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101.
102.
The vibrational overtone induced unimolecular dissociation of HMHP (HOCH(2)OOH) and HMHP-d(2) (HOCD(2)OOH) into OH and HOCH(2)O (HOCD(2)O) fragments is investigated in the region of the 4nu(OH) and 5nu(OH) bands. The unimolecular dissociation rates in the threshold region, corresponding to the 4nu(OH) band, exhibit measurable differences associated with excitation of the OH stretch of the alcohol versus the peroxide functional group, with the higher energy alcohol OH stretching state exhibiting a slower dissociation rate compared to the lower energy peroxide OH stretch in both HMHP and HMHP-d(2). Predictions using the Rice-Ramsperger-Kassel-Marcus theory give rates that are in reasonably good agreement with the measured dissociation rate for the alcohol OH stretch but considerably differ from the measured rates for the peroxide OH stretch in both isotopomers. The present results are interpreted as suggesting that the extent of intramolecular vibrational energy redistribution (IVR) is different for the two OH stretching states associated with the two functional groups in HMHP, with IVR being substantially less complete for the peroxide OH stretch. Analysis of the OH fragment product state distributions in conjunction with phase-space theory simulation gives a D(0) value of 38+/-0.7 kcal/mole for breaking the peroxide bond in HMHP. 相似文献
103.
Rachael Alvir Sophia Dever Benjamin Lovitz James Myer Christino Tamon Yan Xu Hanmeng Zhan 《Journal of Algebraic Combinatorics》2016,43(4):801-826
For a graph G and a related symmetric matrix M, the continuous-time quantum walk on G relative to M is defined as the unitary matrix \(U(t) = \exp (-itM)\), where t varies over the reals. Perfect state transfer occurs between vertices u and v at time \(\tau \) if the (u, v)-entry of \(U(\tau )\) has unit magnitude. This paper studies quantum walks relative to graph Laplacians. Some main observations include the following closure properties for perfect state transfer. If an n-vertex graph has perfect state transfer at time \(\tau \) relative to the Laplacian, then so does its complement if \(n\tau \in 2\pi {\mathbb {Z}}\). As a corollary, the join of \(\overline{K}_{2}\) with any m-vertex graph has perfect state transfer relative to the Laplacian if and only if \(m \equiv 2\pmod {4}\). This was previously known for the join of \(\overline{K}_{2}\) with a clique (Bose et al. in Int J Quant Inf 7:713–723, 2009). If a graph G has perfect state transfer at time \(\tau \) relative to the normalized Laplacian, then so does the weak product \(G \times H\) if for any normalized Laplacian eigenvalues \(\lambda \) of G and \(\mu \) of H, we have \(\mu (\lambda -1)\tau \in 2\pi {\mathbb {Z}}\). As a corollary, a weak product of \(P_{3}\) with an even clique or an odd cube has perfect state transfer relative to the normalized Laplacian. It was known earlier that a weak product of a circulant with odd integer eigenvalues and an even cube or a Cartesian power of \(P_{3}\) has perfect state transfer relative to the adjacency matrix. As for negative results, no path with four vertices or more has antipodal perfect state transfer relative to the normalized Laplacian. This almost matches the state of affairs under the adjacency matrix (Godsil in Discret Math 312(1):129–147, 2011). 相似文献
104.
本工作报道了用31P NMR谱定量分析活体肝胵Fasiciola hepatica中含磷化合物的实验方法及一些初步结果,测定了活体肝胵体内含磷化合物的弛豫时间T1,观察了无灌注循环系统时肝胵体内pH值变化。利用高氯酸萃取物测得的31P NMR谱,定出了各谱峰的归属,观察了用含糖及缺糖培养液培养的肝胵糖类养料的代谢变化,并利用13C NMR谱肯定了肝胵体内主要含磷化合物之一的α-甘油磷酰胆碱31P NMR谱峰的归属。 相似文献
105.
106.
Craig Aalseth Erica Andreotti Dirk Arnold Joan-Albert Sanchez Cabeza Detlev Degering Andrea Giuliani Raquel Gonzales de Orduña Rodolfo Gurriaran Mikael Hult Martin Keillor Matthias Laubenstein Gilbert le Petit Romul Mircea Margineanu Murray Matthews Harry Miley Iolanda Osvath Monica Pellicciari Wolfango Plastino Hardy Simgen Marc Weber Robert Werzi 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(3):731-735
Aerosol samples collected on filter media were analyzed using HPGe detectors employing varying background-reduction techniques in order to experimentally evaluate the opportunity to apply ultra-low background measurement methods to samples collected, for instance, by the Comprehensive Test Ban Treaty International Monitoring System (IMS). In this way, realistic estimates of the impact of low-background methodology on the sensitivity obtained in systems such as the IMS were assessed. The current detectability requirement of stations in the IMS is 30 μBq/m3 of air for 140Ba, which would imply ~106 fissions per daily sample. Importantly, this is for a fresh aerosol filter. One week of decay reduces the intrinsic background from radon daughters in the sample allowing much higher sensitivity measurement of relevant isotopes, including 131I. An experiment was conducted in which decayed filter samples were measured at a variety of underground locations using Ultra-Low Background (ULB) gamma spectroscopy technology. The impacts of the decay and ULB are discussed. 相似文献
107.
108.
In this paper we investigate some notions of completion of partial metric spaces, including the bicompletion, the Smyth completion, and a new “spherical completion”. Given an auxiliary relation, we show that it arises from a totally bounded partial metric space, and the spherical completion of such a space is its round ideal completion. We also give an example of a totally bounded partial metric space whose bicompletion and Smyth completion are not continuous posets. Finally, we present an example of a totally bounded partial metric giving rise to the Scott and lower topologies of a continuous poset, but whose spherical completion is not a continuous poset. 相似文献
109.
Photolysis of solutions of M(CO)(6) (M = Cr, W) at low temperature in the presence of hydrogen gas affords Cr(CO)(5)(H(2)) (1) and W(CO)(5)(H(2)) (2). Complexes 1 and 2 are characterized as dihydrogen complexes based on short T(1) values for the hydride resonances and the observation of a large HD coupling in the HD derivatives. Irradiation of a phosphine-substituted derivative (PMe(3))Cr(CO)(5) in the presence of hydrogen gas gave similar results. Thus cis-(PMe(3))Cr(CO)(4)(H(2)) (3) and trans-(PMe(3))Cr(CO)(4)(H(2)) (4) were prepared and characterized by (1)H and (31)P NMR spectroscopy. When the photolysis reactions were carried out in methylene chloride, solvent binding competitive with hydrogen binding was observed. This was not observed in less coordinating solvents such as alkanes. Subsequent displacement of solvent by H(2) leads to the dihydrogen complexes. Complexes 1 and 2 are moderately acidic, with deprotonation effected by mild bases. 相似文献
110.
Qiu JX Petersson EJ Matthews EE Schepartz A 《Journal of the American Chemical Society》2006,128(35):11338-11339
Folded polymers in nature are assembled from simple monomers and adopt complex folded structures through networks of stabilizing noncovalent interactions. These interactions define secondary and tertiary structure and in most cases specify a unique three-dimensional architecture. Individual secondary or tertiary structures can also associate with one another to form multi-subunit quaternary structures. Nonnatural folded polymers have potential for similar structural versatility. Here we describe a pair of beta3-peptides whose sequences were designed to promote a 14-helix structure in water, favor hetero-oligomer formation, and disfavor nonspecific aggregation. These beta3-peptides assemble noncovalently into a well-defined hetero-oligomer characterized by a defined stoichiometry, a highly stabilized secondary structure, and a cooperative melting transition (TM > 55 degrees C). This work demonstrates that beta3-peptides can assemble into defined, cooperatively folded quaternary structures and constitutes an important step toward designing protein-like assemblies from nonnatural polymers. 相似文献