含硫化合物的量子化学性质及选择性氧化动力学

采用半经验量子力学分子轨道的PM3算法计算了油品中各典型含硫化合物的量子化学性质,通过数学回归建立了在甲酸/双氧水体系下硫原子的电荷密度与反应常数的关系。同时,选用二苯并噻吩(DBT)作为模型化合物进一步研究了该体系下含硫化合物的动力学性质。研究结果表明:含硫化合物硫原子所带电荷密度与反应常数线性相关,DBT在甲酸/双氧水体系中氧化的活化能为60kJ/mol。

Layer Combination Effect on Band Gap Shift of InGaAsP/InP MQWs by Impurity-free Vacancy Disordering

InGaAsP/InP multiple quantum wells with quantum well intermixing have been prepared by impurity-free vacancy disordering.The luminescent characteristics were investigated using photoluminescence and photoreflectance,from which the band gap blue shift was observed.Si3N4,SiO2 and SOG were used for the dielectric layer to enhance intermixing from the outdiffusion of group III atoms.All samples were annealed by rapid thermal annealing.The results indicate that the band gap blue shift varies with the dielectric layers and the annealing temperature.The SiO2 capping with an InGaAs cladding layer was successfully used to induce larger band tuning effect in the InGaAsP/InP MQWs than the Si3N4 capping with an InGaAs cladding layer.On the other hand, samples with the Si3N4-InP cap layer combination also show larger energy shifts than that with SiO2-InP cap layer combination.

Linear and Nonlinear Optical Properties in Spherical Quantum Dots

We calculate the energy eigenvalues and the sate functions of one-electron Quantum Dot （QD） by using a combination of Quantum Genetic Algorithm （QGA） and Hartre-Fock-Roothaan （HFR） method. The linear and the third-order nonlinear optical absorption coefficients for the 1s-1p, 1p-1d, and 1d-1f transitions are examined as a function of the incident photon energy for three different values of the stoichiometric ratio. The results show that the stoichiometric ratio, impurity, relaxation time, and dot size have great influence on the optical absorption coefficients of QDs.

Notes on Quantitative Structure-Properties Relationships （QSPR） Part Four： Quantum Multimolecular Polyhedra, Collective Vectors, Quantum Similarity, and Quantum QSPR Fundamental Equation

The nature and origin of a fundamental quantum QSPR （QQSPR） equation are discussed. In principle, as any molecular structure can be associated to quantum mechanical density functions （DF）, a molecular set can be reconstructed as a quantum multimolecular polyhedron （QMP）, whose vertices are formed by each molecular DF. According to QQSPR theory, complicated kinds of molecular properties, like biological activity or toxicity, of molecular sets can be calculated via the quantum expectation value of an approximate Hermitian operator, which can be evaluated with the geometrical information contained in the attached QMP via quantum similarity matrices. Practical ways of solving the QQSPR problem from the point of view of QMP geometrical structure are provided. Such a development results into a powerful algorithm, which can be implemented within molecular design as an alternative to the current classical QSPR procedures.

Variation in soil properties in a transformed ecosystem in Southwestern Nigeria

Variation in soil properties as a result of the conversion of the tropical rainforest to a monospecific plantation of teak, tectona grandis, was examined in Akure forest reserve in Southwestern Nigeria. Comparison was made in the active rooting zone of 50 cm soil depth. It was discovered that there were no significant differences in the physical properties except in the value of organic matter content at the top 10 cm layer but chemical properties such as the pH and organic carbon changed significantly at the top 10 cm layer. Differences in other chemical properties, such as the available P, exchangeable cations K, Ca and Mg, the exchangeable acidity and the cation exchange capacity were minor. This showed that no nutrient was limiting or was likely to be limiting in the soil for subsequent short rotation of plantation development.

Non-noble metal single-atom catalyst of Co_(1)/MXene(Mo_(2)CS_(2))for CO oxidation

MXene is a variety of new two-dimensional(2D)materials with early transition metal carbides,nitrides,and carbonitrides.Quantum chemical studies have been carried out on the geometries,electronic structures,stability and catalytic properties of a non-noble metal single-atom catalyst(SAC)with single Co atom anchored on MXene materials of Mo_(2)CS_(2).The Co adatom anchored on top of the Mo atom of this MXene is found to be rather stable,and this SAC is appropriate for CO oxidation.The charge transfers from the surface to the adsorbed CO and O2 play a significant role in the activation of these molecules on Co_(1)/Mo_(2)CS_(2).With this catalyst,the Eley-Rideal(ER),Langmuir-Hinshelwood(LH),and Termolecular Eley-Rideal(TER)mechanisms are explored for CO oxidation.We find that,while all the three mechanisms are feasible at low temperature,Co_(1)/Mo_(2)CS_(2) possesses higher catalytic activity for CO oxidation through the TER mechanism that features an intriguing OC(OO)CO intermediate(IM)adsorbed on Co single atom.The calculated activation energy barriers of the rate-limiting step are 0.67 eV(TER),0.78 eV(LH)and 0.88 eV(ER),respectively.The present study illustrates that it is promising to develop and design low-cost,non-noble metal SACs using MXene types of 2D materials.

Entropy, Fisher Information and Variance with Frost-Musulin Potenial

This study presents the Shannon and Renyi information entropy for both position and momentum space and the Fisher information for the position-dependent mass Schr¨odinger equation with the Frost-Musulin potential. The analysis of the quantum mechanical probability has been obtained via the Fisher information. The variance information of this potential is equally computed. This controls both the chemical properties and physical properties of some of the molecular systems. We have observed the behaviour of the Shannon entropy. Renyi entropy, Fisher information and variance with the quantum number n respectively.

Noble and valuable: atomically precise gold nanoclusters

Atomically precise gold nanoclusters have recently attracted intensive attention due to their significance in catalysis,chemical sensing,and bio-application.These nanoclusters often possess unique optical,chemical or physical properties originated from the quantum size effect（i.e.size andshapemorphology）.

Interaction between water molecules and 3C-SiC nanocrystal surface

The influence of water permeates almost all areas including biochemistry,chemistry,physics and is particularly evident in phenomena occurring at the interfaces of solid surface such as SiC nanocrystals,which are promising nanomaterials and exhibit unique surface chemical properties.In this paper,the quantum confinement effect and stability of 3C-SiC nanocrystals in aqueous solution as well as photoluminescence properties in water suspensions with different pH values are reviewed based on design and analysis of surface structures.On this basis,the significant progress of 3C-SiC nanocrystals in efficiently splitting water into usable hydrogen is summarized and the relative mechanisms are described.In addition,the water-soluble 3C-SiC quantum dots as robust and nontoxic biological probes and labels also are introduced as well as future prospects given.

Laser induced oxidation and optical properties of stoichiometric and non-stoichiometric Bi2Te3 nanoplates

Bi-Te nanoplates （NPs） grown by a low pressure vapor transport method have been studied by Raman spectroscopy, atomic force microscopy （AFM）, energy- dispersive X-ray spectroscopy （EDS）, and Auger electron spectroscopy （AES）. We find that the surface of relatively thick （more than tens of nanometers） Bi2Te3 NPs is oxidized in the air and forms a bump under heating with moderate laser power, as revealed by the emergence of Raman lines characteristic of Bi2O3 and TeO2 and characterization by AFM and EDS. Further increase of laser power burns holes on the surface of the NPs. Thin （thicknesses less than 20 nm） NPs with stoichiometry different from Bi2Te3 were also studied. Raman lines from non-stoichiometric NPs are different from those of stoichiometric ones and display characteristic changes with the increase of Bi concentration. Thin NPs with the same thickness but different stoichiometries show different color contrast compared to the substrate in the optical image. This indicates that the optical absorption coefficient in thin Bi-Te NPs strongly depends on their stoichiometry.

Density-functional-theory formulation of classical and quantum Hooke's law

A fundamental property of solid materials is their stress state. Stress state of a solid or thin film material has profound effects on its thermodynamic stability and physical and chemical properties. The classical mechanical stress （σ^M） originates from lat- tice strain （e）, following Hooke＇s law： σ^M=Cε, where C is elastic constant matrix. Recently, a new concept of quantum electronic stress （o-QE） is introduced to elucidate the extrinsic electronic effects on the stress state of solids and thin films, which follows a quantum analog of classical Hooke＇s law： ~QE=E（An）, where E is the deformation potential of electronic states and An is the variation of electron density. Here, we present mathematical derivation of both the classical and quantum Hooke＇s law from density functional theory. We further discuss the physical origin of quantum electronic stress, arising purely from electronic excitation and perturbation in the absence of lattice strain （g=0）, and its relation to the degeneracy pressure of electrons in solid and their interaction with the lattice.