(H2O)6的稳定结构及异构过程研究

(H₂O)₆是形成三维立体结构的最小水分子团簇并具有能量较低的多个稳定异构体.本文利用从头计算方法研究了各稳定结构的异构化过程.(H₂O)₆的环状结构与最稳定结构的能量差0.31 eV为一个氢键的键能.水分子团簇的异构化是分子间氢键打开或重组的过程,不同异构体之间的转化每次只涉及一个氢键的打开或重组,异构化的能垒高度在0.07—0.21 eV之间. 关键词： 水分子团簇 2O)₆')" href="#">(H₂O)₆ 异构化过程 从头计算     

分子动力学模拟方解石和白云石润湿性

利用分子动力学模拟研究油水分子在方解石和白云石表面的吸附,分析体系的平衡构型、相对浓度、径向分布函数和吸附能,研究方解石和白云石的亲水性并对比二者差异.根据油水分子吸附规律分析方解石/白云石-油水体系作用机理.研究表明：白云石-油水体系更易达到热力学稳定状态并且体系更加稳定;方解石和白云石表面均能够优先吸附水分子并在表面形成双层结构的水膜.其中,白云石表面对水分子吸附强度大于方解石;稳定吸附过程分为两步：范德华力、静电力和O（CaCO₃,CaMg（CO₃）₂）-H（H₂O）氢键共同影响下水分子向晶体表面移动并吸附形成紧密吸附层;O（H₂O）-H（H₂O）氢键作用下游离的H₂O向晶体表面靠近形成扩散层.从分子尺度解释方解石/白云石亲水特性,为碳酸盐岩储层润湿性研究奠定理论基础.     

激发态下甘氨酸与水分子间氢键性质研究

在生物体中氨基酸通常以水作为溶剂,是形成细胞的重要成分.在该环境下,分子间氢键的产生会对氨基酸分子与水分子的结构和性质产生影响.为了研究其在基态和激发态下的性质,本文利用密度泛函理论(DFT)和含时密度泛函理论(TD-DFT)对甘氨酸分子和H₂O分子在基态和激发态下的分子间氢键的静电势、键长、自然键轨道(NBO)电荷、分子中的原子理论(AIM)分析、Wiberg键级b、红外(IR)光谱、空穴-电子轨道和基态与激发态之间的电子转移进行了理论研究.结果表明：分子间氢键的形成会导致分子结构的改变和红外光谱振动频率的移动.在激发态下,分子间氢键有不同程度的增强或减弱.该计算结果为氢键的形成和激发态下分子间氢键的研究提供理论依据.     

[1ChCl∶2EG]/CrCl3·6H2O离子液体中Cr(Ⅲ)配合物的研究

利用电喷雾质谱(ESI-MS)和紫外-可见吸收光谱(UV-Vis)分析,研究了CrCl₃·6H₂O 浓度为0.1～0.6 mol·L-1的水溶液和[1ChCl∶2EG]/CrCl₃·6H₂O ILs中,Cr(Ⅲ)配合物的存在形式。研究结果表明,在含有CrCl₃·6H₂O的溶液中,Cr(Ⅲ)与Cl-和H₂O形成[Cr(H₂O)_nCl_6-n]n-3配合物,其配合物的优势物种受CrCl₃·6H₂O浓度的影响。水溶液中Cr(Ⅲ) 的优势配合物为[Cr(H₂O)₆]3+与[Cr(H₂O)₅Cl]2+,并随CrCl₃·6H₂O浓度增加,水溶液的UV-Vis吸收光谱峰红移,[Cr(H₂O)₅Cl]2+的相对含量增加。而[1ChCl∶2EG]/CrCl₃·6H₂O ILs中的优势配合物为[Cr(H₂O)₂Cl₄]-和[Cr(H₂O)₃Cl₃],且随CrCl₃·6H₂O 浓度增加,溶液的颜色从浅橙红色逐渐变为深绿色,溶液的UV-Vis吸收光谱峰蓝移,[Cr(H₂O)₃Cl₃]的相对量增加。说明CrCl₃·6H₂O的浓度变化,将影响配体Cl-和H₂O与Cr(Ⅲ)配位结合的配位数,从而影响配合物优势物种的相对量。     

［Co(tren)(amino acidato-N,O)］X2·nH2O在溶液中的NMR研究

报道了配合物［Co(tren)(DL-phenylalaninato)］(ClO₄)₂ (Ⅰ)、Co(tren)(L-prolinato)］I₂·H₂O (Ⅱ)、［Co(tren) (L-valinato)］I₂·1/3H₂O (Ⅲ)、［Co(tren)(L-isoleucinato)］I₂ (Ⅳ)、［Co(tren) ( L-leucinato)］I₂ (Ⅴ) 在溶液中的NMR研究. 通过同核和异核二 维核磁共振实验归属了配合物的¹H和¹³C NMR ，发现在配合物的空间结构 中，四齿配体(tren)的3个螯合臂中有两个构象稳定，而另一个构象不稳定，这与晶体学数据吻合. 通过变温实验和溶剂效应实验，发现在配合物Ⅲ、Ⅳ、Ⅴ中存在分子内氢键，而在晶体结构中，所有配合物都存在分子间氢键. 配合物Ⅰ、Ⅱ在溶液中的行为需进一步的研究 .     

几种易溶性有机溶剂水溶液的1H、13C、17O和31P NMR研究

本文用络合平衡及快交换的方法定量描述了磷酸三乙酯(TEP)、四氢呋喃(THF)、二氧六环(DO)和乙腈(AN)水溶液中化学位移随浓度变化的曲线。发现体系中未配位水的¹H化学位移与其浓度的关系为:H₂O δ₀=1.07+3.71e^{k(0.018-1)/[H₂O]}。K值与溶剂的供电性和分子量有关。溶剂破坏水结构的能力取决于它的供电性。     

磷掺杂硼钒氧簇化合物的二维相关红外光谱研究

一个新颖的磷掺杂硼钒氧簇化合物[Li(H₂O)₂]₂[Cu(en)₂]₃[H₂en]₂[V₁₂P₁₂B₆O₆₈(OH)₄(H₂O)]·3(H₂O)1通过水热法合成,通过Li⁺连接成一维无限结构,再通过氢键连成三维立体结构。针对该化合物,通过二维红外相关光谱并作了详细分析,化合物1簇阴离子振动偶极矩对磁场和温度的变化均有响应峰,2D-IR COS提供了一种结构表征新方法。     

丙烯腈γ辐射聚合的NMR研究

用¹H NMR、¹³C NMR谱、自旋-晶格弛豫时间（T₁）和自旋-自旋弛豫时间（T₂）研究了丙烯腈在⁶⁰Co γ射线辐射聚合后的大分子结构变化与大分子链的运动. 结果表明随着辐射剂量增大，在单体形成聚合物的过程中，聚合物主链上出现了少量的-OH基团，继续增大辐射剂量， -OH部分被氧化. 对聚合物溶液的变温氢谱的研究表明，溶剂中的残余水与上述-OH形成氢键，且随着温度升高氢键被破坏，同时H₂O与-OH之间还存在着质子交换. 利用¹³C NMR谱对丙烯腈辐射聚合的产物进行了序列结构分析. 对T₁和T₂的研究表明，辐射剂量的增大并未影响到聚丙烯腈的链运动，证明了在丙烯腈的辐射聚合过程交联反应未发生.     

KxCoO2·yH2O(x<0.2,y≤0.8)的晶体结构、输运及磁学性质

利用熔融KOH和Co₃O₄在较低温度(480℃)下反应制备出K_0.36CoO₂，然后用高锰酸钾溶液和饱和的过硫酸钾溶液进行氧化处理.氧化的同时伴随有水分子嵌入.K_0.36CoO₂用高锰酸钾和过硫酸钾溶液处理后分别得到K_0.12CoO₂·0.8H₂O和K_0.16CoO₂·0.6H₂O.这两种化合物都属于六角晶系，表现出金属行为，脱水后主相变为正交结构并且呈现出半导体特性.K_0.16CoO₂·0.6H₂O在56K附近可能存在自旋玻璃转变行为或其他涨落.随着钾含量的减少和水含量的增多，样品的自旋玻璃行为受到抑制或发生磁性相分离.样品K_0.12CoO₂·0.8H₂O在零场冷却和有场冷却曲线上的分叉现象基本上消失.还讨论了产生K_xCoO₂与Na_xCoO₂体系结构和物性差别的原因. 关键词： xCoO₂')" href="#">K_xCoO₂ 晶体结构 自旋玻璃态 磁性     

邻啡啰啉─吡啶2,6二甲酸铕二、三元配合物的NMR研究

报道了稀上铕(Eu³⁺)与吡啶-2,6-二甲酸(H₂DPC)及邻啡啉(Phen)形成的二元和三元固体配合物的制备.对它们进行了元素分析,确定该配合物的组成为二元Na₃[Eu(DPC)₃]·2H₂O和三元NaEu(DPC)₂·4H₂O,对上述配合物的结构作了核磁共振氢谱(¹H NMR)、碳谱(¹³CNMR)和氮谱(¹⁴N NMR)及红外光谱(IR)的研究.吡啶-2,6-二甲酸中的羧基以单齿配位(整个分子为三齿配位),二、三元配合物中铕的配位数分别为9和8.     

偏压在隧道效应中的作用

从隧道扫描势垒模型出发。用量子力学导出隧道电流与针尖间的偏压、间距及它们的逸出功之间的关系,并从能带模型的角度导出样品与针尖的间距不变时,隧道电流与偏压成正比关系．指出偏压的作用主要是提高针尖上电子的能量,使针尖上的电子比样品上的电子更容易穿过势垒,从而形成隧道电流．     

Simultaneous Brownian motion of N particles in a temperature gradient

A system of N Brownian particles suspended in a nonuniform heat bath is treated as a thermodynamic system with internal degrees of freedom, in this case their velocities and coordinates. Applying the scheme of nonequilibrium thermodynamics, one then easily obtains the Fokker-Planck equation for simultaneous Brownian motion of N particles in a temperature gradient. This equation accounts for couplings in the motion as a result of hydrodynamic interactions between particles.     

Computational performance of Free Mesh Method applied to continuum mechanics problems

The free mesh method (FMM) is a kind of the meshless methods intended for particle-like finite element analysis of problems that are difficult to handle using global mesh generation, or a node-based finite element method that employs a local mesh generation technique and a node-by-node algorithm. The aim of the present paper is to review some unique numerical solutions of fluid and solid mechanics by employing FMM as well as the Enriched Free Mesh Method (EFMM), which is a new version of FMM, including compressible flow and sounding mechanism in air-reed instruments as applications to fluid mechanics, and automatic remeshing for slow crack growth, dynamic behavior of solid as well as large-scale Eigen-frequency of engine block as applications to solid mechanics.     

Are random walks random?

Random walks have been created using the pseudo-random generators in different computer language compilers (BASIC, PASCAL, FORTRAN, C++) using a Pentium processor. All the obtained paths have apparently a random behavior for short walks (2¹⁴ steps). From long random walks (2³³ steps) different periods have been found, the shortest being 2¹⁸ for PASCAL and the longest 2³¹ for FORTRAN and C++, while BASIC had a 2²⁴ steps period. The BASIC, PASCAL and FORTRAN long walks had even (2 or 4) symmetries. The C++ walk systematically roams away from the origin. Using deviations from the mean-distance rule for random walks, d² ∝ N, a more severe criterion is found, e.g. random walks generated by a PASCAL compiler fulfills this criterion to N < 10 000.     

The dense α-√3 × √3Pb/Si(1 1 1) phase: A comprehensive STM and SPA-LEED study of ordering, phase transitions and interactions

The T-θ phase diagram for the system Pb/Si(1 1 1) was determined in the coverage range 6/5 ML < θ < 4/3 ML from complementary STM and SPA-LEED experiments. This coverage is within the range where a “Devil’s Staircase” (DS) has been realized. The numerous DS phases answer conflicting information in the Pb/Si(1 1 1) literature and update the previously published phase diagram. The measurements reveal the thermal stability of the different linear DS phases with the transition temperature found to be a function of phase period. Because of additional complexity in the experimental system (i.e. two-dimensionality and 3-fold symmetry) the linear DS phases transform at higher temperature into commensurate phases of 3-fold symmetry HIC (historically named “hexagonal incommensurate phase”). Different types of HIC phases have been discovered differing in the size of the supercell built out of √3 × √3 domains separated by domain walls of the √7 × √3 phase. The detailed structures of these HIC phases (coverage, binding site, twist angle, etc.) have been deduced from the comparison of STM images and diffraction patterns. After heating the system to even higher temperature the HIC phase transforms into the disordered phase. For sufficiently high coverage a SIC (“striped incommensurate phase” which is also built from √3 × √3 domains but meandering √7 × √3 domain walls) is observed which also disorders at high temperatures.     

Prediction of compositional ordering and separation in alloy nanoclusters

The statistical-mechanical free-energy concentration expansion method (FCEM) in conjunction with semi-empirical coordination-dependent energetic parameters was used for atomistic modeling of Ni-Cu-Al, Ni-Cu-Rh and the corresponding binary Ni-Cu, Ni-Al and Rh-Cu nanocluster systems, containing from 13 to 923 atoms with icosahedral and cuboctahedral shapes. The high efficiency of FCEM enables computations of such relatively large binary or ternary alloy clusters. Remarkable differences, governed by the opposite Ni-Cu and Ni-Al heteroatomic interactions, were noted in the surface segregated “magic-number” ordered compositional patterns of the two ternary clusters. Due to the strong Ni-Al interactions, the compositional ordering extends into the cluster core, and at elevated temperatures a sharp order-disorder transition occurs, depending on the cluster size, shape and composition. The computed site-specific atomic concentrations form the basis for evaluating pertinent thermodynamic functions. For all the alloy clusters a Schottky-type heat capacity anomaly is predicted and attributed to gradual desegregation excitation processes. In addition, inter-cluster compositional separation is computed for Rh-Cu clusters, and transition temperatures estimated from the disappearance of convexity in the free-energy vs. composition curves.     

N = 4 Supersymmetric Morse Oscillator and Its Spectrum-Generating Algebra

In this paper N = 4 supersymmetry of generalized Morse oscillators in one dimension is studied. Both bound states and scattering states of its four superpartner Hamiltonians are analyzed by using unitary irreducible representations of the noncompact Lie algebra su(1,1). The spectrum-generating algebra governing the Hamiltonian of the N = 4 supersymmetric Morse oscillator is shown to be connected with the realization of Lie superalgebra osp(1,2)or B(0,1) in terms of the variables of a supersymmetric two-dimensional harmonic oscillator.     

The rotating Morse potential energy eigenvalues solved by using the analytical transfer matrix method

We study the eigenvalues of the rotating Morse potential by using the quantization condition from the analytical transfer matrix(ATM) method.A hierarchy of supersymmetric partner potentials is obtained with Pekeris approximation,which can be used to calculate the energies of higher rotational states from the energies of lower states.The energies of rotational states of the hydrogen molecule are calculated by the ATM condition,and comparison of the results with those from the hypervirial perturbation method reveals that the accuracy of the approximate expression of Pekeris for the eigenvalues of the rotating Morse potential can be improved substantially in the framework of supersymmetric quantum mechanics.     

N = 4 Supersymmetric Morse Oscillator and Its Spectrum-Generating Algebra

In this paper N = 4 supersymmetry of generalized Morse oscillators in one dimension is studied. Both bound states and scattering states of its four superpartner Hamiltonians are analyzed by using unitary irreducible representations of the noncompact Lie algebra su（1,1）. The spectrum-generating algebra governing the Hamiltonian of the N = 4 supersymmetric Morse oscillator is shown to be connected with the realization of Lie superalgebra osp（1,2） or B（0,1） in terms of the variables of a supersymmetric two-dimensional harmonic oscillator.     

The translation-rotation paradox in the nucleation theory

The factor of 10¹⁷ proposed by Lothe and Pound in the theory of nucleation of droplets from the vapor phase is studied using classical statistical mechanics. The controversial factor is derived from partition functions for an isolatedn-mer and for ann-molecular cluster imbedded in the bulk liquid phase. The rotational degrees of freedom have no place in, in agreement with Reiss, Katz, and Cohen's treatment. It is proved that the surface free energy of a cluster is proportional to the surface area. The estimate of what Lothe and Pound called the replacement term is different from those of previous authors. It is concluded that is written as a ratio = _g/_l, where _g and _l , are the volumes per molecule in the gas phase and in the liquid phase, respectively. For water at 300K, is approximately equal to 10₄.