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101.
Oström H Ogasawara H Näslund LA Andersson K Pettersson LG Nilsson A 《The Journal of chemical physics》2007,127(14):144702
The electronic structure of methane adsorbed on Pt(977) is investigated using angle-resolved x-ray absorption spectroscopy (XAS) in combination with density functional theory spectrum calculations. XAS, which probes the unoccupied states atom specifically, shows the appearance of the symmetry-forbidden gas-phase lowest unoccupied molecular orbital due to s-p rehybridization. In addition new adsorption-induced states appear just above the Fermi level. A systematic investigation, where computed XA spectra are compared with the experiment, indicates elongation of the C-H bond pointing toward the surface to 1.18+/-0.05 A. The bond elongation arises due to mixing between bonding and antibonding C-H orbitals. Computed charge density difference plots show that no covalent chemical bond is formed between the adsorbate and substrate upon adsorption. The changes in electronic structure arise in order to minimize the Pauli repulsion by polarizing charge away from the surface toward the carbon atom of the methane molecule. 相似文献
102.
103.
L. G. M. Pettersson 《Theoretical chemistry accounts》1994,87(4-5):293-305
Summary The interaction between NO and different possible adsorption sites of the NiO(100) surface is studied. The Ni2+ cation gives a bonding to NO in reasonable agreement with experiment, but only if a crystal potential corresponding to less than completely ionic charges is assumed. The computed angle of 43° is also in good agreement with experiment. O1– sites in both weak and strong crystal potentials also give a strong interaction with NO, 1.3 and 0.5 eV, respectively. In this case the angle is larger or around 70°. The O2– anion and Ni1+ sites do not give any significant bonding irrespective of assumed crystal potential and can be excluded as adsorption sites. The computed vibrational frequency for the adsorbed NO show shifts of +50, –85 and –200 cm–1 for adsorption on Ni2+ in the weak potential, and O1– in strong and weak potential, respectively. Only one, downwards shifted, frequency has been observed in the experiment but the most likely candidate for the experimentally observed adsorption site with a binding of 0.5 eV, is still the Ni2+ in a weak potential. Nitrogen core level shifts are also computed and discussed and the fully screened core-hole state is obtained for a cluster model, NiF4O+NO, of Ni2+ in NiO with an ionicity lower than the standard ± 2.This work is dedicated to Prof. Inga Fischer-Hjalmars 相似文献
104.
Kiviniemi T Pettersson M Khriachtchev L Räsänen M Runeberg N 《The Journal of chemical physics》2004,121(4):1839-1848
IR spectroscopy, laser induced fluorescence (LIF), and thermoluminescence (TL) measurements have been combined to monitor trapping, thermal mobility, and reactions of oxygen atoms in solid xenon. HXeO and O(3) have been used as IR active species that probe the reactions of oxygen atoms. N(2)O and H(2)O have been used as precursors for oxygen atoms by photolysis at 193 nm. Upon annealing of matrices after photolysis, ozone forms at two different temperatures: at 18-24 K from close O ...O(2) pairs and at approximately 27 K due to global mobility of oxygen atoms. HXeO forms at approximately 30 K reliably at higher temperature than ozone. Both LIF and TL show activation of oxygen atoms around 30 K. Irradiation at 240 nm after the photolysis at 193 nm depletes the oxygen atom emission at 750 nm and reduces the amount of HXeO generated in subsequent annealing. Part of the 750 nm emission can be regenerated by 266 nm and this process increases the yield of HXeO in annealing as well. Thus, we connect oxygen atoms emitting at 750 nm with annealing-induced formation of HXeO radicals. Ab initio calculations at the CCSD(T)/cc-pV5Z level show that XeO (1(1)Sigma(+)) is much more deeply bound [D(e) = 1.62 eV for XeO --> Xe+O((1)D)] than previous calculations have predicted. Taking into account the interactions with the medium in an approximate way, it is estimated that XeO (1(1)Sigma(+)) has a similar energy in solid xenon as compared with interstitially trapped O((3)P) suggesting that both possibly coexist in a low temperature solid. Taking into account the computational results and the behavior of HXeO and O(3) in annealing and irradiations, it is suggested that HXeO may be formed from singlet oxygen atoms which are trapped in a solid as XeO (1(1)Sigma(+)). 相似文献
105.
Jensen MB Pettersson LG Swang O Olsbye U 《The journal of physical chemistry. B》2005,109(35):16774-16781
A comparative quantum chemical study of CO2 adsorption on MgO and CaO has been carried out. Theoretical infrared (IR) frequencies are calculated and compared with IR experiments from the literature. The results show that CO2 adsorbs as monodentate on edge sites and bidentate on corner sites on MgO. The former assignment contradicts the common assumption of adsorption of CO2 in a bidentate configuration. On CaO, CO2 adsorbs as monodentate on both edge and corner sites, which is a reinterpretation of earlier experimental work. On terrace (100) sites, none of the adsorption modes on MgO or CaO possess calculated frequencies in agreement with the experimental IR spectra. These experimental bands were tentatively assigned to some slightly perturbed double negatively charged carbonate ions at the surface, rather than the monodentate structure suggested in the literature. 相似文献
106.
P. P. Povinec M. K. Pham J. A. Sanchez-Cabeza G. Barci-Funel R. Bojanowski T. Boshkova W. C. Burnett F. Carvalho B. Chapeyron I. L. Cunha H. Dahlgaard N. Galabov L. K. Fifield J. Gastaud J. -J. Geering I. F. Gomez N. Green T. Hamilton F. L. Ibanez M. Ibn Majah M. John G. Kanisch T. C. Kenna M. Kloster M. Korun L. Liong Wee Kwong J. La Rosa S. -H. Lee I. Levy-Palomo M. Malatova Y. Maruo P. Mitchell I. V. Murciano R. Nelson A. Nouredine J. -S. Oh B. Oregioni G. Le Petit H. B. L. Pettersson A. Reineking P. A. Smedley A. Suckow T. D. B. van der Struijs P. I. Voors K. Yoshimizu E. Wyse 《Journal of Radioanalytical and Nuclear Chemistry》2007,273(2):383-393
A reference material designed for the determination of anthropogenic and natural radionuclides in sediment, IAEA-384 (Fangataufa
Lagoon sediment), is described and the results of certification are presented. The material has been certified for 8 radionuclides
(40K, 60Co, 155Eu, 230Th, 238U, 238Pu, 239+240Pu and 241Am). Information values are given for 12 radionuclides (90Sr, 137Cs, 210Pb (210Po), 226Ra, 228Ra, 232Th, 234U, 235U, 239Pu, 240Pu and 241Pu). Less reported radionuclides include 228Th, 236U, 239Np and 242Pu. The reference material may be used for quality management of radioanalytical laboratories engaged in the analysis of radionuclides
in the environment, as well as for the development and validation of analytical methods and for training purposes. The material
is available from IAEA in 100 g units.
Retired from IAEA in 2003. 相似文献
107.
N-Benzoxycarbonylglycyl-L-proline (L-ZGP) has been introduced as a chiral selector for enantioseparation of amines in non-aqueous capillary electrophoresis. Methanol mixed with different proportions of dichloromethane, 1,2-dichloroethane or 2-propanol containing L-ZGP and ammonium acetate was used as the background electrolyte. Enantioseparation of different types of pharmacologically active amines was performed, e.g. the local anaesthetic bupivacaine and the beta-adrenoceptor blocking agent pindolol. Addition of the solvents (dichloromethane, 1,2-dichloroethane or 2-propanol) gave an improved chiral separation partly due to a distinct decrease in the electroosmotic flow. The use of 1,2-dichloroethane in the background electrolyte gave higher precision in migration time (RSD 2.2%) compared to the systems containing dichloromethane. An enantiomeric separation of mepivacaine was performed within 72 s by use of short-end injection with an effective capillary length of 8.5 cm. 相似文献
108.
(-)-2,3:4,6-Di-O-isopropylidene-2-keto-L-gulonic acid [(-)-DIKGA] has been introduced as a chiral counter ion in non-aqueous capillary electrophoresis. High enantioresolutions (R(s)> or =3) were obtained for amines, e.g., pronethalol, labetalol and bambuterol. Methanol containing NaOH and (-)-DIKGA was used as the background electrolyte. The counter ion concentration and the nature of the injection medium were found to affect the chiral separation. Covalent coating of the fused-silica capillary reduced the electro-osmotic flow resulting in improved enantioresolutions. 相似文献
109.
L. H?glund P.O. Holtz H. Pettersson C. Asplund Q. Wang S. Almqvist H. Malm E. Petrini J.Y. Andersson 《Infrared Physics & Technology》2009,52(6):272-275
Resonant optical pumping across the band gap was used as artificial doping in InAs/In0.15Ga0.85As/GaAs quantum dots-in-a-well infrared photodetectors. Through efficient filling of the quantum dot energy levels by simultaneous optical pumping into the ground states and the excited states of the quantum dots, the response was increased by a factor of 10. Low temperature photocurrent peaks observed at 120 and 148 meV were identified as intersubband transitions emanating from the quantum dot ground state and the quantum dot excited state, respectively by a selective increase of the electron population in the different quantum dot energy levels. 相似文献
110.
Oström H Triguero L Nyberg M Ogasawara H Pettersson LG Nilsson A 《Physical review letters》2003,91(4):046102
The adsorption of octane on Cu(110) was studied by x-ray absorption and x-ray emission spectroscopy, in combination with spectrum calculations in the framework of density functional theory, as a model system for alkane adsorption on transition metals. Significant electron sharing between the adsorbate and metal surface and involvement of both bonding and antibonding C-H molecular orbitals in the molecule-metal bond was found. The calculations were extended to the case of octane adsorbed on Ni(110), and the position of the metal d band was found to be important for the bonding. The results were generalized to show that this is important for the efficiency as an alkane dehydrogenation catalyst. 相似文献