全文获取类型
收费全文 | 179篇 |
免费 | 6篇 |
专业分类
化学 | 120篇 |
晶体学 | 1篇 |
数学 | 35篇 |
物理学 | 29篇 |
出版年
2023年 | 2篇 |
2021年 | 3篇 |
2020年 | 2篇 |
2018年 | 3篇 |
2017年 | 5篇 |
2016年 | 9篇 |
2015年 | 9篇 |
2014年 | 9篇 |
2013年 | 10篇 |
2012年 | 14篇 |
2011年 | 17篇 |
2010年 | 3篇 |
2009年 | 2篇 |
2008年 | 8篇 |
2007年 | 13篇 |
2006年 | 8篇 |
2005年 | 10篇 |
2004年 | 1篇 |
2003年 | 4篇 |
2002年 | 4篇 |
2001年 | 1篇 |
2000年 | 3篇 |
1999年 | 6篇 |
1998年 | 3篇 |
1997年 | 1篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 1篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1988年 | 1篇 |
1987年 | 1篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 2篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1973年 | 1篇 |
排序方式: 共有185条查询结果,搜索用时 15 毫秒
31.
32.
X-ray fluorescence spectrometry (XRF) was applied to determine aluminium in AlCl3- and Al2O3-modified silica catalyst supports that were prepared by gas-solid reactions in an atomic layer epitaxy (ALE) process using
aluminium chloride or aluminium chloride and water as adsorbates and silica as support. INAA and AAS were used as reference
methods to determine the aluminium content of the supports. The calibration of XRF results was done by plotting the Al/Si
intensity ratios against the aluminium content as determined by atomic absorption spectrometry (AAS) and verified by instrumental
neutron activation analysis (INAA). Correlation factors for the calibration graphs were 0.984 for AlCl3/SiO2 and 0.995 for Al2O3/ SiO2 samples in the aluminium content range 0–2.6 g Al per 100 g of sample.
Received: 19 October 1998 / Accepted: 14 December 1998 相似文献
33.
We have studied the vibrational high-frequency spectrum of the water trimer computationally. We expand an earlier study [J. Chem. Phys. A 2009, 113, 9124-9132] where we approximated the water trimer as three individually vibrating water monomer units. Some intramolecular potential energy coupling terms are now included in the previous model. The six OH bond lengths and the three HOH bending angles are used as the internal coordinates. The kinetic energy operator is a sum of the kinetic energy operators of the monomer units. We use the coupled cluster method with single, double, and perturbative triple excitations method [CCSD(T)] with augmented correlation consistent polarized valence triple-ζ (aug-cc-pVTZ) basis set to calculate the potential energy surface (PES). The counterpoise correction is included in the one-dimensional part of the PES. We calculate the vibrational energy eigenvalues using the variational method. The corresponding eigenfunctions are used to obtain the absorption intensities. 相似文献
34.
We prove an Itô–Tanaka formula and existence of pathwise stochastic integrals for a wide class of Gaussian processes. Motivated by financial applications, we define the stochastic integrals as forward-type pathwise integrals introduced by Föllmer and as pathwise generalized Lebesgue–Stieltjes integrals introduced by Zähle. As an application, we illustrate the importance of the Itô–Tanaka formula for pricing and hedging of financial derivatives. 相似文献
35.
Dr. Agnes Kütt Prof. Dr. Gunnar Jeschke Dr. Lauri Toom Dr. Jaak Nerut Prof. Christopher A. Reed 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(41):8871-8874
Hydride abstraction from diarylamines with the trityl ion is explored in an attempt to generate a stable diarylnitrenium ion, Ar2N+. Sequential H-atom abstraction reactions ensue. The first H-atom abstraction leads to intensely colored aminium radical cations, Ar2NH.+, some of which are quite stable. However, most undergo a second H-atom abstraction leading to ammonium ions, Ar2NH2+. In the absence of a ready source of H-atoms, a unique self-abstraction reaction occurs when Ar=Me5C6, leading to a novel iminium radical cation, Ar=N.+Ar, which decays via a second self H-atom abstraction reaction to give a stable iminium ion, Ar=N+HAr. These products differ substantially from those derived via photochemically produced diarylnitrenium ions. 相似文献
36.
We have performed Monte Carlo simulations of homogeneous and heterogeneous nucleations of Lennard-Jones argon clusters. The simulation results were interpreted using the major concept posing a difference between the homogeneous and heterogeneous classical nucleation theories-the contact parameter. Our results show that the multiplication concept of the classical heterogeneous nucleation theory describes the cluster-substrate interaction surprisingly well even for small molecular clusters. However, in the case of argon nucleating on a rigid monolayer of fcc(111) substrate at T=60 K, the argon-substrate atom interaction being approximately one-third as strong as the argon-argon interaction, the use of the classical theory concept results in an underestimation of the heterogeneous nucleation rate by two to three orders of magnitude even for large clusters. The main contribution to this discrepancy is induced by the failure of the classical theory of homogeneous nucleation to predict the energy involved in bringing one molecule from the vapor to the cluster for clusters containing less than approximately 15 molecules. 相似文献
37.
Abnormal inversion splitting in NH2D: rotational analysis of the nu5 bending vibrational band system
A high-resolution Fourier transform infrared spectrum of the nu(5) bending vibrational band system region of the partially deuterated ammonia molecule NH(2)D has been measured and rotationally analyzed. The spectrum consists of strong a-type transitions between the states of same vibrational symmetry and weaker c-type transitions between the states of different vibrational symmetry. The Hamiltonian model used includes interaction terms between the rotational states of both upper and lower inversion doublets. The vibrational term values for the symmetric and the antisymmetric component of the upper-inversion doublet are 1,605.637 965(620) cm(-1) and 1,590.993 82(100) cm(-1), respectively, where the numbers in parentheses are one-standard deviations in the least significant digit. These figures are close to the corresponding values 1,605.62 cm(-1) and 1,590.72 cm(-1) obtained recently from results based on high-level ab initio calculations. The order of the vibrational term values is abnormal in the ammonia family, as typically the symmetric state is lower in wavenumber than the antisymmetric one. 相似文献
38.
We employ ab initio methods to find stable geometries and to calculate potential energy surfaces and vibrational wavenumbers for sulfuric acid monohydrate. Geometry optimizations are carried out with the explicitly correlated coupled-cluster approach that includes single, double, and perturbative triple excitations (CCSD(T)-F12a) with a valence double-ζ basis set (VDZ-F12). Four different stable geometries are found, and the two lowest are within 0.41 kJ mol(-1) (or 34 cm(-1)) of each other. Vibrational harmonic wavenumbers are calculated at both the density-fitted local spin component scaled second-order M?ller-Plesset perturbation theory (DF-SCS-LMP2) with the aug-cc-pV(T+d)Z basis set and the CCSD-F12/VDZ-F12 level. Water O-H stretching vibrations and two highly anharmonic large-amplitude motions connecting the three lowest potential energy minima are considered by limiting the dimensionality of the corresponding potential energy surfaces to small two- or three-dimensional subspaces that contain only strongly coupled vibrational degrees of freedom. In these anharmonic domains, the vibrational problem is solved variationally using potential energy surfaces calculated at the CCSD(T)-F12a/VDZ-F12 level. 相似文献
39.
40.
Eskola AJ Geppert WD Rissanen MP Timonen RS Halonen L 《The journal of physical chemistry. A》2005,109(24):5376-5381
The kinetics of the reactions of chlorinated methyl radicals (CH2Cl, CHCl2, and CCl3) with NO2 have been studied in direct measurements at temperatures between 220 and 360 K using a tubular flow reactor coupled to a photoionization mass spectrometer. The radicals have been homogeneously generated at 193 or 248 nm by pulsed laser photolysis of appropriate precursors. Decays of radical concentrations have been monitored in time-resolved measurements to obtain the reaction rate coefficients under pseudo-first-order conditions with the amount of NO2 being in large excess over radical concentrations. The bimolecular rate coefficients of all three reactions are independent of the bath gas (He or N2) and pressure within the experimental range (1-6 Torr) and are found to depend on temperature as follows: k(CH2Cl + NO2) = (2.16 +/- 0.08) x 10(-11) (T/300 K)(-1.12+/-0.24) cm3 molecule(-1) s(-1) (220-363 K), k(CHCl2 + NO2) = (8.90 +/- 0.16) x 10(-12) (T/300 K)(-1.48+/-0.13) cm3 molecule(-1) s(-1) (220-363 K), and k(CCl3 + NO2) = (3.35 +/- 0.10) x 10(-12) (T/300 K)(-2.2+/-0.4) cm3 molecule(-1) s(-1) (298-363 K), with the uncertainties given as one-standard deviations. Estimated overall uncertainties in the measured bimolecular reaction rate coefficients are about +/-25%. In the reactions CH2Cl + NO2, CHCl2 + NO2, and CCl3 + NO2, the products observed are formaldehyde, CHClO, and phosgene (CCl2O), respectively. In addition, a weak signal for the HCl formation has been detected for the CHCl2 + NO2 reaction. 相似文献