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951.
The extended Koopmans’ theorem is related to Fukui function, which measures the change in electron density that accompanies
electron attachment and removal. Two approaches are used, one based on the extended Koopmans’ theorem differential equation
and the other based directly on the expression of the ionized wave function from the extended Koopmans’ theorem. It is observed
that the Fukui function for electron removal can be modeled as the square of the first Dyson orbital, plus corrections. The
possibility of useful generalizations to the extended Koopmans’ theorem is considered; some of these extensions give approximations,
or even exact expressions, for the Fukui function for electron attachment. 相似文献
952.
Shigeru Arimoto 《Journal of mathematical chemistry》2007,41(3):231-269
The present article is the first part of a series devoted to extending the Repeat Space Theory (RST) to apply to carbon nanotubes
and related molecular networks. Four key problems are formulated whose affirmative solutions imply the formation of the initial
investigative bridge between the research field of nanotubes and that of the additivity and other network problems studied
and solved by using the RST. All of these four problems are solved affirmatively by using tools from the RST. The Piecewise
Monotone Lemmas (PMLs) are cornerstones of the proof of the Fukui conjecture concerning the additivity problems of hydrocarbons.
The solution of the fourth problem gives a generalized analytical formula of the pi-electron energy band curves of nanotube
(a, b), with two new complex parameters c and d. These two parameters bring forth a broad class of analytic curves to which the PMLs and associated theoretical devices apply.
Based on the above affirmative solutions of the problems, a central theorem in the RST, called the asymptotic linearity theorem
(ALT) has been applied to nanotubes and monocyclic polyenes. Analytical formulae derived in this application of the ALT illuminate
in a new global context (i) the conductivity of nanotubes and (ii) the aromaticity of monocyclic polyenes; moreover an analytical
formula obtained by using the ALT provides a fresh insight into Hückel’s (4n+2) rule. The present article forms a foundation of the forthcoming articles in this series.
The present series of articles is closely associated with the series of articles entitled ‘Proof of the Fukui conjecture via
resolution of singularities and related methods’ published in the JOMC. 相似文献
953.
原位氧化还原沉淀水热合成法制备LixMn2O4尖晶石 总被引:3,自引:0,他引:3
Li xMn2O4尖晶石是新一代的锂离子二次电池正极材料 [1], 其合成方法对材料的电化学性质影响很大[2].常规合成大多采用高温固相反应法, 此法具有反应温度高, 反应时间长, 容易产生缺陷和产物不纯净等缺点, 导致所合成的锂离子二次电池正极材料的性能较差. 目前用水热合成法制备电池正极材料Li xMn2O4尖晶石尚未见文献报道. 本文在常规水热合成法的基础上采用原位氧化还原沉淀水热合成法 [3]制备前驱物, 该法合成条件更温和, 而且使材料的综合性能得到了改善和提高. 相似文献
954.
A simple and very sensitive spectrophotometric method for the direct determination of copper ions 总被引:1,自引:0,他引:1
A sensitive spectrophotometric method for the direct determination of copper in aqueous samples without a preconcentration step has been developed. It is based on the formation of a yellow complex with the chromogenic reagent di-2-pyridyl ketone benzoylhydrazone (dPKBH) in an alkaline medium. The complex stoichiometry was 1:2 (Cu:dPKBH) and presents maximum absorbance at 370 nm. The influence of chemical variables affecting the behaviour of the system such as pH, concentration of dPKBH, buffer solution and ethanol, order of addition of the reagents and stability of the complex, were evaluated. The molar absorptivity (epsilon) was 3.92x10(4) L mol(-1) cm(-1), and Beer's law was obeyed up to 3 mg L(-1) of copper. The relative standard deviation was 0.46% (n=11) for a sample containing 1 mg L(-1) Cu(II). The limit of detection was 2.5 micro g L(-1) and was therefore more sensitive than the direct methods reported previously. Finally, the method was successfully validated by analysing several real samples with different matrices, such as tap water, natural water or copper alloys, with an average relative error of 2.46%. 相似文献
955.
Xiufang Xu Yumei Xing Xia Yang Guichang Wang Zunsheng Cai Zhenfeng Shang Yinming Pan Xuezhuang Zhao 《International journal of quantum chemistry》2005,101(2):160-168
A total of eight possible isomers of C50O, an oxide of fullerene C50 (D5h), have been investigated by B3LYP/3‐21G calculations. The isomer, which has an annulene‐like structure with oxygen bridging across a [5,6] type C? C bond at the site between the pole and the equatorial belt, is found being the ground state of C50O. Four isomers are relatively more stable and the energy differences between them are not large. This result indicates that more than one C50O isomer will coexist once C50O is synthesized. The relative stabilities of the C50O isomers may be determined mainly by the strain release and by the formation of the cyclic phenylene substructure at the equatorial belt of the cage. The calculated nucleus independent chemical shifts (NICS) of the C50O isomers will be useful because from them one can expect outstanding NMR properties that can lead to their identification and characterization. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
956.
The preparation of pure Y3Al5O12 (YAG) and 50 vol% Al2O3–YAG
composite powders by a wet chemical route is presented. The role of the synthesis
temperature during reverse-strike precipitation has been investigated, showing
its relevant effect on the purity and homogeneity of YAG powder.
The
composite material was prepared by comparing two different synthesis routes.
A composite powder was synthesized via reverse-strike temperature-controlled
co-precipitation. In the latter case, a pure-alumina precursor was firstly
reverse-strike precipitated and then doped with an yttrium salt solution.
For both syntheses, the role of thermal and mechanical pre-treatments on the
phase development was demonstrated. 相似文献
957.
Reza Behjatmanesh-Ardakani 《Theoretical chemistry accounts》2007,118(4):799-805
In some works on the lattice Monte Carlo simulation of amphiphilic systems additional peaks in the cluster size distribution
has been interpreted as a clue for the phase or shape transition of micellar aggregates. On the other hand, some other works
showed that the additional peaks are a result of finite size of the lattice box. In this paper using calculating energy-auto-correlation
function and statistical error in correlated data, it is shown that how these apparently contradictory results are the same.
To do this, we have simulated a pure system containing amphiphile and water molecules. A simple model of potential containing
the main feature for these systems (the hydrophobicity of surfactant molecules) that cause the aggregates to be formed is
considered to avoid any synthetic results due to additional non-real parameters. To relax the initial configuration faster,
configurational bias Monte Carlo move is used in addition to reptation move. Periodic boundary condition and self-avoiding
walks are used as former published works in this field. It is shown that the additional peaks is a result of the statistical
errors for averaged cluster size distribution and can not be interpreted as a clue for shape or phase transition. 相似文献
958.
N. A. Mohamed Farook 《Journal of solution chemistry》2007,36(3):345-356
The oxidation kinetics of substituted and unsubstituted 4-oxoacids (S) by N-chlorosaccharin (NCSA) have been studied in aqueous acetic acid media. The reaction follows first-order kinetics in each
of the 4-oxoacids, NCSA and H+. The effect of changes in the electronic nature of the substrate reveals that positive charge develops in the transition
state. Based on the kinetic results and product analysis, a suitable mechanism has been proposed for the reaction of NCSA
with 4-oxoacids. 相似文献
959.
Electroactive conducting copolymers of aniline (ANI) and o-aminophenol (OAP) and two-layered poly(o-aminophenol) (POAP)/polyaniline (PANI) composites were prepared in aqueous acidic solution by electrode potential cycling.
Copolymerization was carried out at different feed concentrations of OAP and ANI on a gold electrode. A strong inhibition
of electropolymerization was found at a high molar fraction of OAP in the feed. The copolymers showed good adherence on the
electrode surface and gave a redox response up to pH=10.0. Two transitions were observed in the in situ conductivities of
the copolymers (as with PANI), but the conductivities were lower by 2.5–3 orders of magnitude as compared to PANI. Electrosynthesis
of PANI on POAP modified electrodes showed copolymer formation after reaction initiation and finally formation of a PANI layer
at the copolymer/solution interface. The ‘memory effect’ of the bilayer structures of both polymers was discussed in terms
of protonation/deprotonation and anion consumption taking place during redox processes of both polymers. 相似文献
960.
Gamil A. Al-Hazmi Mohammed S. El-Shahawi Ahmed A. El-Asmy 《Transition Metal Chemistry》2005,30(4):464-470
The redox properties of the title mono- and binuclear copper(II) chelates have been investigated by cyclic voltammetry in DMF at a working platinum electrode. The cathodic reduction and anodic oxidation of the investigated chelates produced the corresponding electrochemical CuI and CuIIIspecies stable only in the voltammetric time scale, The effects of substituents on E1/2, redox properties and stability towards oxidation of the complexes were related to the electron-withdrawing or releasing ability of the substituents on the C=N1[H, CH3 or C6H5] and/or N4H [H, C2H5, C6H5 or pClC6H4] groups, The electron attracting substituents stabilize the Cu(II) complexes while electron-donating groups favor oxidation to Cu(III). Changes in the E1/2 for the complexes due to remote substituent effects could be related to changes in basicity of N4H.Thus, variation in N41-J has more influence on E1/2 than changes in C=N1. The correlation between E1/2 of the complexes and pKa of the ligands has been attributed to the spherical potential generated by the electron density of the donor atoms at the antibonding d orbitals. 相似文献