一氧化二氮的光电离质谱研究

在入射电子能量2500eV、能量分辨200meV的条件下测量了一氧化二氮分子在7.8～24.5 eV的光学振子强度密度谱和光电离质谱,报道了N2O+、NO+、O+、N2+和N+等离子在较高能量分辨下的部分光学振子强度密度,首次给出了一氧化二氮分子在13.0～21.0 eV能区中性解离的振子强度密度.并在对这些数据进行分析的基础上阐述了一氧化二氮分子超激发态的不同退激发道的竞争过程.     

Density functional theory studies on the dissociation energies of metallic salts: relationship between lattice and dissociation energies

The formation and physicochemical properties of polymer electrolytes strongly depend on the lattice energy of metal salts. An indirect but efficient way to estimate the lattice energy through the relationship between the heterolytic bond dissociation and lattice energies is proposed in this work. The heterolytic bond dissociation energies for alkali metal compounds were calculated theoretically using the Density Functional Theory (DFT) of B3LYP level with 6‐311+G(d,p) and 6‐311+G(2df,p) basis sets. For transition metal compounds, the same method was employed except for using the effective core potential (ECP) of LANL2DZ and SDD on transition metals for 6‐311+G(d,p) and 6‐311+G(2df,p) calculations, respectively. The dissociation energies calculated by 6‐311+G(2df,p) basis set combined with SDD basis set were better correlated with the experimental values with average error of ca. ±1.0% than those by 6‐311+G* combined with the LANL2DZ basis set. The relationship between dissociation and lattice energies was found to be fairly linear (r>0.98). Thus, this method can be used to estimate the lattice energy of an unknown ionic compound with reasonably high accuracy. We also found that the dissociation energies of transition metal salts were relatively larger than those of alkaline metal salts for comparable ionic radii. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 827–834, 2001     

Calculation of sequence‐dependent free energies of hydration of dipeptides formed by alanine and glycine

The relative free energies of hydration of the dipeptides glycylalanine and alanyl‐glycine in their naturally occurring form have been calculated both for the zwitterionic and protonated species. Emphasis was laid on comparisons between the conventional cutoff method and the Particle Mesh Ewald method to account for possible differences in electrostatic contributions to the free energy. Furthermore, the convergence behavior of the total free energy and its individual contributions were examined. The results, obtained by means of the thermodynamic integration technique as implemented in the free energy module of the AMBER program suite, suggest that in aqueous solution glycylalanine is more stable than alanylglycine by 2.7 kcal/mol in the zwitterionic form and by 3.5 kcal/mol in the protonated form. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 846–860, 2001     

Synthesis and Photophysical Properties of C60‐carbazole Adducts

Three C₆₀‐carbazole adducts have been synthesized by 1, 3‐dipolar cycloaddition reaction. Intramolecular energy/electron transfer from carbazole to C₆₀ was observed by steady‐state absorption and fluorescence spectra. The fluorescence spectra of these adducts were similar to each other and dependent on the excitation wavelength and solvent.     

Quantum chemical characterization of the cytosine: 2‐Aminopurine base pair

The nature of the base pairing between cytosine and 2‐aminopurine is investigated by means of quantum mechanical calculations including electron correlation and accounting for the effects of aqueous solvation. At neutral pH, both a neutral wobble base pair and a Watson–Crick‐like base pair having a protonated 2‐aminopurine are predicted to be close to one another in energy; other previously proposed forms are found to be too high in energy to be of significant chemical interest. Accounting for the energetics of helix embedding suggests that the equilibrium between the two low‐energy motifs is quite sensitive to local environment. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1167–1179, 2001     

Multicanonical parallel simulations of proteins with continuous potentials

The determination of the three‐dimensional (3D) structure of a protein or peptide is a very important research problem in biological and medical sciences. Anfinsen's experiments (Science 1973, 181, 223) on renaturation of denatured proteins have shown that the native 3D structure of a (small) protein at low (room) temperatures is uniquely determined by its amino acid sequence, which suggests that it might be possible to determine the 3D structure of a protein from its amino acid sequence by pure computations. As a step toward that goal, in this article we present a simple approach for parallelization of multicanonical Monte Carlo simulations of proteins with continuous potentials. Our method is based on the parallel calculation of the protein energy function. The algorithm is tested by simulated annealing and multicanonical simulations of two small peptides, and known results are reproduced accurately. An acceptable degree of parallelization can be achieved in the simulation of Protein L using up to 30 PCs. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1287–1296, 2001     

Electronegativity Scaled as a Average Attracting Energy of Valence‐Shell Electrons in a Ground‐State Free Atom

The total capability of an atom attracting valence electrons can be measured by the sum of ionization energies of valence electron in a ground‐state free atom plus its electron affinity called Total Attracting Energy, TAE = Σn_iE_i + EA, where, E_i is the ionization energy of the ith valence‐shell electron in a ground‐state free atom, n_i is the number of valence‐shell electron bearing energy E_i, and EA is the electron affinity. And the electronegativity χ_CL is proportional to the average of TAE, AAE = TAE_av, divided by Σn_i, the number of atomic valence‐shell electrons. χ_CL = 0.1813 TAE_av = 0.1813 AAE = 0.1813 TAE/Σn_i, = 0.1813 (Σn_iE_I + EA)/Σn_i. Further, the atomic valence orbital electronegativity can be also obtained from the TAE value of an atom. Some discussions were made on several special aspects such as scale of rare gases, comparisons with Pauling's and Allen's scales, etc.     

General Formulations of Finite-field Method Classified by Symmetry for Molecular Linear and Nonlinear Polarizabilities

1 INTRODUCTIONWith the invention of lasers[1] and the observation of second-harmonic generation in quartz[2], nonlinear optics(NLO), as a cornerstone of photonics, has been booming since 1960's. And intense interest has been aroused to search materials exhibiting appropriate nonlinear optical properties suitable for the construction of practical optical devices for the important techniques such as frequency converting, signal processing and optical computing[3～6]. In order to determine …     

Legendre transform of the noninteracting kinetic energy: Especially from March–Murray perturbation theory based on plane waves

The Legendre transform of the noninteracting kinetic energy is derived from the March–Murray perturbation theory based on plane waves. Further useful relations are summarized, and it is shown that insight can be gained from simple model systems where nonperturbative equations can be derived. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 82: 138–142, 2001     

WO3/碳布柔性非对称超级电容器的组装及性能研究

以超级电容器的电极材料制备、性质研究及对组装的非对称超级电容器的性能研究为核心内容,提高超级电容器电化学性能为主要目的,采用水热合成法在碳布基底上合成三氧化钨/碳布和活化后的碳布为超级电容器的电极材料。采用SEM、XRD表征方法对制备的材料进行了形貌表征及物相分析;使用上海辰华电化学工作站对电极材料进行了循环伏安、恒流充放电、交流阻抗等电化学性能测试. 最终得到以三氧化钨/碳布为正极材料、活化后的碳布为负极材料组装成不对称柔性电容器,进行电化学测试,其电位窗口提高到0~1.6 V,电流密度61.9 mA·cm^-2时,电容达到58.96 F·cm-2,功率密度0.48 W·cm^-2时,能量密度为20.36 mWh·cm^-2,同时在电流密度8 mA·cm^-2时,循环3000次时表现出良好的循环性能,相较于对称型超级电容器,倍率性能更加优异.