Equilibrium and kinetic Si isotope fractionation factors and their implications for Si isotope distributions in the Earth's surface environments

Several important equilibrium Si isotope fractionation factors among minerals,organic molecules and the H_4SiO_4 solution are complemented to facilitate the explanation of the distributions of Si isotopes in Earth's surface environments.The results reveal that,in comparison to aqueous H_4SiO_4,heavy Si isotopes will be significantly enriched in secondary silicate minerals.On the contrary,quadra-coordinated organosilicon complexes are enriched in light silicon isotope relative to the solution.The extent of ^(28)Si-enrichment in hyper-coordinated organosilicon complexes was found to be the largest.In addition,the large kinetic isotope effect associated with the polymerization of monosilicic acid and dimer was calculated,and the results support the previous statement that highly ^(28)Sienrichment in the formation of amorphous quartz precursor contributes to the discrepancy between theoretical calculations and field observations.With the equilibrium Si isotope fractionation factors provided here,Si isotope distributions in many of Earth's surface systems can be explained.For example,the change of bulk soil δ^(30)Si can be predicted as a concave pattern with respect to the weathering degree,with the minimum value where allophane completely dissolves and the total amount of sesquioxides and poorly crystalline minerals reaches their maximum.When,under equilibrium conditions,the well-crystallized clays start to precipitate from the pore solutions,the bulk soil δ^(30)Si will increase again and reach a constant value.Similarly,the precipitation of crystalline smectite and the dissolution of poorly crystalline kaolinite may explain the δ^(30)Si variations in the ground water profile.The equilibrium Si isotope fractionations among the quadracoordinated organosilicon complexes and the H_4SiO_4solution may also shed light on the Si isotope distributions in the Si-accumulating plants.

A New Class of Exactly Solvable Models within the Schrodinger Equation with Position Dependent Mass

The study of physical systems endowed with a position-dependent mass (PDM) remains a fundamental issue of quantum mechanics. In this paper we use a new approach, recently developed by us for building the quantum kinetic energy operator (KEO) within the Schrodinger equation, in order to construct a new class of exactly solvable models with a position varying mass, presenting a harmonic-oscillator-like spectrum. To do so we utilize the formalism of supersymmetric quantum mechanics (SUSY QM) along with the shape invariance condition. Recent outcomes of non-Hermitian quantum mechanics are also taken into account.

A Kinetic Approach to Photomineralization of Methane in Air by Membranes Based on TiO2/WO3

Photomineralization of methane in air(10.0-1,000 ppm(mass/volume)of C)at 100%relative humidity(dioxygen as oxygen donor),was systematically studied at 318±3 K,in an annular laboratory-scale reactor,by photocatalytic membranes immobilising titanium dioxide and tungsten trioxide as co-photocatalysts.Kinetics of both substrate disappearance,to yield intermediates,and total organic carbon(TOC)disappearance,to yield carbon dioxide,were followed.A kinetic model was employed,from which,by a set of differential equations,four final optimised parameters,k1 and K1,k2 and K2,were calculated,able to fit the whole kinetic profile adequately.Modelling of quantum yields,as a function of substrate concentration and irradiance,as well as of concentration of photocatalysts,was carried out very satisfactorily.Kinetics of hydroxyl radicals reacting between themselves,leading to hydrogen peroxide,other than with substrate or intermediates leading to mineralization,were considered,paralleled by second competition kinetics involving superoxide radical anion.When using appropriate blends of the two photocatalysts,limiting quantum yieldsF∞values increase considerably and approach the maximum allowable value for the investigated molecule,in a much wider range of irradiances than that shown by the single catalysts mainly at low irradiances.This may be interpreted by strong competition kinetics of superoxide radicals generated by the catalyst defects,in the corresponding range of high irradiances.By this way,operation at high irradiance values is possible,without losing any efficiency for the mineralization process.

Quantum“contact”friction:The contribution of kinetic friction coefficient from thermal fluctuations

A thermal model of kinetic friction is assigned to a classical loaded particle moving on a fluctuating smooth surface.A sinusoidal wave resembles surface fluctuations with a relaxation time.The Hamiltonian is approximated to the mean energy of the wave describing a system of Harmonic oscillators.The quantization of amplitudes yields in terms of annihilation and creation operators multiplied by a quantum phase.Further,we consider acoustic dispersion relation and evaluate the friction coefficient from the force autocorrelation function.While the sliding particle remains classical describing a nano-particle or a tip with negligible quantum effects like tunneling or delocalization in the wave function,the quantized model of the surface fluctuations results in the temperature dependence of the kinetic friction coefficient.It follows an asymptotic value for higher temperatures and supper-slipperiness at low temperatures.

金银花与山银花绿原酸提取动力学比较研究

目的利用已建立的中药材成分封闭体系提取动力学模型,探讨金银花与山银花绿原酸的提取动力学差异。方法采用HPLC测定金银花与山银花绿原酸有效含量W0及分配系数ρ2,采用吸水法测定工艺参数V1、V2再计算V0,利用SPSS19.0软件非线性拟合得到参数M、N、L、α、β、π,用Excel2016按公式计算k、k1′、k2′、ρ1、t_(max)、c_(max)、AUC、P%、D%。运用总量统计矩相似度法计算两者的相似度。结果金银花的V0、V1、V2分别为18.69、9.50、30.20 m L,金银花绿原酸W0为3.75%、ρ2为0.884;山银花的V0、V1、V2分别为12.79、7.80、37.00 m L,山银花绿原酸W0为5.67%、ρ2为1.020。金银花与山银花绿原酸药时曲线呈三室模型,其主要提取动力学参数k分别为0.110 1、0.3755 h-1,k1′分别为3.632、3.288 h-1,k2′分别为53.12、55.28 h-1,ρ1分别为2.731、2.751,tmax分别为0.299 5、0.216 3 h,cmax分别为0.134 0、0.252 7 mg/m L,AUC分别为3.405、1.560 h,P%分别为35.73%、44.57%,D%分别为0.916 2%、2.680 7%。总量统计矩相似度为0.963 8,表明金银花与山银花绿原酸提取动力学行为基本相似。结论金银花与山银花绿原酸的溶出行为及其差异可以用中药提取动力学数学模型客观且有效地表达,本研究可以为进一步开展金银花与山银花提取工艺的优化及其制剂研究提供一定参考。

甲烷分子在煤大分子骨架内吸附量子动力学研究

通过对比分析煤分子5大结构模型特征,结合煤样红外光谱实验数据及van der Waals力作用半径,构建了煤大分子骨架模型以及煤对CH4吸附的量子动力学模型;采用量子化学Hartree-Fock方法,在6-311G基组上对煤分子及甲烷分子结构进行了优化,通过煤大分子骨架模型的Mulliken atomic charges分析,由煤分子电负性最大的原子为吸附中心,并在不同的吸附距离下对吸附模型进行优化,得到了吸附平衡态的几何构型以及吸附能与吸附距离的关系.

Water chemistry influences on long-term dissolution kinetics of CdSe/ZnS quantum dots

Widespread usage of engineered metallic quantum dots(QDs)within consumer products has evoked a need to assess their fate within environmental systems.QDs are mixed-metal nanocrystals that often include Cd2+which poses a health risk as a nanocrystal or when leached into water.The goal of this work is to study the long-term metal cation leaching behavior and the factors affecting the dissolution processes of mercaptopropionic acid(MPA)capped CdSe/ZnS QDs in aphotic conditions.QD suspensions were prepared in different water conditions,and release of Zn2+and Cd2+cations were monitored over time by size exclusion chromatography-inductively coupled plasm a-mass spectrometry.In most conditions with dissolved 02 present,the ZnS shell degraded fairly rapidly over^1 week,while some of the CdSe core remained up to 80 days.Additional MPA,Zn2+,and Cd2+temporarily delayed dissolution,indicating a moderate role for capping agent detachment and mineral solubility.The presence of H2 O2 and the ligand ethylenediaminetetraacetate accelerated dissolution,while NOM had no kinetic effect.No dissolution of CdSe core was observed when 02 was absent or when QDs formed aggregates at higher concentrations with 02 present.The shrinking particle model with product layer diffusion control best describes Zn2+and Cd2+dissolution kinetics.The longevity of QDs in their nanocrystal form appears to be partly controlled by environmental conditions,with anoxic,aphotic environments preserving the core mineral phase,and oxidants or complexing ligands promoting shell and core mineral dissolution.

DSMC量子动理学化学反应模型的数值模拟

为评估直接模拟蒙特卡罗(DSMC)方法中新近发展的一种量子动理学(QK)化学反应模型,在自研高超声速稀薄气体流动数值模拟软件RariHV中实现该模型,并进行了单个绝热单元内的热泳平衡/非平衡反应测试。结果表明,数值解与理论解吻合良好,QK模型具有很好的预测化学反应流动的能力。为进一步验证QK模型在真实流动中的表现,还计算了高超声速绕圆柱的化学反应流动,QK模型计算的驻点线上温度和组分分布都与总碰撞能(TCE)模型结果吻合良好。相较于TCE模型,QK模型的优势是不再依赖反应速率系数的实验数据,在深空探测等化学反应数据缺乏的领域具有一定的应用前景。

DSMC量子动理学模型在火星再入流动中的应用

为解决化学反应模型高温数据缺乏的难题,探索DSMC方法量子动理学(QK)模型在实际中的应用,本文将该模型进一步应用于火星探测器稀薄气动特性的数值预测。通过计算探路者号在85km、95km和110km高度的稀薄绕流,评估了QK模型的性能和稀薄气体效应的影响规律。结果表明,QK模型不依赖宏观的化学反应速率系数,适用于火星再入流动计算。化学反应及其模型对气动力的影响很小,但对气动热特性的影响不容忽略,考虑化学反应后的驻点热流可以下降约12%~14%。

正己烷裂解反应自由基模型的理论研究

采用量子化学法研究了模型化合物正己烷裂解过程,并计算其动力学参数。依据自由基理论,建立由216个基元反应组成的正己烷裂解反应自由基模型,用CBS-QB3法计算链引发和终止反应动力学参数,用MPW1B95/6-311+G(2d,2p)法计算链增长反应动力学参数。根据动力学参数计算结果,忽略相对不重要的反应,将模型简化为160个基元反应。模拟计算表明,在相同的裂解条件下,简化模型模拟结果与完整模型模拟结果一致,各组分相差不大于0.1%wt;建立的动力学模型对主要产物收率预测较好,与实验值相差小于0.7%wt,可正确地预测正己烷裂解产物的组成和各组分含量沿反应管长度的分布,为进一步研究复杂的烃裂解过程提供了基础。

从能谱中提取核子-核子碰撞截面的信息

用同位旋相关的量子分子动力学(IQMD)模型计算了入射能量在30～200MeV/u内,不同中质比的反应系统(76Zn+76Zn,76 Ge+76 Ge,76Se+76Se和76 Kr+76 Kr)碰撞产生的原子核阻止和反应产物能谱。发现原子核阻止和不同方向的动能比值有很强的关联性,且可以用垂直方向和平行方向的碎片总动能比值的平方根近似地代替原子核阻止,用来提取同位旋相关介质中的核子-核子碰撞截面的信息。在核反应实验中,很容易测量到该物理量,它是一个较好的探针。

Challenges and perspectives of combustion chemistry research

In the past decades, combustion chemistry research grew rapidly due to the development of combustion diagnostic methods,quantum chemistry methods, kinetic theory, and computational techniques. A lot of kinetic models have been developed for fuels from hydrogen to transportation fuel surrogates. Besides, multi-scale research method has been widely adopted to develop comprehensive models, which are expected to cover combustion conditions in real combustion devices. However, critical gaps still remain between the laboratory research and real engine application due to the insufficient research work on high pressure and low temperature combustion chemistry. Besides, there is also a great need of predictive pollutant formation model. Further development of combustion chemistry research depends on a closer interaction of combustion diagnostics, theoretical calculation and kinetic model development. This paper summarizes the recent progress in combustion chemistry research briefly and outlines the challenges and perspectives.