量子电化学的交换电流表达式

本文根据热活化理论的电流密度一般式得到了交换电流表达式,计算了Fe和Ni电化学沉积反应的交换电流,计算值与实验值基本一致。

21世纪电化学的若干发展趋势

本文简要回顾 2 0世纪后五十年电化学在理论、实验技术、新现象发现和应用等领域的重要进展 ,提出了 2 1世纪前期电化学的若干发展趋势 ,强调应重视电化学新体系的研究 ,以迎接 2 1世纪能源、材料、生命。

电子的量子跃迁

电极过程的一个最重要的特征是电子从一类导体向二类导体的转移。以往对这一过程的描述是基于传统电化学的理论。随着电子微制造应用的发展,工艺实践中金属离子获得电子还原为原子并进行晶格组装过程中,控制过程和路径需要有更为清晰的说明。电子的作用和动向需要有更为细致的描述,需要引入量子电化学来进行探讨。

理论创新对发展电子电镀技术的重要意义

0前言近几年,我已经在多个技术交流会上提出了用量子电化学理论来研究和考察电极过程和电镀技术问题的设想和建议。量子电化学的概念最先是由J.O.M博[1,2]克里斯提出的。他和他的合作者一起于1979年出版了《量子电化学》一书,我国于1988年翻译出版了这本专著。但是,似乎没有在这个领域引起多少重视。这是我在自己构思“量子电化学”概念后从旧书网上查到的唯一一本量子电化学的专著,如获至宝。

Transport Properties of Two Coupled Quantum Dots Under Optical Pumping

Using the Keldysh-Green function,we present a theoretical study on the electron transport properties of two coupled quantum dots under optical pumping. Plateaus in the I-V curve and resonant peaks in the transmission coefficient occur and can be explained by the local electron density of states in the quantum dots. The effects of the optical pumping frequency and intensity on the transport properties of the system are also discussed. The electron dynamical localization phenomenon occurs when the optical pumping frequency is equal to the discrete hole energy level. This result can be used to realize optical control switches.

Theoretical Investigation on Photoionization and Dissociative Photoionization of Toluene

The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods. The geometries and frequencies of the reactants, transition states and products have been performed at B3LYP/6-311＋＋G（d,p） level, and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level. The ionization energies of toluene and the ap- pearance energies for major fragment ions, C7H7＋, C6H5＋, C5H6＋, C5H5＋, are determined to be 8.90, 11.15 or 11.03, 12.72, 13.69, 16.28 eV, respectively, which are all in good agree- ment with published experimental data. With the help of available published experimental data and theoretical results, four dissociative photoionization channels have been proposed： CTHT＋＋H, C6Hs＋＋CH3, C5H6＋WC2H2, CsHs＋＋C2H2＋H. Transition structures and intermediates for those isomerization processes are determined in this work. Especially, the structures of C5H6＋ and C5H5＋ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.

2,3,5-Triphenyl-2H-tetrazolium Chloride and 2,4,6-Tri（2-pyridyl）-s-triazine on the Corrosion of Mild Steel in HCl

Electrochemical measurement, quantum chemical method, and scanning electron microscopy （SEM） were performed to investigate the inhibitive effect of 2,3,5-triphenyl-2H-tetrazolium chloride （TTC） and 2,4,6-tri（2-pyridyl） -s-triazine（TPT） on the corrosion of mild steel in lmol.L^-1 HCl at room temperature. Impedance spectroscopy measurement showed that the polarization resistance increased and that double layer capacitance decreased with the increase in the inhibitive concentration, and the results of potentiodynamic polarization showed that the inhibitors suppressed both cathodic and anodic processes of steel corrosion without change in the mecha-nism. Higher the orbital density distribution strength of the lowest unoccupied molecular orbital, higher is the molecule dipole, and lower energy gap between the energy of the highest occupied molecular orbital and the energy of the lowest unoccupied molecular orbital resulted in higher inhibitory efficiency. The results of SEM analysis showed that the metal-was protected from aggressive corrosion by the addition of TTC and TPT.

ZnIn_2S_4 flowerlike microspheres embedded with carbon quantum dots for efficient photocatalytic reduction of Cr(Ⅵ)

Development of efficient heterostructured photocatalysts that respond to visible light remains a considerable challenge.We herein show the synthesis of ZnIn2S4/carbon quantum dot hybrid photocatalysts with flowerlike microspheres via a facile solvothermal method.The ZnIn2S4/carbon quantum dot flowerlike microspheres display enhanced photocatalytic and photoelectrochemical activity compared with that of pure ZnIn2S4.With a content of only 0.5 wt%carbon quantum dots,93%of Cr(VI)is reduced under visible‐light irradiation at 40 min.As a co‐catalyst,the carbon quantum dots improve the light absorption and lengthen the lifetime of charge carriers,consequently enhancing the photocatalytic and photoelectrochemical activity.

Oxidation of chalcopyrite in air-equilibrated acidic solution: Inhibition with phenacyl derivatives

The effects of 4-(2-hydroxyphenyl)-2-(morpholin-4-yl)-1,3-thiazole(Pr02), 1-(3,5-dibromo-2-hydroxyphenyl)-1-oxoethan-2-yl-N,N-diethyldithiocarbamate(Pr04) and 1-(5-bromo-2-hydroxy-3-methylphenyl)-1-oxoethan-2-yl-Oethyl xanthate(Pr06) on the aqueous oxidation of chalcopyrite(CuFeS2) in air-equilibrated solution at a temperature of 25 ℃ and a pH of 2.5 were studied. The effects were investigated by using potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), scanning electron microscopy coupled with energy dispersive X-ray(SEM/EDX) analysis, aqueous batch experiments, Fourier transform infrared(FTIR) spectroscopy, Raman scattering and quantum chemical calculations. It is found that the anodic current densities decrease in the order of EtOH > Pr02 > Pr04 > Pr06. These results, along with those of the EIS measurements, show that Pr02, Pr04 and Pr06 are effective anodic inhibitors of chalcopyrite aqueous oxidation. Both Raman scattering and FTIR spectroscopy indicate that the elemental sulfur, polysulfide and ferric oxyhydroxides that form on the surface of the mineral are not responsible when it comes to the aqueous oxidation inhibition of chalcopyrite. Quantum chemical calculations show that the adsorption of the tested compounds on the chalcopyrite surface is energetically favorable and so, it can explain the inhibiting effects that were observed.

Molecular Dipole Moment Computed with Ab Initio MKS Charges

Molecular dipole moments computed at the levels of HF/STO-3G, HF/6-31G(d, p), HF/6-311+G(2d, 2p), MP2/6-31G(d, p) and MP2/6-311+G(2d, 2p) have been investigated. HF/6-311+G(2d, 2p) was found to be the relatively good choice to compute MKS charges for reproducing the experimental values of molecular dipole moments. Root mean square deviation of computed dipole moments for 21 small polar molecules is about 0.1969 D.

Structural and Bonding Properties of Al_(n)C_(4)^(−/0)(n=2−4)Clusters:Anion Photoelectron Spectroscopy and Theoretical Calculations

We measured the photoelectron spectra of Al_(n)C_(4)^(−)(n=2−4)clusters by using size-selected anion photoelectron spectroscopy.The structures of Al_(n)C_(4)^(−/0)(n=2−4)clusters were explored with quantum chemistry calculations and were determined by comparing the theoretical results with the experimental spectra.It is found that the most stable structure of Al_(2)C_(4)^(−) anion is a C_(2v)symmetry planar structure with two Al atoms interacting with two C_(2)units.In addition,Al_(2)C_(4)^(−) anion also has a D∞h symmetry linear structure with two Al atoms located at the two ends of a C_(4)chain,which is slightly higher in energy than the planar structure.The most stable structure of neutral Al_(2)C_(4)has a D∞h symmetry linear structure.The most stable structure of Al_(3)C_(4)^(−) anion is a planar structure with three Al atoms interacting with two C_(2)units.Whereas neutral Al_(3)C_(4)cluster has a C_(2v)symmetric V-shaped bent structure.The global minima structures of both Al_(4)C_(4)^(−) and neutral Al_(4)C_(4)are C_(2)h symmetry planar structures with four Al atoms interacting with the ends of two C_(2)units.Adaptive natural density partitioning analyses of Al_(n)C_(4)^(−)(n=2−4)clusters show that the interactions between the Al atoms and C_(2)units have bothσandπcharacters.

Study of the Adherence Mechanism Between the Metal and Inorganic Coating with Mill Addition of Li_2Ni_8O_(10) Nano Powder

The adherence strength between the metal and the inorganic coating can be greatly increased by mill addition of Li2Ni8O10. The interface structure between metal and the inorganic coating with excellent adherence has been studied by investigating the chemical composition and the microstrncture as well as elements valence bond on the interface with the help of scanning electron microscope （SEM）, electron microprobe, and Auger elctron spectroscope （AES）. The results show that there is a non-stoichiometrieal transitional layer on the interface between metal and the inorganic coating with excellent adherence, the adherence between metal and the non-stoichiometrical transitional layer is achieved by the metallic bond and the adherence between the non- stoichiometrical transitional layer and the inorganic coating is produced by ionic and covalent bond. The non-stoichiometrical transitional layer results in the strong adherence.

Inhibiting Effect of Ciprofloxacin,Norfloxacin and Ofloxacin on Corrosion of Mild Steel in Hydrochloric Acid

The inhibiting effect of ciprofloxacin,norfloxacin and ofloxacin on the corrosion of mild steel in 1 mol·L-1 HCl and the mechanism were studied at different temperatures using mass loss measurement,electrochemical method,and X-ray photoelectron spectroscopy(XPS) .Effective inhibition was shown by mass loss,potentiodynamic polarization and impedance spectroscopy measurement.The corrosion rate of the metal in the mass loss measurement,and the corrosion reaction on cathode and anode in the electrochemical measurement were accelerated when temperature was increased.XPS results showed that the inhibitors adsorbed effectively on the metal surface.

Synthesis of Li_2Fe_(0.9)Mn_(0.1)SiO_4/C composites using glucose as carbon source

Li2Fe0.9Mn0.1SiO4/C composites were synthesized by using X-ray diffractometry （XRD）, scanning electron microscopy （SEM） glucose as carbon source. The samples were characterized by and electrochemical measurements. All Li2Fe0.9Mn0.1SiO4/C composites are of the similar crystal structure. With increasing the carbon content in the range of 5%-20% （mass fraction）, the diffraction peaks in XRD patterns broaden and the particle sizes and the tap density of samples decrease. The Li2Fe0.9Mn0.1SiO4/C composites with carbon content of 14.12% show excellent electrochemical performances with an initial discharge capacity of 154.7 mA.h/g at C/16 rate, and the capacity retention remains 92.2% after 30 cycles.

Quantum Chemistry Modeling of Formation of Graphene and Graphene Nanowalls for Emission Electronics

The system ＂substrate--graphene island on its surface＂ was modeled with using semi-empirical quantum chemistry methods for various substrates. Such system imitates the graphene nucleation and growth when using CVD （chemical vapor deposition） technique. Herewith the carbon atoms can enter the island from both the substrate and the bulk of the CVD reactor. The authors show that for a wide island size range the carbon nanowalls placed perpendicularly as to the substrate is the most favorable configuration. But a transfer to this configuration is only possible providing two conditions are realized： the CVD technique is stimulated by plasma, when a strong electrical field exists near the substrate surface and preliminary decomposition of carbon carrier is realized in the bulk of the CVD-reactor.

Nonlinear Optical Response of Conjugated Polymer to Elec tric Field

The organic π-conjugate d polymers are of major interest materials for the use in electro-optical and no nlinear optical devices. In this work, for a selected polyacetylene chain, the optical absorption spectra in UV/Vis regime as well as the linear polarizabiliti y and nonlinear hyperpolarizability are calculated by using quantum chemical ab initio and semiempirical methods. The relationship of its optical property to el ectric field is obtained. Some physical mechanism of electric field effect on mo lecular optical property is discussed by means of electron distribution and intr amolecular charge transfer.

Effects of Electric and Magnetic Fields on Pure Dephasing of Exciton Qubits

In a two-dimensional quantum dot （QD） with parabolic confinement potential, we investigate pure dephasing due to deformation potential exciton-bulk longitudinal acoustic phonons （LAP） interaction for exciton qubits under the influence of external static electric and magnetic fields by adopting the full quantum-mechanical method of Kunihiro Kojima and Akihisa Tomita. The wave function is found and the dependence of the pure dephasing factor on the confinement length of the QD and time and temperature is discussed. We find the external electric and magnetic fields have important effects on pure dephasing of exciton qubits because exciton-LAP interaction increases, leading to more pure dephasing.

Series Solution for Localization and Entanglement of an Exciton in a Quantum Dot Molecule by an ac Electric Field

The Schroedinger equation involving the phenomenon of the localization and entanglement for an exciton in a quantum dot molecule by an ac electric field is analytically investigated. New exact series solutions for the Schroedinger equation have been obtained for the first time. The analytical expressions can further describe the dynamical behaviors of an interacting electron-hole pair in a double coupled quantum dot molecule under an ac electric field accurately.

First principles calculation on electronic structure,chemical bonding,elastic and optical properties of novel tungsten triboride

The electronic structures,chemical bonding,elastic and optical properties of the novel hP24 phase WB3 were investigated by using density-functional theory(DFT) within generalized gradient approximation(GGA).The calculated energy band structures show that the hP24 phase WB3 is metallic material.The density of state(DOS) and the partial density of state(PDOS) calculations show that the DOS near the Fermi level is mainly from the W 5d and B 2p states.Population analysis suggests that the chemical bonding in hP24-WB3 has predominantly covalent characteristics with mixed covalent-ionic characteristics.Basic physical properties,such as lattice constant,bulk modulus,shear modulus and elastic constants Cij were calculated.The elastic modulus E and Poisson ratio υ were also predicted.The results show that hP24-WB3 phase is mechanically stable and behaves in a brittle manner.Detailed analysis of all optical functions reveals that WB3 is a better dielectric material,and reflectivity spectra show that WB3 can be promised as good coating material in the energy regions of 8.5-11.4 eV and 14.5-15.5 eV.

Spectroscopic Parameters of X^3∑^-, a^1△, and A^＇3△ Electronic States of SO Radical

The potential energy curves （PECs） of three low-lying electronic states （X^3∑, a^1△, and a^3△） of SO radical have been studied by ab initio quantum chemical method. The calcula- tions were carried out with the full valence complete active space self-consistent field method followed by the highly accurate valence internally contracted multireference configuration in- teraction （MRCI） approach in combination with correlation-consistent basis sets. Effects of the core-valence correlation and relativistic corrections on the PECs are taken into account. The core-valence correlation correction is carried out with the cc-pCVDZ basis set. The way to consider the relativistic correction is to use the second-order Douglas-Kroll Hamiltonian approximation, and the correction is performed at the level of cc-pV5Z basis set. To obtain more reliable results, the PECs determined by the MRCI calculations are also corrected for size-extensivity errors by means of the Davidson modification （MRCI＋Q）. These PECs are extrapolated to the complete basis set limit by the two-point energy extrapolation scheme. With these PECs, the spectroscopic parameters are determined.