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1.
2.
The angular variations of the five-fold differential cross section obtained by using different wave functions of helium are
compared with experimental data. It is found that in the coplanar geometry two kinematical arrangements, (i) equal energy
sharing between the two ejected electrons with one of them ejected along the momentum transfer direction and the other along
varying direction and (ii) the Bethe ridge condition with fixed sum of ejected electron energies and varying angle between
them, are very sensitive to e-e correlations contained in the target wave function. This comparison has been used to show
that open-shell class of wave functions better incorporate e-e correlations than the closed-shell class. 相似文献
3.
4.
Daniel C.S. Tse Theodore Kuwana Garfield P. Royer 《Journal of Electroanalytical Chemistry》1979,98(2):345-353
Methylaminopropylviologen (MAV) was covalently attached to glassy carbon electrodes via cyuranic chloride. X-ray photoelectron spectroscopy (XPS) analysis confirmed the presence of bound MAV on the electrode surfaces. Electrochemical experiments of these electrodes indicated that the bound MAV was stable and electrochemically active for extended periods of time in aqueous media. The surface coverage of MAV was in the range, of 2.0–3.0×10?10 mol cm?2. 相似文献
5.
In the presence of [Ru(terpyridine)(2,6‐pyridinedicarboxylate)], aliphatic and benzylic alcohols are oxidized to the corresponding aldehydes or ketones with high selectivity by using hydrogen peroxide as the oxidant. There is no need for the addition of co‐catalysts or organic solvents. By applying an optimized reaction protocol, high catalyst productivity (turnover number>10 000) and activity (turnover frequency up to 14 800 h?1) has been achieved. 相似文献
6.
Boddy CN Hotta K Tse ML Watts RE Khosla C 《Journal of the American Chemical Society》2004,126(24):7436-7437
Engineered biosynthetic pathways provide a powerful method for generating complex molecules. Precursor-directed biosynthesis, which combines chemical synthesis and enzymatic transformations, allows non-native starting materials to be incorporated into biosynthetic pathways. Using this approach, we achieved the production of the anticancer agent epothilone C in Escherichia coli. An E. coli strain was engineered to express the last three modules of the epothilone biosynthetic pathway (epoD-M6, epoE, and epoF) and the substrate required to complement the biosynthetic enzymes was obtained by chemical synthesis. Under high-density cell culture conditions, the E. coli strain processed exogenously fed synthetic substrate into epothilone C at levels comparable to the native host (1 mg/L) and at higher levels than other heterologous hosts. Importantly, this precursor-directed approach will allow chemical modifications to be introduced into the polyketide backbone and may ultimately provide access to epothilone analogues with improved pharmacological properties in quantities sufficient for clinical development. 相似文献
7.
8.
Variable-energy valence and inner-valence photoelectron spectra have been recorded for the CpNiNO complex (Cp = eta(5)-C(5)H(5)) between 21.2 and 100 eV, using He I radiation and synchrotron radiation. The ground state electronic structure has been calculated by using the Xalpha-SW method. Photoionization cross sections (sigma) have also been calculated for the valence ionizations using the Xalpha-SW method. The theoretical branching ratios (sigma(i)/ summation operatorsigma) have been compared with the observed branching ratios (A(i)()/ summation operatorA) between 21.2 and 100 eV. The assignment of the photoelectron spectrum based on the analysis of intensity variations and width of vibrational peaks is consistent with the ion state orbital ordering 5e(1)(1) < 7a(1)(2) < 3e(2)(3) < 4e(1)(4) (band numbers are in parentheses) and is inconsistent with another recently proposed ordering 5e(1)(1), 5e(1)(2) < 7a(1), 3e(2)(3) < 4e(1)(4), which takes the 5e(1) vibronic effects into consideration. The experimental branching ratio results indicate a Ni 3p resonance effect around 75 eV in the photoionization process. The inner-valence spectrum has also been assigned with the aid of the Xalpha-SW calculations. 相似文献
9.
Jerald S. Bradshaw Ralph B. Nielsen Pui-Kwan Tse Giuseppi Arena Bruce E. Wilson N. Kent Dalley John D. Lamb James J. Christensen Reed M. Izatt 《Journal of heterocyclic chemistry》1986,23(2):361-368
A series of macrocyclic polyether (crown) ligands containing the proton-ionizable s-triazole subcyclic unit were prepared by reacting the 1-THP blocked 3,5-bis(chloromethyl)-1H-1,2,4-triazole with various oligoethylene glycols. The starting bis(chloromethyl)triazole is a vessicant and must be used with caution. Triazolo-18-crown-6 ( 5 ) formed stable complexes with barium, strontium, copper and benzylammonium cations but not with potassium or lithium. The crystal structure of 5 showed the triazole proton to be on nitrogen 3 which is outside the macroring cavity. 相似文献
10.
We report computational studies on Al(+)(H(2)O)(n), and HAlOH(+)(H(2)O)(n-1), n = 6-14, by the density functional theory based ab initio molecular dynamics method, employing a planewave basis set with pseudopotentials, and also by conventional methods with Gaussian basis sets. The mechanism for the intracluster H(2) elimination reaction is explored. First, a new size-dependent insertion reaction for the transformation of Al(+)(H(2)O)(n), into HAlOH(+)(H(2)O)(n-1) is discovered for n > or = 8. This is because of the presence of a fairly stable six-water-ring structure in Al(+)(H(2)O)(n) with 12 members, including the Al(+). This structure promotes acidic dissociation and, for n > or = 8, leads to the insertion reaction. Gaussian based BPW91 and MP2 calculations with 6-31G* and 6-31G** basis sets confirmed the existence of such structures and located the transition structures for the insertion reaction. The calculated transition barrier is 10.0 kcal/mol for n = 9 and 7.1 kcal/mol for n = 8 at the MP2/6-31G** level, with zero-point energy corrections. Second, the experimentally observed size-dependent H(2) elimination reaction is related to the conformation of HAlOH(+)(H(2)O)(n-1), instead of Al(+)(H(2)O)(n). As n increases from 6 to 14, the structure of the HAlOH(+)(H(2)O)(n-1) cluster changes into a caged structure, with the Al-H bond buried inside, and protons produced in acidic dissociation could then travel through the H(2)O network to the vicinity of the Al-H bond and react with the hydride H to produce H(2). The structural transformation is completed at n = 13, coincident approximately with the onset of the H(2) elimination reaction. From constrained ab initio MD simulations, we estimated the free energy barrier for the H(2) elimination reaction to be 0.7 eV (16 kcal/mol) at n = 13, 1.5 eV (35 kcal/mol) at n = 12, and 4.5 eV (100 kcal/mol) at n = 8. The existence of transition structures for the H(2) elimination has also been verified by ab initio calculations at the MP2/6-31G** level. Finally, the switch-off of the H(2) elimination for n > 24 is explored and attributed to the diffusion of protons through enlarged hydrogen bonded H(2)O networks, which reduces the probability of finding a proton near the Al-H bond. 相似文献