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61.
The Zeeman effect facilitates certain rotational assignments in bands of the electronic system of NO2. A partial analysis of two bands of this system is reported. 相似文献
62.
T. J. Hardwick 《国际化学动力学杂志》1969,1(3):325-337
The kinetics of the thermally and radiation initiated chain reaction between trichloroethylene and cyclopentane to produce 1,1-dichlorovinylcyclopentane and hydrogen chloride have been investigated in the temperature range 250–360°C at high pressure in the gas phase. The rate governing step in the chain is (k3 = 3.3 × 109 exp ?(4800/RT) cc mole?1 sec ?1). The rate of the unimolecular decomposition of trichloroethylene is 1.4 × 1014 exp ?(61,200/RT) sec?1. 相似文献
63.
Bai D Hardwick CL Berron BJ Jennings GK 《The journal of physical chemistry. B》2007,111(39):11400-11406
We have investigated the effects of film composition and thickness on the rate of pH-induced response of a copolymer film containing predominately polymethylene with randomly distributed carboxylic acid side groups (denoted as PM-CO2H). These responsive films are prepared directly onto a gold electrode surface by surface-catalyzed polymerization and subsequent hydrolysis. We measured electrochemical impedance at fixed frequency (100 Hz) to monitor the barrier properties of the polymer film during a step change in pH. At a 1-3% molar acid content, the copolymer films exhibit a 2 order of magnitude change in impedance at 100 Hz when the contacting solution pH changes from 11 to 4 (or 4 to 11). For all films, the rate of protonation is slower than that of ionization, consistent with a more gradual transfer of protons through an increasingly hydrophobic film at the outermost nanometers during the protonation step. Increased acid content within the film accelerates both the rate of protonation and ionization. Thinner films (50 nm) with the same acid content show faster response rate in both directions, since water and ions have a shorter transfer path. A large and reversible pH response was obtained for all films studied, but selection of appropriate film composition and thickness can greatly influence the rate of response. 相似文献
64.
Continuous flow chemical synthesis is already known to have many attributes that give it superiority over batch processes in several respects. To expand these advantages with those from automation will only drive such enabling technologies further into the faster producing, more efficient 21st century chemical world. In this report we present several examples of algorithmic chemical search, along with flow platforms that link hardware and digital chemical operations on software. This enables organic syntheses to be automatically carried out and optimised with as little human intervention as possible. By applying such enabling technologies to the production of small organic molecules and pharmaceutical compounds in end-to-end multistep processes, a range of reaction types can be accessed and, thus, the flexibility of these single, compact flow designs may be revealed. Automated systems can allow several reactions to take place on the same setup, enabling direct comparison of reactions under different conditions. Moreover, the production of new and known target compounds can be made faster and more efficient, the recipes of which can then be stored as digital files. Some of the automating software has employed machine-powered learning to assist the chemist in developing intelligent algorithms and artificial intelligence (AI) driven synthetic route planning. This ultimately produces a continuous flow platform that can design its own viable pathway to a particular molecule and then carry it out on its own, allowing the chemists, at the same time, to apply their expertise to other pressing challenges in their fields.Automated flow chemistry: humans and machines working together to create faster, safer, more efficient laboratories of the future where computers help to design and control experiments, allowing researchers to focus on other scientific pursuits. 相似文献
65.
Freunberger SA Chen Y Peng Z Griffin JM Hardwick LJ Bardé F Novák P Bruce PG 《Journal of the American Chemical Society》2011,133(20):8040-8047
The nonaqueous rechargeable lithium-O(2) battery containing an alkyl carbonate electrolyte discharges by formation of C(3)H(6)(OCO(2)Li)(2), Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li, CO(2), and H(2)O at the cathode, due to electrolyte decomposition. Charging involves oxidation of C(3)H(6)(OCO(2)Li)(2), Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li accompanied by CO(2) and H(2)O evolution. Mechanisms are proposed for the reactions on discharge and charge. The different pathways for discharge and charge are consistent with the widely observed voltage gap in Li-O(2) cells. Oxidation of C(3)H(6)(OCO(2)Li)(2) involves terminal carbonate groups leaving behind the OC(3)H(6)O moiety that reacts to form a thick gel on the Li anode. Li(2)CO(3), HCO(2)Li, CH(3)CO(2)Li, and C(3)H(6)(OCO(2)Li)(2) accumulate in the cathode on cycling correlating with capacity fading and cell failure. The latter is compounded by continuous consumption of the electrolyte on each discharge. 相似文献
66.
The rotational structure of bands of NO2 vapor in the region 8300–9000 Å has been partially analyzed and the absorption assigned to the (000)-(000) and (000)-(010) vibronic bands of the electronic transition. Irregular weak perturbations in the N-structure of the upper-state manifold are accompanied by larger resonance-type crossings in the K-structure. The larger perturbation is attributed to vibronic coupling between the à state and excited vibrational levels of the ground state, characterized by a low density of ground state levels and a large vibronic coupling matrix element between the à and X? states. The reconstituted, deperturbed bands have blue-degraded N-structure and strongly red-degraded K-structure, indicating that the bond angle decreases sharply in the excited state. The physical structure of the 2B2 state is uncertain but some suggestions are made. The electronic energy of the 2B2 state is T0 = 11 962.9 cm?1. 相似文献
67.
This paper obtains solitons as well as other solutions to a few nonlinear evolution equations that appear in various areas of mathematical physics. The two analytical integrators that are applied to extract solutions are tan–cot method and functional variable approaches. The soliton solutions can be used in the further study of shallow water waves in (1+1) as well as (2+1) dimensions. 相似文献
68.
AC conductivity and 1H NMR relaxation time measurements are reported for the heteropolyacids H3PM12O40. 21H2O (M = W, Mo) over a range of tempereatures.Ambient temperature proton conductivites are ? 1 S m-1, with conductivity activation energies E ? 40 kJ mol-1.The NMR results are interpreted in terms of a range of motional processes leading to distributions of translational correlation times. The behaviour is compared to motions in zeolites and of water sorbed by charcoal. 相似文献
69.
P.J. Bussey C. Raine J.G. Rutherglen P.S.L. Booth L.J. Carroll P.R. Daniel C.J. Hardwick J.R. Holt J.N. Jackson J.H. Norem W.H. Range F.H. Combley W. Galbraith V.H. Rajaratnam C. Sutton M.C. Thorne P. Waller 《Nuclear Physics B》1976,104(2):253-276
An experiment has been completed at the Daresbury synchrotron to measure the asymmetry in the photoproduction cross section of neutral pions on hydrogen, for photons polarised normal to and in the production plane. The source of polarised photons was coherent bremsstrahlung of electrons traversing the lattice structure of diamond and the polarisation P of the γ beam was calculated from the measured intensity of the coherent spike. The asymmetry parameter Σ, defined as Σ = (σ⊥ ? σ|)/(σ⊥ + σ|) where σ⊥(σ|) are the cross sections for photons polarised perpendicular (parallel) to the production plane, has been measured over a range of photon energies from 1.2 to 2.8 GeV and over a range of ?t (the square of the four-momentum transfer) from 0.13 (GeV/c)2 to 1.4 (GeV/c)2. A marked energy variation in the value of Σ is found over the energy region 1.6–1.8 GeV. 相似文献
70.
Fan Y Tysoe B Sim J Mirkhani K Sinclair AN Honarvar F Sildva H Szecket A Hardwick R 《Ultrasonics》2003,41(5):369-375
A resonance acoustic spectroscopy technique is assessed for nondestructive evaluation of explosively welded clad rods. Each rod is modeled as a two-layered cylinder with a spring-mass system to represent a thin interfacial layer containing the weld. A range of interfacial profiles is generated in a set of experimental samples by varying the speed of the explosion that drives the copper cladding into the aluminum core. Excellent agreement is achieved between measured and calculated values of the resonant frequencies of the system, through appropriate adjustment of the interfacial mass and spring constants used in the wave scattering calculations. Destructive analysis of the interface in the experimental specimens confirms that key features of the interfacial profile may be inferred from resonance acoustic spectroscopy analysis applied to ultrasonic measurements. 相似文献