全文获取类型
收费全文 | 1748篇 |
免费 | 46篇 |
国内免费 | 5篇 |
专业分类
化学 | 1193篇 |
晶体学 | 15篇 |
力学 | 40篇 |
数学 | 122篇 |
物理学 | 429篇 |
出版年
2023年 | 21篇 |
2022年 | 27篇 |
2021年 | 33篇 |
2020年 | 32篇 |
2019年 | 47篇 |
2018年 | 32篇 |
2017年 | 30篇 |
2016年 | 37篇 |
2015年 | 21篇 |
2014年 | 46篇 |
2013年 | 99篇 |
2012年 | 132篇 |
2011年 | 125篇 |
2010年 | 77篇 |
2009年 | 54篇 |
2008年 | 108篇 |
2007年 | 85篇 |
2006年 | 74篇 |
2005年 | 105篇 |
2004年 | 62篇 |
2003年 | 48篇 |
2002年 | 30篇 |
2001年 | 42篇 |
2000年 | 28篇 |
1999年 | 25篇 |
1998年 | 14篇 |
1997年 | 21篇 |
1996年 | 17篇 |
1995年 | 20篇 |
1994年 | 14篇 |
1993年 | 16篇 |
1992年 | 12篇 |
1991年 | 13篇 |
1990年 | 7篇 |
1989年 | 10篇 |
1988年 | 14篇 |
1986年 | 10篇 |
1985年 | 20篇 |
1984年 | 20篇 |
1983年 | 10篇 |
1982年 | 15篇 |
1981年 | 9篇 |
1980年 | 10篇 |
1979年 | 8篇 |
1978年 | 12篇 |
1976年 | 8篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1971年 | 8篇 |
1970年 | 9篇 |
排序方式: 共有1799条查询结果,搜索用时 15 毫秒
41.
A Koll A Filarowski D Fitzmaurice E Waghorne A Mandal S Mukherjee 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2002,58(1):197-207
Two new orthohydroxy Schiff bases, 7-phenylsalicylidene benzylamine (PSBA) and 7-ethylsalicylideneaniline (ESA) have been synthesized. The excited state intramolecular proton transfer (ESIPT) and the structure of PSBA and ESA in its crystalline form and in the solvents n-hexane, n-heptane and 1,4-dioxane have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and 77K. One ground state species has been detected both in neutral and basic solutions of both PSBA and ESA: the cis-enol form with an intramolecular hydrogen bond. The ESIPT and formation of keto tautomer are evidenced by a large Stokes shifted emission (approximately 12000 cm(-1)) at room temperature only in the case of ESA. On the other hand the keto tautomer is the predominant species at 77K in a solid matrix and as a solid sample at room temperature both in the case of ESA and PSBA. In the case of both ESA and PSBA the more intense, higher energy emission is due to the species which has not undergone ESIPT and attributed mainly due to cis-enol form. The trans-enol form is also observed by changing the excitation wavelength. Both the compounds are found to undergo a structural change to a zwitterionic and intermolecular hydrogen bonded form in the presence of a strong base like triethylamine. From the nanosecond measurements and quantum yield of fluorescence we have estimated the decay rates of proton transfer reaction in the case of PSBA. Our theoretical calculation at the AM1 level of approximation shows that the ground singlet state has a rather large activation barrier both in the case of PSBA and ESA. The barrier height is much lower on the corresponding excited singlet surface only in the case of ESA. The process is predicted to be endothermic in the ground state and exotherrmic in the excited singlet state. 相似文献
42.
A. Mandal A. Koll A. Filarowski D. Majumder S. Mukherjee 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》1999,55(14):2861
A new orthohydroxy Schiff base, 7-ethylsalicylidenebenzylamine (ESBA) has been synthesised. The excited state intramolecular proton transfer (ESIPT) processes have been investigated by means of absorption, emission and nanosecond spectroscopy at room temperature and at 77 K in non polar solvents. The ESIPT is evidenced by a large Stokes shifted emission (11 000 cm−1) only at 77 K. From fluorescence and excitation spectra it is suggested that at least three different species are present in the excited state at room temperature. Our theoretical calculation at AM1 level confirm the cis-isomer to be the only viable form in the ground state. 相似文献
43.
B. Saha T. K. Mukherjee A. K. Das P. K. Mukherjee 《International journal of quantum chemistry》2003,91(5):626-632
Dipole‐allowed transitions have been studied for the first few members of the Si isoelectronic sequence. Transition energies, oscillator strengths, transition probabilities and quantum defect values have been estimated for the low‐ and high‐lying excited states of s and d symmetries up to the principal quantum number n=7 for these 3p open shell ions from P+ to Cr10+. Time‐dependent coupled Hartree–Fock (TDCHF) theory has been utilized to calculate such transition properties. Most of the results for transition energies, oscillator strengths, and transition probabilities for higher excited states are new. The transition energies for low‐lying excited states agree well with experimental data wherever available. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
44.
The semiquinone radicals produced by one-electron reduction of 9, 10-anthraquinone, 1-amino-9, 10-anthraquinone and 1-hydroxy-9, 10-anthraquinone have been characterized in aqueous-organic mixed solvent comprising of 30.2 mol dm−3 water, 5 mol dm−3 isopropanol and 1 mol dm−3 acetone, using the pulse radiolysis technique. Spectroscopic characteristics, the kinetic parameters of formation and decay and one acid dissociation constants of the semiquinones and one-electron reduction potentials of the quinones have been estimated. The characteristics of the present semiquinone systems have been compared with those of other similar systems. The observed differences in characteristics of the semiquinones due to different substitutions have been analysed. 相似文献
45.
The isotropic proton shifts for the pyridine N-oxide and γ-picoline N-oxide protons have been observed in the penta coordinated adducts of these bases with bis[di(p-tolyl)dithiophosphinato] cobalt(II). The contribution to the observed shifts due to dipolar interaction has been calculated. From the dipolar shifts, it was ascertained that the pyridine N-oxide complexes have a bent structure in solution with a Co-O-N angle of 125°. An estimate of the paramagnetic anisotropy of the cobalt complex yields K?-K⊥ = 4244 × 10?6 cm3/mole. 相似文献
46.
A Sarkar N Biswas S Kapoor H S Mahal C K K Nair T Mukherjee 《Research on Chemical Intermediates》2005,31(9):857-866
The oxidation of flavonoids is of great interest because of their action as antioxidants with the ability to scavenge radicals
by means of electron-transfer processes. The redox reactions of the flavonoid derivative troxerutin, (2-[3,4-bis-(2-hydroxyethoxy)
phenyl]-3[[6-deoxy-α-L-manno-pyranosyl)-β-(D-glucopyranosyl]-oxy]-5-hydroxy-7-(2-hydroxyethoxy)-4H-1-benzo-pyran-4-one), were investigated over a wide range of conditions,
using pulse radiolysis and cyclic voltammetry. The oxidation mechanism proceeds in sequential steps. One-electron redox potentials
for troxerutin were found to be +1.196, +0.846 and −0.634 V vs. NHE. 相似文献
47.
A general partial summation method for including arbitrary classes of diagrams to all orders in the coupled cluster based size consistent energy functional for closed shell states is developed. Since the various reduced density matrices which appear in the energy functional are essentially the time-independent analogues of the corresponding many body Green functions, it is possible to derive Dyson-like equations for these quantities. By expanding the associated proper self energy parts in terms of the T-amplitudes, one can carry out partial summations in the reduced density matrices and thus in energy. At a higher level, higher order terms in a proper self energy can also be generated by renormalizing the internal propagators in it, and considering only the irreducible self-energy terms. 相似文献
48.
Chaudhuri RK Freed KF Hose G Piecuch P Kowalski K Włoch M Chattopadhyay S Mukherjee D Rolik Z Szabados A Tóth G Surján PR 《The Journal of chemical physics》2005,122(13):134105
Tests have been made to benchmark and assess the relative accuracies of low-order multireference perturbation theories as compared to coupled cluster (CC) and full configuration interaction (FCI) methods. Test calculations include the ground and some excited states of the Be, H(2), BeH(2), CH(2), and SiH(2) systems. Comparisons with FCI and CC calculations show that in most cases the effective valence shell Hamiltonian (H(v)) method is more accurate than other low-order multireference perturbation theories, although none of the perturbative methods is as accurate as the CC approximations. We also briefly discuss some of the basic differences among the multireference perturbation theories considered in this work. 相似文献
49.
Asok K. Mukherjee 《Journal of mathematical chemistry》1988,2(3):279-286
Squares of the adjacency matrices of bipartite cycles (Cv) can be block-factored into matrices which correspond to vertex-weighted complete graphs forv = 6, vertex-weighted strongly regular graphs forv = 8 and 10, and vertex-weighted metrically regular graphs forv > 10. Using this fact and some properties of strongly and metrically regular graphs, it is shown that eigenvalues of large bipartite C
v
graphs (i.e. large even annulenes) can be expressed by the general formula ± (2 ± (2 ± (... ± (2 +r
p)) ...), wherev = 2
n
×p,n is the number of surd () signs required andp = 3, 4 and 5. Here,r
3,r
4, andr
5, are the eigenvalues of the complete graphK
3 and the strongly regular graphsS
4 andS
5 respectively. The procedure does not require construction of characteristic polynomials for the determination of eigenvalues, and brings out a common topological origin for the two-fold degeneracies observed in the eigenvalue spectra of all even cycles and many odd cycles. 相似文献
50.
Redox reactions of disulfiram (DSF) were studied in aqueous solutions using the pulse-radiolysis technique. Reactions of DSF with one-electron oxidants Br2
- and N3, generated pulse radiolytically in aqueous solution at pH 7, yielded a transient (max = 480 nm) which exhibited the characteristics of a disulphide cation radical and decayed by second-order kinetics. Reactions of DSF with halogenated peroxyl radicals CCl3O2, CHCl2O2, CH2ClO2 and CBr3O2 led to the formation of an adduct absorbing at 580 nm. The reduction potential was estimated to be 1.24 ± 0.06 V vs. NHE. 相似文献