Quasi-classical Trajectory Study of Ba+HI→BaI+H Reaction

The quasi-classical trajectory calculations based on extended London-Eyring-Polanyi-Sato potential energy surface have been used to study the reaction of Ba+HI→BaI+H system. The rotational, vibrational, translational, and angular distributions of the product BaI have been calculated. The calculated results are in good agreement with the experimental ones.     

RbIO3·2HI03晶体结构的再修正及其中心对称度

RbIO_3·2HIO_3的晶体结构用重原子法解得并作了修正。晶体属三斜晶系, 晶胞参数a=0.8332 nm, b=0.8232 nm, c=0.8264 nm; α=60.66°,β=85.80°,γ=66.10°。晶胞中含化学式数z=2. 测量密度D_m =4.61g cm~(-3)。实验和分析结果表明, 结构为非中心对称, 即晶体属P1空间群, 但具有高中心对称度, 作为中心对称度的一种量度<|△r|>w=0.009 nm。⒌玫奖镀敌вΦ挠≈ぁＦ胍蜃覴=0.076.每个碘原子同三个最近邻氧原子成共价键, 平均键长约为0.18 nm, 形成一个畸变的10_3~-三角锥; 此外还同三个次近邻氧原子以0.25-0.33 nm的距离结合, 这六个氧原子形成一个畸变的八面体, 碘原予位于其中心。每个铷原子与邻近九个氧原子以0.286-0.351 nm的距离结合, 形成RbO_9多面体。     

Cl_2 2HI=2HCl I_2反应机理的理论研究

分别在MP2/3-21G!!、CCSD(T)/3-21G!!//MP2/3-21G!!和B3LYP/3-21G!!3种水平上,计算研究了气相反应Cl2 2HI=2HCl I2的机理,求得一系列四中心和三中心的过渡态.通过比较六种反应通道的活化能大小,得到了相同的结论:双分子基元反应Cl2 HI"HCl ICl和ICl HI"I2 HCl的最小活化能小于Cl2、HI和ICl的解离能,从理论上证明了反应Cl2 2HI=2HCl I2将优先以分子与分子作用形式分两步完成.用内禀反应坐标(IRC)验证了MP2/3-21G!!方法计算得到的过渡态.     

Amperometric Biosensor for Evaluation of Competitive Cholinesterase Inhibition by the Reactivator HI‐6

Abstract

Amperometric biosensors containing enzymes butyrylcholinesterase or acetylcholinesterase were prepared. The biosensors were employed for studying of cholinesterase reactivator: HI‐6. Competitions between HI‐6 and acetylthiocholine as enzyme substrate were used for determination of IC₅₀ value. Biosensors with butyrylcholinesterase from human serum determined IC₅₀ as (1.00±0.02)×10^?6 M; the biosensor with acetylcholinesterase from human erythrocytes performance provided IC₅₀ (3.31±0.13)×10^?6 M, the one with human recombinant acetylcholinesterase (2.00±0.06)×10^?6 M and finally biosensor with acetylcholinesterase from electric eel (6.17±0.17)×10^?6 M when 5 mM acetylthiocholine as substrate was used. We are encouraged to consider presented biosensors as a very useful for evaluation of newly prepared cholinesterase reactivators.     

RbIO_3·2HI0_3晶体结构的再修正及其中心对称度

RbIO_3·2HIO_3的晶体结构用重原子法解得并作了修正。晶体属三斜晶系,晶胞参数a=8.332,b=8.232,c=8.264;a=60.66°,β=85.80°,γ=66.10°.晶胞中含化学式数x=2.测量密度D_m =4.61g cm~(-3)。实验和分析结果表明,结构为非中心对称,即晶体属P1空间群,但具有高中心对称度,作为中心对称度的一种量度<|△r|>w=0.09.并得到倍频效应的印证。偏离因子R=0.076.每个碘原子同三个最近邻氧原子成共价键,平均键长约为1.8,形成一个畸变的10_3~-三角锥;此外还同三个次近邻氧原子以2.5-3.3的距离结合,这六个氧原子形成一个畸变的八面体,碘原予位于其中心。每个铷原子与邻近九个氧原子以2.86-3.5的距离结合,形成RbO_9多面体。     

F2＋2HI=2HF＋I2反应机理的研究

根据氯离子型层状复合氢氧化物(LDH-Cl)制备过程中溶液浓度变化的监测结果和不同反应进程时产物的EDS、IR、XRD、TEM、TG-DTA表征结果,研究了合成LDH-Cl的共沉淀反应动力学特征及机理.实验结果表明, LDH-Cl的生成符合多核层表面反应动力学模型;反应过程中LDH的晶胞参数c从2.421 nm变为2.399 nm,通道高度h由0.3321 nm减小为0.3228 nm,粒子直径Da由6.40 nm增大为15.16 nm, Dc由7.43 nm增大到10.93 nm,纵横比由0.86增大为1.39; IR和TG-DTA特征变化表明了层板对阴离子作用的强度和层板的结构稳定性随反应进程而提高.     

Cl2+2HI=2HCl+I2反应机理的理论研究

分别在MP2/3-21G**、CCSD(T)/3-21G**//MP2/3-21G**和B3LYP/3-21G**3种水平上, 计算研究了气相反应Cl₂+2HI=2HCl+I₂的机理, 求得一系列四中心和三中心的过渡态. 通过比较六种反应通道的活化能大小, 得到了相同的结论：双分子基元反应Cl₂+HIHCl+ICl和ICl+HII₂+HCl的最小活化能小于Cl₂、HI和ICl的解离能, 从理论上证明了反应Cl₂+2HI=2HCl+I₂将优先以分子与分子作用形式分两步完成. 用内禀反应坐标(IRC)验证了MP2/3-21G**方法计算得到的过渡态.     

Br2+2HI=2HBr＋I2应机理的密度泛函理论

用密度泛函理论(DFT)B3LYP方法，取3-21G**基组研究了气相反应Br2＋2HI=2HBr＋I2的机理，求得一系列四中心和三中心的过渡态.双分子基元反应Br2＋HI→HBr＋IBr和IBr＋HI→I2＋HBr的活化能(81.02和121.08 kJ•mol－1)小于Br2、HI和IBr的解离能(249.21、320.16和232.42 kJ•mol－1)，故从理论上证明了标题反应将优先以分子与分子作用形式分两步完成.同时发现I原子与Br2分子反应生成较稳定的IBr2是一个无能垒过程，IBr2分解为IBr和Br原子的能垒为70.88 kJ•mol－1.     

Quasiclassical trajectory study of the reaction O(3P) + HI → OH + I

Three-dimensional quasiclassical trajectory calculations were carried out for the reaction of oxygen atoms O(³P) with hydrogen iodide molecules (HI and DI) for the temperature range 200–550 K, using a LEPS potential-energy surface. The calculated results include reaction cross sections, rate constants, kinetic isotope effects, the influence of vibrational and rotational excitation of the reactants on the dynamics, and the product energy partitioning and angular distribution. The calculated results are in good agreement with the available experimental results. The dynamics of the O + HI reaction is discussed in view of the associated mass combination H + LH′ (H and H′ are heavy atoms and L is a light atom), and in relation to earlier trajectory results for the reactions O + HCl and O + HBr.     

Dynamic factors in the reactions between the magic cluster Al(13)⁻ and HCl/HI

The icosahedral Al is a "magic" cluster with remarkable stability due to its high symmetry and closed valence shells. Its reactivity has provided a molecular model for understanding oxidation and dissolution processes in bulk metals. By first principles calculations, we demonstrated the importance of dynamic factors in the Al + HX reactions, with HX being either HCl or HI. There was a barrier to the dissociative adsorption of HX on the surface of an Al cluster, which involved charge transfer from Al. Furthermore, the H atom could be bonded to the cluster in multiple ways, similar to the top, bridge and hollow adsorption sites on Al(111) surface. With a large amount of energy (～40 kcal mol(-1)) deposited during the formation of Al(13)HX(-), the H atom could easily migrate among these sites, similar to the diffusion of hydrogen on metal surfaces. These factors were therefore important considerations in the formation and dissociation of Al(13)HX(-), and more generally in reactions involving other metal clusters.     

I+HI′(v)→IH(v′)+I′反应几率振荡行为的量子散射理论研究

本文基于振动绝热性分析,用量子散射理论研究I+HI′(v)→IH(V′)+I′反应几率的振荡行为,其中双原子间相互作用势和振动本征态是Morse振子的严格解.在计算反应几率时采用分布高斯基(Distributed Gaussian Basis Sets;DGBS)展开方法,既保持了反应几率的解析表达式,又有效地简化了计算.计算结果明显地揭示了反应几率在低碰能区域的振荡行为.对反应机理也作了探讨.     

I+HI(υ=0)→IH(υ′=0)+I体系散射共振态的理论研究

在QCISD(T)//MP2水平下,分别采用6-311++G**基组和SDD基组对重-轻-重反应I+HI(υ=0)→IH(υ′     

I+HI(v=0)→IH(v′=0)+I体系散射共振态的理论研究

在 QCISD ( T) / / MP2水平下 ,分别采用 6-3 1 1 ++G* * 基组和 SDD基组对重 -轻 -重反应 I+HI(ν=0 )→ IH(ν′=0 ) +I中的 H和 I的偏分势能面进行了 ab initio计算 ,指认出在 0～ 0 .5 8e V碰撞能范围内所产生的 6个散射共振态为 Feshbach共振 ,并与文献报道的量子散射理论计算与高分辨阈值光分离光谱实验结果进行了比较 .     

八-4-(四氢糠氧基)酞菁铕(HI)的双酞菁衍生物LB膜特性

合成了八-4-(四氢糠氧基)酞菁铕(Ⅲ)(A)、八-4-(正壬氧基)酞菁铽(Ⅲ)(B)、双酞菁铽(C)和八-4-硝基酞菁铽(D),通过元素分析、红外光谱、质谱和紫外-可见光谱加以确认.测定了配合物A的π-A曲线,表明有很好的成膜性,Z型沉积形成的石英LB膜具有很强的荧光响应,随着LB膜厚度增加,荧光强度增加.掺杂邻菲咯啉的混合LB膜荧光强度比纯膜强,但不是邻菲咯啉加入的量越多发光性越强.研究结果表明nA:nphen=1:10时有最好的荧光行为.同时研究了A和LB膜对于NH3,NOx(x=1,2)和Cl2的气敏性.当A和LB膜分别在NH3和NOx(x=1,2)为5×10-5时,未观察到响应.而Cl2气中,在2×10-6的情况下,迅速产生了响应.在低体积分数条件下(2×10-6～8×10-5),电导率随着Cl2体积分数的改变而呈直线变化.     

I＋HI（y=0）→IH（y′=0）＋I体系散射共振态的理论研究

在QCISD(T)//MP2水平下，分别采用6-311 G基组和SDD基组对重-轻-重反应I HI(p=0)→IH(√=0) I中的H和I的偏分势能面进行了abinitio计算.指认出在0～0.58eV碰撞能范围内所产生的6个散射共振态为Feshbach共振，并与文献报道的量子散射理论计算与高分辨阈值光分离光谱实验结果进行了比较.     

Scattering Resonance States and Partial Potential Energy Surface of Reaction I+HI(v=0)→IH(v′=0)+I

The partial potential energy surface of the I HI→IH I reaction involving the translational and vibrational motions has been constructed at the QCISD(T)//MP4SDQ level with the pseudo potential method that is helpful to interpreting the scattering resonance states. The lifetimes of the scattering resonance states in the title reaction obtained from the partial potential energy surface are about 90-120 fs, which agrees with the result of high-resolved threshold photodetachment spectroscopy of anion IHI- measured by Neumark.     

Scattering Resonance States and Partial Potential Energy Surface of Reaction I+HI(v=0)→IH(v′=0) +I

Introduction Scattering resonance states in chemical reactionsattract much interest of both theorists and experimental-ists because the rate of a chemical reaction, state distri-bution and space distribution of the products are con-trolled by those states[1]. Scattering resonance states,also called quasi-bound states, are formed in theprocesses of energy transitions, such as collision andray radiation processes. Those states are very closelyrelated to the structure and spectroscopy of the tran…     

Scattering Resonance States and Partial Potential Energy Surface of Reaction I ＋ HI （ v = 0 ） → IH （ v＇ = 0 ） ＋ I

The partial potential energy surface of the I ＋ HI →IH ＋ I reaction involving the translational and vibrational motions has been constructed at the QCISD（ T ）//MP4SDQ level with the pseudo potential method that is helpful to interpreting the scattering resonance states. The lifetimes of the scattering resonance states in the title reaction obtained from the partial potential energy surface are about 90-120 fs, which agrees with the result of high-resolved threshold photodetachment spectroscopy of anion IHI^- measured by Neumark.