格林公式在物理化学计算中的应用

本文说明了状态函数的微分为全微分的数学基础；并导出用TS表示体系在第循环过程所做的功的公式。

《物理化学实验计算机过程管理系统》的开发与应用

用VB 开发的《物理化学实验计算机过程管理系统》,采用计算机与常用实验设备联机,管理学生实验的全过程。由于数据的客观性和封闭性,提高了对学生实验操作的要求。软件设计注重学生参与实验及数据处理过程,达到了相应的训练目的。

A first-principle calculation of structural,mechanical and electronic properties of titanium borides

The first-principle calculations are performed to investigate the structural,mechanical and electronic properties of titanium borides （Ti2B,TiB and TiB2）.Those calculated lattice parameters are in good agreement with the experimental data and previous theoretical values.All these borides are found to be mechanically stable at ambient pressure.Compared with parent metal Ti （120 GPa）,the larger bulk modulus of these borides increase successively with the increase of the boron content in three borides,which may be due to direction bonding introduced by the boron atoms in the lattice and the strong covalent Ti-B bonds.Additionally,TiB can be regarded as a candidate of incompressible and hard material besides TiB2.Furthermore,the elastic anisotropy and Debye temperatures are also discussed by investigating the elastic constants and moduli.Electronic density of states and atomic Mulliken charges analysis show that chemical bonding in these titanium borides is a complex mixture of covalent,ionic,and metallic characters.

Ag-SO_3^(2-)-H_2O系在银还原中的研究

本文通过对Ag-SO32--H2O体系的基本物理化学计算,得出了该体系的E-log[SO32-]和E-pH关系图。分析表明,亚硫酸钠可使银得到还原,还原反应初期溶液中酸度越大或NO3-浓度越高,亚硫酸钠的消耗越大;亚硫酸钠在量不足或过量的情况下都将影响Ag的沉淀率。这些结果为亚硫酸钠还原银的条件控制提供了理论依据。

Mechanistic study on the cellulose dissolution in ionic liquids by density functional theory

Ionic liquids （ILs） have attracted many attentions in the dissolution of cellulose due to their unique physicochemical properties as green solvents. However, the mechanism of dissolution is still under debate. In this work, computational investigation for the mechanisms of dissolution of cellulose in [Bmim]Cl, [Emim]C1 and [Emim]OAc ILs was performed, and it was focused on the process of breakage of cellulose chain and ring opening using cellobiose as a model molecule. The detailed mechanism and reaction energy barriers were computed for various possible pathways by density functional theoretical method. The key finding was that 1Ls catalyze the dissolution process by synergistic effect of anion and cation, which led to the cleavage of cellulose chain and formation of derivatives of cellulose. The investigation on ring opening process ofcellobiose suggested that carbene formed in ILs played an important role in the side reaction of cellulose, and it facilitated the formation of a covalent bond between cellulose and imidazolium core. These computation results may provide new perspective to understand and apply ILs for pretreatment of cellulose.

Two-dimensional Pd-based nanomaterials for bioapplications

Noble metal nanomaterials have been extensively explored in cancer diagnostic and therapeutic applica- tions owing to their unique physical and chemical properties, such as facile synthesis, straightforward surface functionalization, strong photothermal effect, and excellent biocompatibility. Herein, we summa- rize the recent development of two-dimensional （2D） Pd-based nanomaterials and their applications in cancer diagnosis and therapy. Different synthetic strategies for Pd nanosheets and the related nanostruc- tures, including Pd@Au, Pd@Ag nanoplates and mesocrystalline Pd nanocomlla, are first discussed. Together with their unique properties, the potential bioapplications of these 2D Pd nanomaterials are then demonstrated. With strong absorption in near-infrared （NIR） region, these nanomaterials have great potentials in cancer photothermal therapy （PTr）. They also readily act as contrast agents in photoacoustic （PA） imaging or X-ray computed tomography （CT） to achieve image-guided cancer therapy. Moreover, significant efforts have been devoted to studying the combination of PTr and other treatment modalities （e.g., chemotherapy or photodynamic therapy） based on Pd nanomaterials. The remarkable synergistic or collaborative effects to achieve better therapeutic efficacy are discussed as well. Additionally, the biosaf- ety of 2D Pd-based nanomaterials in vitro and in vivo was evaluated. Finally, challenges for the applica- tions of Pd-based nanomaterials in cancer diagnosis and therapy, and future research prospects are highlighted.

Influence of Cl substitution on the electronic structure and catalytic activity of ceria

Cl-containing cerium dioxide(Ce O2) catalysts have been found to exhibit unique catalytic activities. In the present work, using density functional theory calculations with the inclusion of on-site Coulomb correction, we systematically studied the effect of Cl on the physicochemical properties of Ce O2 surfaces by substituting one subsurface O with Cl. The calculated results show that substituting an O atom with a Cl atom results in structural distortion and the reduction of one surface Ce4+ cation to Ce3+. The protruding Ce3+ cation greatly improves the adsorption energy of O2 to produce an active O2- species, and maintains the catalytic oxidation cycle of CO on Ce O2(110). These results may help us obtain a better understanding of Cl-ceria interacting systems and provide some guidance for the design of effective Ce O2-based catalysts.

Theoretical energy consumption analytical method for metal separation process

The theoretical energy consumption(TEC)analytical methods and the calculated models for the electrolytic and thermal reduction metal separation processes have been put forward based on thermodynamics and physical chemistry principles,providing theoretical foundation for choosing the optimum metal separation methods.Based on the models,the TECs of the Mg separation processes are taken as an example,and have been calculated and analyzed contrastively,including the MgCl_2 electrolytic method,the MgO electrolytic method with inert electrode and with carbon anode,and the silicothermic method.It is shown that the thermal method is more reasonable than the electrolytic methods to separate Mg under low efficiency of coal power generation.

Point defects in L1_0 FePt studied by molecular dynamics simulations based on an analytic bond-order potential

The point defects and their related physical properties in L10 FePt are investigated by molecular dynamics simulations based on an analytic bond-order potential. The calculated results agree well with the experimental value, indicating that the analytic bond-order potential is suitable to describe the structural properties and surface energies of the FePt alloy in the L10 phase. However, the calculated vacancy formation energy of an Fe atom is higher than that of a Pt atom, which disagrees with some other previously calculated results. This result indicates that the analytic bond-order potential is unable to describe the related point defect properties. The analytic bond-order potential needs to be modified in order to study these defect properties of an FePt alloy.

Lattice Dynamics Study of Magnesium Chalcogenides

First-principles calculations,which are based on the plane-wave pseudopotential approach to density functional perturbation theory within the local density approximation,have been performed to investigate the structural,lattice dynamical and thermodynamic properties of zinc blende(B3) structure magnesium chalcogenides:MgS,MgSe and MgTe.The results of ground state parameters and phonon dispersion are compared and agree well with the experimental data available and other calculations.We obtain the change of Born effective charge and LO-TO splitting under hydrostatic pressure.Finally,by the calculations of phonon frequencies,some thermodynamic properties such as the entropy,heat capacity,internal energy,and free energy are also successfully obtained.