2):87-101
Critical micelle concentrations were determined by conductance measurements for decyl-, dodecyl-, tetradecyl- and hexadecyltrimethylammonium bromide in water at 25, 60, 95, 130, and 160°C. The results are discussed in terms of the equilibrium model and the nonlinear Poisson-Boltzmann model for micelle formation. The free energies of transferring a methylene group from water to the oil-like interior of the micelle are found to be –781 at 25°C, –796 at 60°C, –819 at 95°C, –815 at 130°C, and –787 at 160°C cal-mol–1. 相似文献
46.
Hepatocellular carcinoma (HCC) is the major histological form of primary liver cancer. It has usually reached the disease state once the patient is diagnosed since there are no specific symptoms in the early stages of HCC. This fact increases the difficulty of curing HCC. Recently, quantities of evidence have shown that many mathematical methods (such as dynamic network biomarkers, DNB) can be used to detect critical states or tipping points of complex diseases. However, it is difficult to apply the DNB theory to the clinic since multiple samples are generally unavailable for individual patient. This paper constructs a novel method based on landscape dynamic network biomarkers (L-DNB), which aims to detect early warning signals from cirrhosis state to very advanced HCC state in individual patient. The selected dataset contains multiple samples for each HCC state. A score that indicates the disease characteristics is calculated for each sample by RNA-seq data, and several scores constitute a distribution in the same state. Quantifying the statistical characteristics of these distributions and determining that low-grade dysplastic and high-grade dysplastic are the critical states of HCC. These results can provide scientific advice for early warning indicators and optimal treatment time for HCC. 相似文献
47.
System ringing is one of the most important factors affecting the quality of data obtained in high speed dynamic material tests using servo-hydraulic machines. This phenomenon is characterized by vibrations originated by the excitation of predominant modes of the machine during tests, producing distinctive waves in material curves that severely distort the required results. In the specialized literature, the quantitative study of these vibrations has mainly been carried out considering the testing machine as a single degree of freedom system, which has led to a general understanding of the variables involved in the process. However, discrepancies between analytical predictions and experimental observations have been detected using the single degree of freedom approach, so the need for further detailed study of machine dynamic characteristics has been reported. The work presented in this paper addresses this requirement by means of a detailed characterization of the dynamic behavior of a MTS 819.10 high rate testing system. Natural frequencies, mode shapes and damping factors have been obtained from an experimental modal analysis performed on the machine and a mathematical model of the process has been developed from these modal parameters. This model has been used to detect the modes that have the greatest influence in system ringing when testing rubber at high strain rates, and to predict quantitatively the amplitudes of vibrations produced in the process. Material curves have been corrected by subtracting the predicted undulations from the original measurements, obtaining smooth curves that adequately reflect the real material behavior at high strain rates and, thus, demonstrating the effectiveness of the proposed procedure. Although the research conducted in this work has been focused on rubber, the procedure can be extended equally to characterize other materials, thus constituting a valuable tool to correct experimental measurements contaminated by ringing. 相似文献
48.
Dynamic surface tensions, σ(t) for aqueous solutions of nonyl phenol ethoxylates (NPEOs) at the temperature 298.15 K were measured using a Lauda drop volume tensiometer. The non-ionic surfactants analyzed in this work were Tergitol NP-9, NP-35 and NP-40. By using the classical Ward and Torday equation, the diffusion coefficient for each bulk surfactant concentration was calculated. The equilibrium surface tension values were determined by extrapolating the dynamic surface tension to t → ∞ on the σ(t) vs. t−1/2 curves. These values were used to determine the critical micelle concentrations (CMC) of the surfactant aqueous solutions as well as to calculate the infinite dilution activity coefficient of the surfactant, following a model that combines the Volmer surface equation of state and the Gibbs adsorption equation. 相似文献
49.
50.
《Physics and Chemistry of Liquids》2012,50(2):143-157
Abstract n-alkane critical constants as determined experimentally for n ≤ 18 are first compared and contrasted with the predictions of various models. Qualitative accord is found, but only one quantitative prediction, that of Wertheim's model for the critical temperature Tc, is found to fit the experimental data over the admittedly limited range of n available. Reference is then made to critical properties of the heavy fluid alkali metals, and especially Rb and Cs, where some evidence is cited for the existence of long chains of alkali atoms. The relative constancy of the product of the critical pressure Pc and the critical volume Vc for the three heaviest alkalis is noted, a fact consistent with one of the more recent ‘polymer’ models. 相似文献