OH+C2H3F的反应机理及产物支化比反应的理论研究

本文对HOC₂H₃F可能解离通道的势能面进行从头算CCSD(T)/CBS//B3LYP/6-311G(d,p)计算,同时对速率常数进行Rice-Ramsperger-Kassel-Marcus计算. 生成主要产物CH₂CHO+HF最有利的反应途径是OHC₂H₃F→i2→TS14→i6→TS9→i3→TS3→CH₂CHO+HF,其中速率决定步骤是HF通过TS11从CO桥接位置解离,能量比反应物高3.8 kcal/mol. 借助中间态TS14,F原子从C_α迁移到C_β位置生成CH₂O+CH₂F,然后通过中间态TS16,H从O迁移到C_α位置;通过中间态TS5,C-C键断裂生成产物,其能量比反应物低1.8 kcal/mol,比TS11低4.0 kcal/mol.     

双原子分子激发态势能的自旋相关局域Hartree-Fock密度泛函理论方法

基于自旋相关局域Hartree-Fock (SLHF)势函数,本文提出了一种计算双原子分子激发态势能的密度泛函理论(DFT)方法,并将该方法应用于和的激发态势能曲线的计算。在只考虑交换能的情况下,本文的DFT计算结果与文献中精确方法和Hartree-Fock (HF)方法的结果符合的非常好,说明采用SLHF势函数作为交换势的DFT方法是一个很好的计算激发态势能的方法。本文还计算和探讨了电子的关联势函数和关联能,发现传统的近似方法在较大核间距的情况下大大低估了电子的关联能.     

Large momenta fluctuations of charm quarks in the Quark-Gluon Plasma<Superscript>⋆</Superscript>

We show that large fluctuations of D-mesons kinetic-energy (or momentum) distributions might be a signature of a phase transition to the Quark-Gluon Plasma (QGP). In particular, a jump in the variance of the momenta or kinetic energy, as a function of a control parameter (temperature or Fermi energy at finite baryon densities) might be a signature for a first-order phase transition to the QGP. This behavior is completely consistent with the order parameter defined for a system of interacting quarks both at zero temperature (and finite baryon densities) or at finite temperatures which shows a jump in correspondence with a first-order phase transition to the QGP. The J/Ψ displays exactly the same behavior of the order parameter and of the variance of the D-mesons. We discuss implications for relativistic heavy-ion collisions within the framework of a transport model and possible hints for experimental search.     

Linearisation and potential symmetries of certain systems of diffusion equations

We consider systems of two pure one-dimensional diffusion equations that have considerable interest in Soil Science and Mathematical Biology. We construct non-local symmetries for these systems. These are determined by expressing the equations in a partially and wholly conserved form, and then by performing a potential symmetry analysis on those systems that can be linearised. We give several examples of such systems, and in a specific case we show how linearising and hodograph-type mappings can lead to new solutions of the diffusion system.     

Hamiltonian description and 6D calculations on the ammonia vibrational levels

In this work, a Hamiltonian formalism and a 6D vibrational calculation procedure is described and implemented, designed for the exploration of vibrational motion in ammonia (and any XH₃ molecule). The 6D potential energy surface of ammonia was modelled in simple analytical form (including the inversion potential) at the planar, totally symmetric (D_3h) reference configuration. Using the described method (which is an adaptation of the formalism, previously developed and applied to benzene), 6D calculations were carried out on the vibrational level system of ammonia ¹⁴NH₃, at the lower levels of vibrational excitation. On the basis of the satisfactory agreement between the calculated and the experimentally measured vibrational frequencies, the values of some important harmonic and anharmonic force constants, characterizing the ammonia PES were determined.     

Lie-optics, geometrical phase and nonlinear dynamics of self-focusing and soliton evolution in a plasma

It is useful to state propagation laws for a self-focusing laser beam or a soliton in group-theoretical form to be called Lie-optical form for being able to predict self-focusing dynamics conveniently and amongst other things, the geometrical phase. It is shown that the propagation of the gaussian laser beam is governed by a rotation group in a non-absorbing medium and by the Lorentz group in an absorbing medium if the additional symmetry of paraxial propagation is imposed on the laser beam. This latter symmetry, however, needs care in its implementation because the electromagnetic wave of the laser sees a different refractive index profile than the laboratory observer in this approximation. It is explained how to estimate this non-Taylor paraxial power series approximation. The group theoretical laws so-stated are used to predict the geometrical or Berry phase of the laser beam by a technique developed by one of us elsewhere. The group-theoretical Lie-optic (or ABCD) laws are also useful in predicting the laser behavior in a more complex optical arrangement like in a laser cavity etc. The nonlinear dynamical consequences of these laws for long distance (or time) predictions are also dealt with. Ergodic dynamics of an ensemble of laser beams on the torus during absorptionless self-focusing is discussed in this context. From the point of view of new physics concepts, we introduce a stroboscopic invariant torus and a stroboscopic generating function in classical mechanics that is useful for long-distance predictions of absorptionless self-focusing.     

黄河甘宁蒙段表层沉积物中重金属元素含量及其形态分析

到目前为止,关于水环境中重金属浓度和形态分布的研究有许多报道。但是关于黄河上游,特别是对黄河甘宁蒙段区域重金属的研究报道仍需进一步深入。在相关研究工作的基础上,使用HR-ICP-MS和BCR连续提取法主要对2011年丰水期黄河甘宁蒙段12个采样点表层沉积物Cd,Pb,Cr,V,Co,Ni,Cu和Zn重金属元素的含量,形态和潜在风险进行测定与分析。结果表明：所有采样点各重金属元素含量顺序相同：Cr>V>Zn>Cu>Ni>Pb>Co>Cd,与各采样点所在区域土壤中背景值相比,S5采样点Cd元素的含量水平最高(1.30 μg·g-1) 约为背景值(0.103 μg·g-1)的13倍。通过I_geo对重金属进行污染评价,结果显示S5采样点Cd元素为强污染水平(I_geo=3.08),内蒙古段四个采样点(S1—S4)Cd表现为中强度污染水平,I_geo位于2.02~2.90之间;此外,富集因子(EF)评价结果发现,研究区域表层沉积物中八种重金属均受到人为活动的污染。根据潜在生态风险指数(RI)结果,S5和S3采样点为高生态风险,其他采样点为中等生态风险。BCR连续提取法结果显示Cd的有效性最高,其次为Co和Ni,V和Cr有效性最低。根据形态分析风险评估准则 (RAC),Cd在S1—S4采样点有高风险,在S5采样点有很高风险;而对于Ni和Co来说,12个采样点中均表现为中等风险。研究结果和结论可为相关政府部门提供重要的研究信息。     

UH和UH2分子的结构与势能函数

用相对论有效原子实势(RECP)和密度泛函(B3LYP/SDD)方法研究了UH,UH₂基态和低激发态的结构和势能函数,导出了分子的光谱数据.结果表明,UH和UH₂的基电子状态分别为X⁴Π和X³A₂,离解能分别为2.886eV和5.249eV,UH₂具有C2v对称性,得到了UH和UH₂的几个不同的低激发态的结构与光谱数据.应用多体项展式理论以及数字拟合方法 关键词： UH 2')" href="#">UH₂ 势能函数 分子结构     

基于扩散势能和自由体积的自扩散系数模型

在考虑自由体积和局部临界扩散势能的基础上,提出一种新的计算自扩散系数模型,并给出新模型中各个因子物理含义．同时还提出一种计算局部临界扩散势能的新方法,并应用于新模型．另外将衍生van der Waals状态方程应用于求解自由体积,式中所需径向分布函数由Morsali-Goharshadi方程得到．在相同条件下,新模型比原自由体积模型更准确．     

铁分子Fe2的自旋极化效应

采用密度泛函方法(B3P86)对 Fe_2分子结构进行了优化.计算结果中未观察到自旋污染,基态波函数与高态波函数并未混杂,结果表明,Fe_2中有8个未配对电子,这些电子空间分布不同和自旋平行产生的自旋极化效应,使 Fe_2能量最低.计算结果表明,Fe_2分子的基态是~9∑_g~ ,并非~7Δ_u,进而表明 Fe_2的自旋平行效应比电子自旋配对效应要强.计算得到该分子基态的二阶、三阶和四阶力常数分别为1.4115×10~(-2)aJ/nm~2、-37.1751×10~3aJ/nm~3和 98.7596×10~4aJ/nm~4；光谱数据ω_eχ_e、B_e、α_e分别为0.3522、0.0345、 0.4963×10~(-4)cm~(-1)；离解能为3.5522eV,平衡键长为0.2137nm,振动频率为292.914cm~(-1)；并得到了 Murrel-Sorbie 函数.