苯的硝基和叠氮基衍生物热力学性质的构效关系

苯的硝基和叠氮基衍生物是一类重要的含能材料,为了揭示其热力学性质与分子结构之间的关系,采用第一性原理进行了计算研究。通过计算平衡电负性连接指数,结合分子结构描述符,对苯的硝基和叠氮基衍生物的热力学性质建立了构效关系模型。模型检验结果表明,构建的模型具有良好的稳健性和预测能力,所得模型为苯的硝基和叠氮基衍生物的爆轰参数计算和分解机理研究提供了一种快速的热力学性质预测方法。     

苯的硝基和叠氮基衍生物热力学性质的构效关系

苯的硝基和叠氮基衍生物是一类重要的含能材料,为了揭示其热力学性质与分子结构之间的关系,采用第一性原理进行了计算研究.通过计算平衡电负性连接指数,结合分子结构描述符,对苯的硝基和叠氮基衍生物的热力学性质建立了构效关系模型.模型检验结果表明,构建的模型具有良好的稳健性和预测能力,所得模型为苯的硝基和叠氮基衍生物的爆轰参数计算和分解机理研究提供了一种快速的热力学性质预测方法 .     

用ab initio方法计算NaLi分子基态（X^1∑^＋）的势能函数及光谱常数

运用原子分子群表示方法，首先确定NaLi分子的电子基态（X^1∑^＋）．然后选用6—311＋＋G（3df，2pd）基组优化计算得到NaLi分子基态（X^1∑^＋）的平衡结构和离解能，采用电子相关QCISD（T）方法结合6—311＋＋G（3df，2pd）基组对NaLi分子基态进行单点能扫描计算．最后用单点扫描计算值结合优化计算所得参数去拟合Murrell—Sorbie函数，得到了NaLi分子基态的势能函数．用该势能函数计算的光谱常数与实验结果符合得很好，表明拟合确定的势能函数能精确地描述基态NaLi分子的结构和性质．     

柚皮苷二氢查尔酮抗氧化活性的构效关系研究

采用DPPH自由基清除实验和Materials Studio软件中的DmoL~3程序对柚皮苷二氢查尔酮的DPPH自由基清除率、几何结构和性质(振动频率、反应活性及热力学性质)进行了理论研究,得到了分子的抗氧化活性数据、稳定几何构型、各原子上的电荷分布、热力学性质、Fukui指数和前线分子轨道参数,计算结果表明柚皮苷二氢查尔酮具有较高的反应活性,分子中酚羟基上的氧原子是影响其反应活性的主要部位,也是发生亲电反应的活性位点,表现出较强的抗氧化性,当柚皮苷二氢查尔酮浓度为0.3mg·mL~(-1)时,DPPH自由基清除率达到86.49%.     

环烷烃及烷烃的折光指数与结构的关系研究

以分子拓扑学点价和自相关函数研究为基础,设计开发出一种新的以点价计算为基础的结构信息自相关拓扑指数tX.基于多元线性回归技术建立了对环烷烃及其烷烃的折光指数作出估算的定量结构性质关系.点价被定义为βi,由βi建构结构信息自相关拓扑指数tX.得到了它们与64种环烷烃的折光指数(nD)的二元回归方程和与27种烷烃的折光指数的二元回归方程.对环烷烃和烷烃折光指数的计算结果表明,计算值与实验值的一致性令人满意,平均误差为0. 25% .利用建立的模型,对另外5种烷烃的折光指数进行了预测.     

氮的三原子化合物的从头算及密度泛函研究

在6－311＋G＊基组水平上,对氮的三原子化合物N3^-、N3、N3^+,用MP2及六种密度泛涵方法进行了研究。结果表明,对于已知结构的化合物和计算结果与实验测定值非常吻合,对实验上未知的化合物分子的稳定几何构型及其有关参数进行了新的探讨和补充,同时比较了N3^-、N3、N3^+间相对稳定性和几何性质,并讨论了几种不同方法对该化合物系列诸性质参数的影响,结合MO理论及成键能的计算结果进行了成键分析。     

金属铍热力学性质的理论研究

使用第一性原理方法结合平均场模型研究了压力从0到150GPa、温度从0到1500K，金属铍六角密排结构(hcp)的热力学性质，包括铍的常态性质，等温高压物态方程，以及常压下平衡体积、体弹模量随温度的变化，Hugoniot曲线等.0K物态方程由广义梯度近似下的密度泛函理论计算，粒子热运动的贡献由平均场模型计算.由于铍的Debye温度比较高，计算自由能时考虑了零点振动能修正.计算结果与已有的静力学和冲击波实验数据符合得非常好. 关键词： 热力学性质 物态方程 第一原理计算     

LLM-105的分子间相互作用和热力学性质

应用第一性原理可以计算含能材料0 K下的结构和物理性质,但温度效应的缺失通常会导致计算数据与实验结果产生偏差.同时,与温度相关的热力学参数是含能材料在宏观和介观尺度下建模的关键输入.为此,本文以高能低感炸药1-氧-2, 6-二氨基-3, 5-二硝基吡嗪(LLM-105)为研究体系,基于准简谐近似,采用色散修正的密度泛函理论研究温度加载下LLM-105的分子间相互作用和热力学性质.晶格参数和热膨胀系数的演化表明LLM-105分子间相互作用具有强烈的各向异性,其中b轴方向(分子层间)的膨胀率远高于ac平面(分子层内). Hirshfeld表面及其指纹图分析进一步证实LLM-105的分子间相互作用主要取决于O···H构成的氢键.结合Mulliken布居数和结构分析,温度加载下氢键相互作用的变化可诱发硝基旋转,并使得C—NO₂键的强度明显减弱,为高温分解反应的触发键提供了理论依据.此外,本文计算了等容和等压条件下的热容、熵以及等温和绝热条件下的体模量等基础热力学参数.其中绝热条件下的体模量与实验值吻合,同时体模量随温度的演化反映了LLM-105在温度加载下的软化行为.上述...     

第一性原理研究压力对Fe2B的结构、机械性质的影响

基于密度泛函理论的第一性原理方法，系统研究了0～30 GPa压力下四方相Fe₂B的结构，稳定性和力学性质等.随着压力的增加，计算得到的晶格参数逐渐减小，所有结构均满足热力学稳定性，体积模量和剪切模量逐渐增大，韧性得到有效改善.硬度呈现先增大后减小的趋势，并在18 GPa压力时达到最大值，各向异性先增大后减小.德拜温度变化趋势与杨氏模量的变化趋势相同.同时还研究了相变结构——正交相的相关性质，结果表明其结构满足热力学稳定性但不满足力学稳定性，是否稳定存在还需要进行后续实验研究.     

液相分层二元合金交互作用参数和热力学量的计算方法

利用亚规则溶液模型及热力学原理讨论液相分层二元合金相交互作用参数和热力学性质,并以Pb-Zn为例计算了相应的活度系数,计算结果与文献报道相符。     

烷基极化效应与羰基13C化学位移

对羰基化合物中羰基碳的¹³C NMR化学位移与烷基（R）极化效应的内在关系 进行了研究. 结果表明：分子中R的极化效应增加使羰基碳的¹³C化学位移值升 高,其关系可表示为δ=a+b·ΣPEI(R),其中a、b为系数,PEI（R）为R极化效应指数.
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Magnetic properties of single grain R–Mg–Cd primitive icosahedral quasicrystals (R=Y,Gd, Tb or Dy)

The growth and characterization of single grains of the primitive icosahedral quasicrystal R–Mg–Cd (R=Y, Gd, Tb or Dy) are described. From the thermodynamic properties, it is confirmed that the system is a spin glass exhibiting the characteristic spin-freezing transition of such systems. There is no evidence for two distinct freezing transitions previously observed for polygrain samples. The bulk magnetic properties and the effect of crystalline electric fields on the spin-freezing temperature are found to be very similar to those of the face-centred icosahedral quasicrystal R–Mg–Zn.     

Structural,elastic, and electronic properties of topological semimetal WC-type MX family by first-principles calculation

Recently, the non-centrosymmetric WC-type materials(i.e., MoP, ZrTe, TaN, etc) have attracted extensive interest due to the discovery of their topological properties.By means of the first-principles calculations, here we have investigated the structural, thermodynamic, elastic, and electronic properties of the WC-type MX compounds(TiS, TiSe, TiTe, ZrS, ZrSe,ZrTe, HfS, HfSe, and HfTe).Among these nine compounds, five of them(TiS, ZrS, ZrSe_(0.9), ZrTe, and Hf0.92 Se) have been experimentally synthesized to crystallize in the WC-type structure and other four members have never been reported.Our calculations demonstrated that they are all structurally, thermodynamically, and dynamically stable, indicating that all of them should be possibly synthesized.We have also derived their elastic constants of single crystalline and their bulk and shear moduli in terms of the R.Hill approximations.Furthermore, in similarity to ZrTe, all these compounds have been theoretically derived to be topological semimetals.Whereas TiS is unique because of the coexistence of the Dirac nodal lines(DNLs) and sixfold degenerate nodal points(sixfold DNPs), the other eight members are revealed to exhibit coexisted Weyl nodes(WPs) and triply degenerate nodal points(TDNPs).Their electronic and topological properties have been further discussed.     

Static and dynamic properties of polymer brush with topological ring structures: Molecular dynamic simulation

By defining a topological constraint value(rn),the static and dynamic properties of a polymer brush composed of moderate or short chains with different topological ring structures are studied using molecular dynamics simulation,and a comparison with those of linear polymer brush is also made.For the center-of-mass height of the ring polymer brush scaled by chain length h~N~v,there is no significant difference of exponent from that of a linear brush in the small topological constraint regime.However,as the topological constraint becomes stronger,one obtains a smaller exponent.It is found that there exists a master scaling power law of the total stretching energy scaled by chain length N for moderate chain length regime,F_(ene)~Np~v,for ring polymer brushes,but with a larger exponent v than 5/6,indicating an influence of topological constraint to the dynamic properties of the system.A topological invariant of free energy scaled by(c)~(5/4) is found.     

Phase transition and thermodynamic properties of BiFeO3 from first-principles calculations

The first-principles projector-augmented wave method employing the quasi-harmonic Debye model,is applied to investigate the thermodynamic properties and the phase transition between the trigonal R3c structure and the orthorhombic Pnma structure.It is found that at ambient temperature,the phase transition from the trigonal R3c phase to the orthorhombic Pnma phase is a first-order antiferromagnetic-nonmagnetic and insulator-metal transition,and occurs at 10.56 GPa,which is in good agreement with experimental data.With increasing temperature,the transition pressure decreases almost linearly.Moreover,the thermodynamic properties including Grneisen parameter,heat capacity,entropy,and the dependences of thermal expansion coefficient on temperature and pressure are also obtained.     

Relation between the Superconducting Transition Temperature and the Axial Ratio in R Ni 2 B 2 C ( R =Y,Ho, Er,Tm, Lu) Under High Pressure

The effect of pressure on the lattice parameters of R Ni 2 B 2 C ( R = Y, Ho, Er, Tm, Lu) has been measured in order to investigate the relation of T C to axial ratio c/a in the tetragonal lattice or the cohesive properties of these materials. The large anisotropies are observed in the lattice compression curves especially for R =Ho and Tm; the c -axis is more compressible than the a -axis. On the other hand, the anisotropy in the lattice compression is found to be relatively small for R =Y and Lu. The close relation between T C and c/a is pointed out particularly for R =Ho.     

A Phase Transition in a Quenched Amorphous Ferromagnet

Quenched thermodynamic states of an amorphous ferromagnet are studied. The magnet is a countable collection of point particles chaotically distributed over \(\mathbb {R}^d\) , \(d\ge 2\) . Each particle bears a real-valued spin with symmetric a priori distribution; the spin-spin interaction is pair-wise and attractive. Two spins are supposed to interact if they are neighbors in the graph defined by a homogeneous Poisson point process. For this model, we prove that with probability one: (a) quenched thermodynamic states exist; (b) they are multiple if the intensity of the underlying point process and the inverse temperature are big enough; (c) there exist multiple quenched thermodynamic states which depend on the realizations of the underlying point process in a measurable way.     

Hierarchy of the non‐covalent interactions in the alanine‐based secondary structures. DFT study of the frequency shifts and electron‐density features

The alanine (Ala)‐based cluster models of C5, C7, and C10 H‐bonds are studied at the DFT/B3LYP level. CPMD/BLYP simulations of the infinite polyalanine α‐helix (C13 H‐bond) and the two‐stranded β‐sheets are performed. Combined use of frequency shifts and electron‐density features enable us to detect and describe quantitatively the non‐covalent interactions (H‐bonds) defining the intrinsic properties of Ala‐based secondary structures. The energies of the primary N? H O H‐bonds are decreasing in the following way: C13 > C5 ≥ C7 > C10. The energies of the secondary N? H O, N?H N, and H H interactions are comparable to those of the primary H‐bonds (～4.5 kcal/mol). Side chain–backbone C? H O interaction is found to be the weakest non‐covalent interaction in the considered species. Its energy is ～0.5 kcal/mol in the infinite polyalanine α‐helix. Quantum‐topological electron‐density analysis is found to be a powerful tool for the detection of secondary non‐covalent interactions (C?O H? C and H H) and bifurcated H‐bonds, while the frequency shift study is useful for the identification and characterization of primary or secondary H‐bonds of the N? H O type. Copyright © 2008 John Wiley & Sons, Ltd.     

Solitary wave solutions of nonlocal sine-Gordon equations

In this paper a nonlocal generalization of the sine-Gordon equation, u(tt)+sin u=( partial differential / partial differential x) integral (- infinity ) (+ infinity )G(x-x('))u(x(') )(x('),t)dx(') is considered. We present a brief review of the applications of such equations and show that involving such a nonlocality can change features of the model. In particular, some solutions of the sine-Gordon model (for example, traveling 2pi-kink solutions) may disappear in the nonlocal model; furthermore, some new classes of solutions such as traveling topological solitons with topological charge greater than 1 may arise. We show that the lack of Lorenz invariancy of the equation under consideration can lead to a phenomenon of discretization of kink velocities. We discussed this phenomenon in detail for the special class of kernels G(xi)= summation operator (j=1) (N)kappa(j)e(-eta(j)mid R:ximid R:), eta(j)>0, j=1,2, em leader,N. We show that, generally speaking, in this case the velocities of kinks (i) are determined unambiguously by a type of kink and value(s) of kernel parameter(s); (ii) are isolated i.e., if c(*) is the velocity of a kink then there are no other kink solutions of the same type with velocity c in (c(*)- varepsilon,c(*)+ varepsilon ) for a certain value of varepsilon. We also used this special class of kernels to construct approximations for analytical and numerical study of the problem in a more general case. Finally, we set forth results of the numerical investigation of the problem with the kernel that is the McDonald function G(xi) approximately K(0)(mid R:ximid R:/lambda) (lambda is a parameter) that have applications in the Josephson junction theory. (c) 1998 American Institute of Physics.     

Experimental results on strong interactions in the NAL hydrogen bubble chamber

This report presents a review of the data obtained on high-energy hadronic interactions in the 30-in. hydrogen bubble chamber at the National Accelerator Laboratory. The emphasis is on a presentation of the experimental results that have been acquired during the Laboratory's first year of operation. The five main topics discussed are (a) topological cross sections and multiplicity distributions, (b) studies of the diffraction process observed in some low multiplicity final states, (c) single particle inclusive spectra, (d) neutral particle production, and (e) multiparticle correlations.

While most of the data come from pp collisions and may be compared to results from the ISR, some of the more recent results from πp interactions are included and are compared to πp data at lower energies as well as to the pp results. The comparison between the πp and pp data indicates the striking result that many of the properties of high energy collisions seem almost independent of the nature of the projectile and target particles and depend primarily on the available center-of-mass energy.