Transferable step potentials for perfluorinated hydrocarbons

The step potential equilibria and discontinuous molecular dynamics (SPEADMD) model is adapted for characterizing the interaction potentials of perfluorocarbons and their mixtures with n-alkanes. We seek to explain the peculiar behavior of these systems, especially with regard to the unfavorable mixing behavior. The methodology is based on discontinuous molecular dynamics (DMD) and second order thermodynamic perturbation theory (TPT). DMD simulation is applied to the repulsive part of the potential. The effects of disperse attractions and hydrogen bonding are treated by TPT, discretizing the attractive potential into four distinct wells of variable depth. This approach accelerates the molecular simulations in general and the parameterization of the transferable potentials in particular. C₃–C₈ straight chain perfluorocarbons are characterized along with perfluorobenzene, perfluorocyclobutane, and heptafluoropropane applying explicit atom models for all fluorine atoms. Each compound is simulated at 21 densities. Interpolation with density combines with TPT to give a complete equation of state. The depths of the attractive wells are optimized by iterating on their values until the vapor pressures computed by the resulting equation of state provide the minimum deviation from experimental data.     

表面修饰CdS和(CdS)ZnS纳米晶的性能研究

在水相中合成了CdS纳米微粒,以ZnS对其进行表面修饰,得到具有核壳结构的(CdS)ZnS水溶性纳米晶。采用红外光谱、X射线衍射(XRD)、透射电镜(TEM)表征其粒度和形貌,紫外-可见吸收光谱(UV)、荧光光谱表征其光学特性。制得的CdS近似呈球形,直径为8nm;CdS纳米颗粒表面经ZnS修饰后,其荧光发射峰强度显著增强,表面态发射减弱。     

纳米ZnS,CdS水热合成及其表征

纳米ＺｎＳ、ＣｄＳ水热合成及其表征苏宜，谢毅，陈乾旺，钱逸泰（中国科学技术大学应用化学系合肥２３００２６）关键词硫化锌，硫化镉，水热技术ⅡＢ～ⅥＡ族化合物是主要的半导体发光材料，广泛应用于各种发光与显示装置［１］可采用气相反应、固气相反应及液相反应等...     

硫化镉与硫化锌纳米材料的界面法合成

采用界面自组装方法制备了CdS纳米线及ZnS球形纳米颗粒,利用TEM和XRD对其形貌和结构进行了表征,并考察了碱的种类和反应物浓度对材料形貌的影响。结果表明,氨水是该合成法必要的试剂,反应物浓度对产物形貌有一定的影响,但界面扩散和反应途径是决定其形貌的主要因素;采用该法合成无机纳米材料具有合成条件温和、易于控制、纯化简单、省去了使用模板/消除模板的过程等优点。     

Coordination Polymer Route to Wurtzite ZnS and CdS Nanorods

Wurtzite MS nanorods were synthesized from coordination polymer [M(tp)(4,4′-bipy)]_∞ at 140°C under solvothermal condition (M=Zn, Cd). The morphology determined by TEM gives the average diameters of width/length as 50/200 nm and 20/75 nm for ZnS and CdS, respectively. X-ray powder diffraction and XPS spectra proved that the as-prepared products were pure ZnS and CdS, respectively.     

ZnS/CdS/ZnS quantum dot quantum well produced in inverted micelles

A ZnS/CdS/ZnS quantum dot quantum well was prepared in AOT micelles successfully and was characterized by absorption spectroscopy and fluorescence spectroscopy. Luminescence in the region of 350-600 nm was observed. The complete ZnS shell might reduce the number of defects on the surface of the CdS well, which were assumed to act as centers for radiationless recombination, resulting in the luminescence enhancement.     

Dendronized Cellulose Nanocrystals as Templates for Preparation of ZnS and CdS Quantum Dots

Cellulose nanocrystals (CNC) isolated from bleached bagasse pulp were modified with a second-generation isocyanate dendron (G2-dendron) to prepare dendronized cellulose nanocrystals (DCN). Transmission electron microscopy (TEM), elemental analysis for nitrogen, Fourier transform infrared (FTIR) and ¹³C magic angle spinning nuclear magnetic resonance (¹³C MAS NMR) proved occurrence of the modification of cellulose nanocrystals surfaces. The dendronized cellulose nanocrystals were used as templates for formation of ZnS and CdS quantum dots with uniform diameter at low temperature in water. The prepared DCN/QDs were highly soluble in water. TEM images showed that the size of the prepared quantum dots was about 5 nm in diameter. UV-Visible and fluorescence spectroscopy showed absorption and emission at wavelength values lower than that reported for bulk ZnS and CdS.     

Synthesis of CdS and ZnS nanowires using single-source molecular precursors

Single-source molecular precursors were used to synthesize II-VI compound semiconductor nanowires for the first time. Cadmium sulfide and zinc sulfide nanowires were prepared using cadmium diethyldithiocarbamate, Cd(S2CNEt2)2, and zinc diethyldithiocarbamate, Zn(S2CNEt2)2, respectively, as precursors in a gold nanocluster-catalyzed vapor-liquid-solid growth process. High-resolution transmission electron microscopy studies show that the CdS and ZnS nanowires are single-crystal wurtzite structures with stoichiometric compositions. In addition, photoluminescence measurements demonstrate that these nanowires exhibit high-quality optical properties. The applicability of our approach to the synthesis of other compound and alloy semiconductors nanowires as well as nanowire heterostructures of these materials is discussed.     

Single-source precursor route for overcoating CdS and ZnS shells around CdSe core nanocrystals

We reported a facile route for overcoating CdS and ZnS shells around colloidal CdSe core nanocrystals. To synthesize such double shelled core/shell nanocrystals, first, CdSe core nanocrystals were prepared in a much “greener” and cheap route, which did not involve the use of hazardous and expensive trioctylphosphine. Then, a low-cost and labor-saving route was adopted for the CdS and ZnS shell growth with the use of thermal decomposition of commercial available air stable single-source precursors cadmium diethyldithio-carbamate and zinc diethyldithiocarbamate in a non-coordinating solvent at intermediate temperatures. Powder X-ray diffraction patterns and transmission electron microscopy images confirm the epitaxial growth of the shell in the core/shell nanocrystals. The photoluminescence quantum yield of the resulting CdSe/CdS/ZnS core/shell nanocrystals can be as high as 90% in organic media and up to 60% after phase transfer into aqueous media. By varying the size of CdSe cores, the emission wavelength of the obtained core/shell nanostructures can span from 554 to 636 nm.     

Nonspherical ZnS colloidal building blocks for three-dimensional photonic crystals

The asymmetry introduced by a complex or nonspherical basis promotes photonic band gap formation in three-dimensional photonic crystals. However, relatively few techniques have been demonstrated to produce uniform nonspherical colloids for use as photonic crystal bases. Here we expand the menu of basis types with high refractive index by preparing nonspherical zinc sulfide colloids of uniform size and shape. Dimers, trimers, and planar tetramers were precipitated from aqueous solution by the thermal decomposition of thioacetamide in the presence of zinc nitrate, manganese nitrate, and nitric acid. The well-defined morphological types were obtained from suspensions aged for 4-6 h at 26-32 degrees C and then for 20-35 min at 85 degrees C. Stereological techniques were used to analyze SEM images and determine the percentage of each particle class. For example, the quantitative characterization of a particle population prepared at 29 degrees C for 6 h and 85 degrees C for 22 min had the composition 59+/-3% spheres, 31+/-2% dimers, 7+/-1% trimers, 0.4+/-0.2% tetramers, and 2.5+/-0.8% complex clusters (encompasses all other varieties of shape). X-ray diffraction and X-ray photoelectron spectroscopy confirmed the zinc blend crystal structure and the stoichiometric composition of the particles. The refractive index was estimated as 2.25 (413 nm) -2.09 (709 nm) by fitting experimental absorption spectra to curves derived from Mie scattering calculations. This indicated an average porosity approximately 24%. Such colloids offer the potential to form diamond-like lattices with large, stable photonic band gaps.     

ZnS@CdS Nanostructure Formed by Mixing ZnS with CdS Nanoparticles

Sodium citrate capped ZnS and CdS nanoparticles were synthesized. Mixing the two partners gave rise to new phenomena in optical and structural properties. The interacting process was probed by UV‐vis absorption, emission spectra, XRD, and TEM. The results confirmed that the Zn@CdS core/shell structure was formed due to Oswald ripening.     

以含铬类水滑石型层状化合物为模板制备硫化物半导体纳米晶

采用类水滑石型混合金属氢氧化物(CdCr-LDH和ZnCdCr-LDH)为前驱体, 通过气-固反应方法, 制备了根植于层状氢氧化物层板中的硫化镉纳米晶和硫化镉/硫化锌复合纳米晶, 通过改变前驱体(CdCr-LDH)中镉和铬的摩尔比可以调控硫化镉纳米晶的粒径.     

Electrochemical preparation of ZnS/CdS superlattice and its photoelectrochemical properties

Superlattice electrodes composed of three molecular layers of CdS and one to three molecular layers of ZnS were prepared on gold (111) film by using electrochemical atomic layer epitaxy. The prepared electrodes exhibited similar behavior to those of n-type semiconductor electrodes. The energy gap was not changed at all by changing the number of molecular layers of ZnS and by increasing the number of periods in the superlattice structure up to four. The magnitude of the anodic photocurrent was, however, influenced by these variables. It increased with an increase in the number of periods in the superlattice structure and decreased with increasing number of molecular layers of ZnS.     

Ab initio pair potentials for the ionic lithium-formate system

The potential energy surfaces for the interatomic interaction in the Li⁺HCOO^– system have been investigated byab initio methods within the rigid-molecule approximation. Analytical potential expressions were fitted to 133 calculated SCF energies for the Li⁺-HCOO^– interaction, 42 SCF energies for the Li⁺-Li⁺ interaction, and 332 SCF energies for the HCOO^–-HCOO^– interaction. The global minimum on the Li⁺-HCOO^– surface is –170 kcal/mol and corresponds to the lithium ion lying on the C₂ axis of the formate ion at 2.2 Å from the carbon atom on the oxygen side. The cation-cation and anion-anion interactions are repulsive everywhere, although the potential surface is markedly anisotropic for the HCOO^–-HCOO^– interaction.     

Fabrication of Ordered Macroporous CdS and ZnS by Colloidal Crystal Template

Ordered macroporous semiconductors CdS and ZnS with regular arrays of spherical pores have been fabricated by poly (styrene-acrylic) (PSA) colloidal crystal template. It was found that the exact three-dimensional (3D) structure of the template had been imprinted in the final material.     

Formation of monodispersed PVP-capped ZnS and CdS nanocrystals under microwave irradiation

Poly (N-vinyl-2-pyrrolidone) (PVP)-capped ZnS, CdS nanoparticles were prepared by a microwave method from Zn(Ac)₂ or Cd(Ac)₂ and thiourea in N,N-dimethylformamide (DMF) solution. The reaction process was monitored by the temporal evolution of the absorption spectrum. With PVP as stabilizer, monodispersed semiconductor nanoparticles, which showed high quantum size effect, have been obtained. Further study showed that the microwave irradiation could influence selectively the nucleation and growing rates of different semiconductor nanoparticles.     

Phase behavior of density-dependent pair potentials

Phase diagram is calculated by a recently proposed third-order thermodynamic perturbation theory (TPT) for fluid phase and a recently proposed first-order TPT for solid phases; the underlying interparticle potential consists of a hard sphere repulsion and a perturbation tail of an attractive inverse power law type or Yukawa type whose range varies with bulk densities. It is found that besides usual phase transitions associated with density-independent potentials, the density dependence of the perturbation tail evokes some additional novel phase transitions including isostructural solid-solid transition and liquid-liquid transition. Novel triple points are also exhibited which includes stable fluid (vapor or liquid)-face-centered cubic(fcc)-fcc and liquid-liquid-fcc, metastable liquid-body-centered cubic(bcc)-bcc. It also is found that the phase diagram sensitively depends on the density dependence and the concrete mathematical form of the underlying potentials. Some of the disclosed novel transitions has been observed experimentally in complex fluids and molecular liquids, while others still remain to be experimentally verified.     

The mother of all pair potentials

This paper presents a computer simulation study of the exponentially repulsive pair potential system. The simulations show that the system has strong virial potential energy correlations in a large part of its thermodynamic phase diagram. Consequences of this are briefly discussed; these include the existence of isomorphs and predictions for general simple liquids and solids.     

Radial-position-controlled doping in CdS/ZnS core/shell nanocrystals

In this paper, we report a new doping approach using a three-step synthesis to make high-quality Mn-doped CdS/ZnS core/shell nanocrystals. This approach allows precise control of the Mn radial position and doping level in the core/shell nanocrystals. On the basis of this synthetic advance, we have demonstrated the first example in which optical properties of Mn-doped nanocrystals strongly depend on Mn radial positions inside the nanocrystals. In addition, we have synthesized nanocrystals with a room-temperature Mn-emission quantum yield of 56%, which is nearly twice as high as that of the best Mn-doped nanocrystals reported previously. Nanocrystals with such a high-emission quantum yield are very important to applications such as nanocrystal-based biomedical diagnosis.