基于最新势能面的C(~1D)+H_2反应的环聚合分子动力学研究（英文）

本文利用环聚合分子动力学方法对C(~1D)+H_2反应开展了详细的理论研究.计算中使用了最近构建的Zhang-Ma-Bian(ZMB)从头算势能面,该势能面对锥形交叉附近区域以及范德华区域均有精确的描述.环聚合分子动力学计算得到的热反应速率常数与最新实验值吻合很好.与前人计算结果比较,发现在?~1A'电子基态的ZMB-a势能面上获得的反应速率常数远大于前人构建的RKHS势能面上的结果,这是由于ZMB势能面上的范德华鞍具有与之前势能面上的范德华阱完全不同的动态学作用,表明环聚合分子动力学方法能够处理范德华作用引起的势能面拓扑结构所导致的动态学效应.本文还揭示了b~1A"电子激发态ZMB-b势能面以及量子效应对反应的重要性.     

F+H2O→HF+OH反应的高精度速率常数的计算研究

F+H₂O→HF+OH是四原子反应的典型代表,并在环境和天体化学中扮演着重要角色. 基于全维势能面,本文采用环-聚合分子动力学(RPMD)方法计算了该反应的速率常数. 该势能面可以重现高精度理论化学水平(FPA和HEAT)上得到的反应能垒和放热数据,它是目前该体系的最准确势能面. RPMD方法重现了之前半经典过渡态理论结合两维主方程得到的速率常数,二者都与实验结果高度吻合. RPMD方法可以高效可靠地考虑量子效应,如量子隧穿和零点能效应等. 另外,RPMD计算结果随珠子数量增加收敛较快,这些都与之前RPMD的诸多计算应用发现的结论一致.     

O(1D)和CD4反应的准经典轨线

在新的全域势能面上, 用准经典轨线方法细致地研究了O(¹D)+CD₄多通道化学反应的动力学．这个势能面是用交换不变多项式方法基于MRC+Q/aug-cc-pVTZ从头算点拟合得到的．通过计算得到了产物OD+CD₃、D+CD₂OD/CD₃O和D₂+DCOD/D₂CO的分支比、平动能分布以及角度分布,结果显示理论与实验吻合得较好, 从而说明了这个反应的同位素取代效应很小． 研究表明,O(¹D)+CD₄反应是经过陷入的抽取机理发生的： 最初主要通过D原子的抽取,并不是之前人们认为的直接C-D键的插入形成CD3OD中间物后再进而解离成各个产物通道．     

CHCl3电子吸附速率常数的离子迁移谱

利用电晕放电离子迁移谱, 使用高纯氮气作为载气和迁移气体, 研究了电场强度在200～500 V/cm变化时CHCl₃的解离电子吸附速率常数, 得到样品所对应的电子吸附速率常数为1.26×10^-8～8.24×10^-9 cm³/(molecules s)．利用该装置测量了固定电场下,样品的电子吸附速率常数与样品浓度之间的关系．此外利用所获得的离子迁移谱图得到了不同电场强度下Cl^-与CHCl₃之间的离子分子反应速率常数.     

反应物NO的转动激发对反应N(4S)+NO(X2Π)→N2(X3Σg-)+O(3P)影响的立体动力学研究

采用准经典轨线方法,在碰撞能为0.6 eV时,研究了反应物NO分子的转动激发对发生在³A"和³A'势能面上的反应N(⁴S)+NO(X²Π)→N₂(X³Σ_g^-)+O(³P)的立体动力学性质的影响. 详细讨论了在反应物分子的不同转动态下发生在两个势能面上反应的矢量性质. 结果表明, 反应物分子NO的转动激发对发生在³A′势能面上的立体动力学性质产生重大影响, 这可能与该势能面上存在一个早期势垒有关.     

D+OD+反应的量子动力学研究：交换通道和抽取通道的竞争

基于精确的势能面,研究D+OD⁺反应在0.0～1.0 eV碰撞能范围内的量子动力学. 用CS近似(centrifugal sudden approx-imation)的含时波包方法研究吸热的抽取反应通道(D+OD⁺→ O+D₂⁺)和热中性的交换反应通道(D+OD⁺→D+OD⁺),计算两个通道的反应几率、总积分反应截面和热速率常数. 发现在交换反应的反应路径上存在一个凸起结构. 计算的总角动量J=0时的波包分布的含时演化清楚地表明凸状结构对两个通道的动力学有非常重要的影响.     

准经典轨线方法研究H(2S)+NO(X2π)→N(4S)+OH(X2π)反应动力学

本文基于精确的势能面,采用准经典轨线方法研究了H(²S)+NO(X²π)→N(⁴S)+OH(X²π)反应的动力学. 对碰撞能量为2.00∽2.80 eV,计算了反应的总反应积分截面,发现它随碰撞能量的增加而单调增加. 特别地,在碰撞能为2.40∽2.57 eV时,计算的反应截面与实验结果吻合. 此外,计算得到的反应速率常数也与实验匹配. 在碰撞能为2.57 eV时,通过对反应轨线的分析,发现该反应由非直接反应主导(是直接反应的1.4倍),揭示了反应在高碰撞能量下的反应动力学特性.     

O-与CH3CN反应机理的密度泛函理论研究

采用G3MP2B3方法研究了氧负离子与乙腈反应的势能剖面.在(U)B3LYP/6-31+G(d,p)理论水平下分别优化了该反应势能面上反应物、产物、中间体和过渡态的分子结构,采用G3MP2B3方法校正了这些关键点的能量. 势能面上的各个反应路径均通过针对过渡态的內禀反应坐标理论计算加以确定. 分别考察了四个可能的热力学产物通道,即质子转移、氢原子转移、H₂⁺转移和双分子亲核取代反应途径. 其中,经H₂⁺转移生成H₂O的反应通道为该反应的主要产物通道.     

克里奇中间体CH2OO与CF3CF=CF2反应的动力学研究

本文使用OH激光诱导荧光方法研究了结构最简单的克里奇中间体CH₂OO和CF₃CF=CF₂的反应动力学. 在压强为10 Torr条件下，测量了温度在283，298，308和318 K的反应速率常数，分别为(1.45±0.14)×10^-13，(1.18±0.11)×10^-13，(1.11±0.08)×10^-13和(1.04±0.08)×10^-13 cm³·molecule^-1·s^-1. 根据阿伦尼乌斯方程，获得该反应的活化能为(-1.66±0.21) kcal/mol. 在6.3∽70 torr压力范围内，未观察到该反应的速率常数存在压力相关.     

BF自由基X1∑+和a3∏态光谱常数和分子常数研究

采用内收缩多参考组态相互作用方法和相关一致基aug-cc-pV6Z, 对BF自由基X¹∑⁺和a³∏ 态的势能曲线进行了研究. 计算是在0.095---1.33 nm的核间距内进行的. 为获得更准确的结果, 计算中还考虑了Davidson修正、相对论修正及核价相关修正对势能曲线的影响. 相对论修正采用的方法是二阶DouglasKroll哈密顿近似, 修正计算是在cc-pV5Z基组水平上进行的. 核价相关修正使用的是cc-pCV5Z基组. 利用得到的势能曲线, 拟合出了各种修正下BF自由基X¹∑⁺和a³∏ 态的光谱常数D_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e和α_e、并与实验结果进行了比较. 结果表明: 考虑Davidson修正、相对论修正和核价相关修正后得到的光谱常数最接近实验结果. 利用修正后的势能曲线, 通过求解径向振转Schrödinger方程, 找到了转动量子数J = 0时这两个电子态的全部振动态, 并计算了每一电子态前20个振动态的振动能级、惯性转动常数和离心畸变常数, 其值与已有的实验结果较为一致. 本文得到的光谱常数和分子常数达到了很高的精度, 能为进一步的光谱实验提供可靠的参考.     

Depolarization currents in the Na0.5Bi8.5Ti2Nb4O27 and Na0.5Bi8.5Ti2Ta4O27 layered ferroelectrics

The influence of the prehistory on the electrical properties of layered ferroelectrics is investigated. It is established that the heating of short-circuited samples of the nonpolarized ceramic material Na_0.5Bi_8.5Ti₂Nb₄O₂₇ leads to the appearance of maxima of the current at temperatures below the Curie point only in the case of preliminary ageing of the samples. Original Russian Text ? A.I. Burkhanov, Yu.V. Kochergin, K. Bormanis, A. Kalvane, M. Dambekalne, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 7, pp. 1393–1394.     

Structural study of the Lu2Si2O7-Sc2Si2O7 system

Different compositions in the Lu₂Si₂O₇-Sc₂Si₂O₇ system have been synthesized following the ceramic method. All XRD patterns are compatible with the thortveitite structure (β-RE₂Si₂O₇ polymorph). Unit cell parameters change linearly with composition, which indicates a complete solid solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇. ²⁹Si MAS NMR spectra show a decrease of the ²⁹Si chemical shift with increasing Sc content. A correlation reported in the literature to predict ²⁹Si chemical shifts in silicates is applied here to obtain the theoretical variation in ²⁹Si chemical shift values in the system Lu₂Si₂O₇-Sc₂Si₂O₇ and the results compare favourably with the values obtained experimentally. The FWHM values of the ²⁹Si MAS NMR curves indicate a random distribution of Lu and Sc in the structure of the intermediate members. Finally, the IR study of the system confirms the solubility of Sc₂Si₂O₇ in Lu₂Si₂O₇, showing the splitting of several modes in the intermediate members and a linear shift of the frequency on going from one end-member to the other.     

Fluoride glasses in the InF3-GaF3-YF3-PbF2-CaF2-ZnF2 system

New glasses have been synthesized in a multicomponent system based on indium fluoride. Samples of a few mm in thickness were obtained. They are transparent and homogeneous. Main physical properties such as density, characteristic temperatures, density, thermal expansion and refractive index have been measured. The evolution versus composition is reported for samples with the formula: (35−x) InF₃-xGaF₃-10YF₃-25PbF₂-15CaF₂-15ZnF₂. T_g lies between 260 and 296 °C while melting starts around 480 °C. Glass samples are stable at room temperature. By comparison with other standard fluoride glasses, they exhibit higher refractive index and density.     

Production and decay of the π−π−π+ system in the reaction π−d → dπ−π−π+ at 9 GeV/c

In this paper we present a study of the reaction π^?d → π^?π^?π⁺d at 9 GeV/c. The mass spectra are in fair agreement with the predictions of a reggeized pion-exchange Deck model. However, the s-channel azimuthal angular distribution indicates a ?-exchange Deck contribution. The results of the partial-wave analysis of the (3π)^? system are compared with those obtained in a hydrogen target: the J^P = 2⁺ contribution is very small (at most 1.5 ± 1.2)% in our data, which are dominated by J^P = 1⁺ for low mass, whereas the J^P = 0^?, 1⁺, 2^? have comparable importance in the higher mass region.     

Zeros of the π+π− → π+π− amplitude

Recent data on the reaction $\text{p}\text{p}\text{→ π}{}^{\mathrm{?}}\text{π}{}^{\mathrm{+}}$ show four conspicuous dips in the angular distribution at fixed values of ν = t?u. The conjecture is made that the channel π^?π⁺ → π^?π⁺ has zeros at the same ν values. Using data of the CERN-Munich group, one can follow the zeros through the whole Mandelstam plane. The zeros pass through the intersections of s and t channel poles, as the Veneziano model predicts; however, away from these intersections, they propagate in a fashion systematically quite different from Veneziano's ansatz.     

Glass formation in the As2Se3-As2Te3-Sb2Te3 system

Chalcogenide glasses from the As₂Se₃-As₂Te₃-Sb₂Te₃ system were synthesized for the first time. The glass-forming region was determined by X-ray diffraction and electron microscopic analyses.The basic physicochemical parameters such as density (d), microhardness (HV) and temperatures of phase transformations (glass transition T_g, crystallization T_cr and melting T_m) were measured. Compactness and some thermomechanical characteristics such as volume (V_h) and formation energy (E_h) of micro-voids in the glassy network as well as the elasticity module (E) were calculated. The glass-forming ability was evaluated according to Hruby's criteria (K_G). The correlation between composition and properties of the (As₂Se₃)_x(As₂Te₃)_y(Sb₂Te₃)_z glasses was established and comprehensively discussed.     

X-ray study of phase transitions in the system of solid solutions K2Pb4Nb10O30-Na2Pb4Nb10O30-K6W4Nb6O30

Boundaries of morphotropic phase transitions region in the system of solid solutions K₂Pb₄Nb₁₀O₃₀-Na₂Pb₄Nb₁₀O₃₀-K₆W₄Nb₆O₃₀ with the structure of the tetragonal tungsten bronze have been specified. Presence of the second morphotropic phase transition, perpendicular to the first one has been revealed. The temperature dependences of the structural parameters of some compounds have been investigated. The compounds with high values of Curie temperatures and working temperatures have been obtained.     

Model-independent analysis of the reaction π+p → π+π−Δ++

The high-statistics data on π⁺p → π⁺π^?Δ⁺⁺ at 7.1 GeV/c are used in a detailed analysis using model-independent means. Positivity conditions are found to be violated, although there is overlap between the positivity domain and the error ellipsoid. Using points modified to satisfy positivity, we confirm certain aspects of a previous model-dependent analysis. In particular, the percentage S-wave is found to be close to the lower limit consistent with the ππ moments alone. A number of quark-model predictions are confronted with the data and also with our modified points, and reasonable but not total agreement is observed.     

Electrical transport and superconductivity in the Al2O3-Bi2Sr1.8Ca1.2Cu2Oy and MgO-Bi2Sr1.8Ca1.2Cu2Oy composites

We have measured the resistivities of Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites with the nominal Bi₂Sr_1.8Ca_1.2Cu₂O_y volume fraction, ₂₂₁₂, ranging from 0.15 to 1.00. For the Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu ₂O_y composites, we find for the samples with ₂₂₁₂≥0.6 that the superconducting transition temperature, T_c, is not disturbed by the addition of Al₂O₃. For ₂₂₁₂<0.3, no zero-resistivity state is observed. For the MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites, T_c is barely disturbed for the samples with ρ₂₂₁₂≥0.7. No superconducting state is observed for the samples with ρ₂₂₁₂<0.35. The variation of (300 K) with ρ₂₂₁₂ indicates a three-dimensional percolating Bi-Sr-Ca-Cu-O matrix occurring at ρ₂₂₁₂≈0.19 and ≈0.15 in Al₂O₃-Bi₂Sr_1.8Ca_1.2 Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y, respectively. Both resistivity and magnetization measurements suggest that the reactions of Bi₂Sr_1.8Ca_1.2Cu₂O_y with MgO are weaker than with Al₂O₃.     

Magnetic structure of the Sm5Ge4-type Tb2Ti3Ge4

The orthorhombic Sm₅Ge₄-type Tb₂Ti₃Ge₄ shows square modulated non-collinear magnetic ordering with wave vector K=[±1/3, 1/2, 1/2] at 2 K. The terbium magnetic moments lie in the bc plane and magnetic moment value of 7.5(2) μ_B/Tb is obtained at 2 K.