双环戊二烯-氯醌体系的CIDNP研究

利用Nd/YAG激光器的三倍频激光脉冲(355nm),对双环戊二烯的光敏化反应进行了CIDNP方面的研究,结合CIDNP理论模拟谱的计算,证实了Roth等人所推测的此光敏化反应自由基中间体结构为双重的烯丙基物种,通过计算,确定了自由基各质子的超精细偶合常数hfc的相对大小和绝对符号以及各碳原子上的未偶电子自旋密度,从而对这个特殊的自由基中间体结构有了更清晰的认识.     

CIDNP及其在光化学中的应用

化学诱导动态核极化(Chemically Induced Dynamic Nuclear Polarization,简称CIDNP)是一种在化学反应体系中观察到的NMR谱线强度反常的现象(常称之为极化谱,包括增强吸收和发射等)。1967年由Bargon和Fischer^[1] (西德)以及Ward和Lawler^[2] (美国)首先发现的。由于他们所研究的反应体系中涉及自由基,因此最初认为这种谱线强度反常现象是由于自由基中间体中的电子-核交叉弛豫引起的。这种机理通常称为:Overhauser型的动态核极化(Dynamic Nnclear Polarization简称DNP)。但很快就发现它不足以解释实验得到的结果,而CIDNP的命名却是这样因袭下来了。     

双自由基CH燃烧反应机理的研究

应用量子理论从头算和密度泛函理论(DFT)对双自由基CH(X2Π)与O2(X3∑g-)的反应机理进行了研究.在B3PW91/6-311G**水平上优化了反应通道上各驻点(反应物、中间体、过渡态和产物)的几何构型,并计算了零点能和过渡态的虚频率.并由B3PW91/6-311G**给出了各物种的总能量.计算表明,反应物中自由基CH与O2反应主要在二重态势能面上进行,CH中的C原子可以插在O2分子中两个氧原子中间形成中间体1(2HCO2),中间体1(2HCO2)可以经过不同的反应通道形成不同的产物P1(1CO2 2H)和P2(1CO 2OH),各反应通道的反应热的计算与实验值吻合较好.     

丙烯腈单体自由基反应及光谱分析的研究

采用密度泛函理论对以偶氮二异丁腈为引发剂形成的丙烯腈单体自由基(CH₃)₂(CN)C—CH₂—(CN)CH的终止方式反应机理进行研究。先用B3LYP/6-31G(d)基组对反应物、偶合中间体、过渡态、歧化产物的几何构型进行优化,并计算了各物种经过零点能校正后的总能量,红外频率和电子结构,同时对过渡态结构进行了验证。研究结果表明,反应物先通过自由基的偶合终止方式形成偶合中间体a,再由此经过氢迁移、裂解等机理得到歧化终止产物P[p₁(CH₃)₂(CN)CCHCHCN+p₂(CH₃)₂(CN)C—CH₂—CH₂CN]。双自由基发生偶合和歧化终止反应分别形成偶合中间体a和歧化终止产物P均为放热反应,且偶合产物有着更低的能量。反应过程的速控步骤a→TS→P在常温下的速率常数表示为k(298.15 K)=2.71×10-59。歧化终止反应随着反应温度的升高易于进行,歧化产物所占的比例也增加。通过对反应过程各物种红外谱图的分析,说明自由基在整个终止反应的化学变化,同时分析了HOMO-LUMO电子密度分布的信息,验证丙烯腈双自由基偶合终止方式和各物种结构的准确性。     

FC(O)O2的结构及其自由基与NO反应的微观机理研究

用密度泛函理论(DFT)和哈特里-福克(HF)从头计算方法和半经验势方法等研究了FC(O)O₂ 的结构和振动性质.在DFT中采用B3LYP方法,在6-311G(d)基组上对FC(O)O₂自由基与NO反应的微观过程进行了分析.首先给出了各反应物、中间体、过渡态和生成物的几何构型,然后计算了它们的能量和频率,通过频谱分析得到反应的中间体和过渡态信息,即FC(O)O₂与NO反应为多反应通道,势垒高度和反应速度给出主要通道是FC(O)O₂     

安息香及其衍生物光反应的CIDNP研究

本文用光照的¹H化学诱导动态核极化技术,研究了安息香及其衍生物的光化反应。并通过不同浓度的自由基捕获剂(PBN)的加入,对所研究体系的CIDNP效应的影响,分析推断了安息香等的光解及其光解自由基的复合的反应机理。并讨论了双取代安息香醚的光反应机理随取代基的变化而有所不同。     

C2（a 3Πu）+NO 的反应机理研究

在G2 (CC ,MP2 )理论水平上研究了C2 (a3 Πu)自由基与NO分子的反应 .计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量 ,揭示了此反应存在两种反应机理 :由NO中的O原子进攻C2 自由基形成CCON中间体的CCON机理和NO中的N进攻C2 自由基形成CCNO中间体的CCNO机理 ,分析了对应与这两种反应机理的五个可能的反应通道 ,得出了由NO中的N原子进攻3 C2 自由基 ,生成中间体CCNO自由基 ,最终得到产物CN +CO的通道是最有利的通道 .     

C2（a^3Пu）＋NO的反应机理研究

在G2(CC，MP2)理论水平上研究了C2(a^3Пu)自由基与NO分子的反应．计算了反应体系最低二重态势能面上各驻点的构型参数、振动频率和能量，揭示了此反应存在两种反应机理：由NO中的O原子进攻C2自由基形成CCON中间体的CCON机理和NO中的N进攻C2自由基形成CCNO中间体的CCNO机理，分析了对应与这两种反应机理的五个可能的反应通道，得出了由NO中的N原子进攻^3C2自由基，生成中间体CCNO自由基，最终得到产物CN+CO的通道是最有利的通道．     

激光引发自由基反应磁效应的光谱学研究

“动态自旋化学”(dynamic spin chemistry)作为一门新兴的交叉研究领域,其重要性已得到广泛的共识。涉及的研究内容包括： 化学反应的磁效应(MFE)、同位素效应(MIE)、化学诱导动态核极化(CIDNP)和化学诱导动态电子极化(CIDEP)。文章简要介绍了激光引发自由基反应的磁效应发展历史及其光谱学研究方法。分析并总结了自由基反应磁效应产生的原因、单-三转换理论及磁效应机理。同时,也为国内同行介绍了自由基反应磁效应研究新的发展动态。     

NH自由基与臭氧反应机理的理论研究

用量子化学从头计算方法,在HF／6－31＋＋G**水平研究了臭氧与NH三线态活性自由基反应的微观机理,优化得到反应物、过渡态、中间体和产物的几何构型。用MP2／6－31＋＋G**／／HF6－31＋＋G**方法计算能量,同时进行零点能校正。研究结果表明： NH三线态活性自由基与O3反应首先成稳定中间体NHO3,然后中裂解生成HNO和O2。     

1-乙酰基-2,3-吲哚二酮的光诱导氢转移反应的CIDNP研究

采用CIDNP方法对UV光照条件下的1-乙酰基-2, 3-吲哚二酮与几类氢给体的光诱导氢转移反应进行了研究.     

Photo-electrochemical properties of multi-layered thin films composed of chalcogenide and superionic conductor glasses

Multi-layered thin films, which consisted of metallic silver, GeSe₃ glass, and silver oxyhalide superionic conductor glass were prepared. Photo- and electrochemical reaction of metallic silver with the chalcogenide glass layer was studied by optical absorbance and cyclic-voltammetry. Photo-doping of silver through the superionic glass layer was observed using evaporated AgI---Ag₂MoO₄ film and it was partly undoped by electrochemical treatment. However, no photo-doping was observed for the cell consisting of a AgI---AgPO₃ dip-coated layer. The doped silver was dissolved into the GeSe₃ layer during the photo-doping process. However, it formed another intermediate compound layer (probably silver selenide) during the electrodoping process.     

Determination of Ce/Ce in electron-beam-damaged CeO2 by electron energy-loss spectroscopy

We followed the reduction of Ce⁴⁺ in CeO₂ by observing changes in the shape of the Ce M_4,5 edge by parallel electron energy-loss spectroscopy with a transmission electron microscope. The energy-loss near-edge structure of the beam-damaged CeO₂ exhibits Ce M_4,5 and O K-edge shapes that are consistent with reduction to a Ce³⁺ oxide. During the damage process the spectrum of CeO₂ changes as follows: (a) decreases in energies of the M₅ and M₄ maxima; (b) changes in shape of the near-edge structure; (c) inversion of the M₅ to M₄ branching ratio; and (d) increase in the M₅ to M₄ area ratio. We simulated M_4,5 edges of damaged CeO₂ with a linear combination of Ce⁴⁺ and Ce³⁺ spectra and observed no intermediate oxidation states.     

A quantum chemical study of ZrO2 atomic layer deposition growth reactions on the SiO2 surface

Zirconium oxide (ZrO₂) is one of the leading candidates to replace silicon oxide (SiO₂) as the gate dielectric for future generation metal-oxide-semiconductor (MOS) based nanoelectronic devices. Experimental studies have shown that a 1–3 monolayer SiO₂ film between the high permittivity metal oxide and the substrate silicon is needed to minimize electrical degradation. This study uses density functional theory (DFT) to investigate the initial growth reactions of ZrO₂ on hydroxylated SiO₂ by atomic layer deposition (ALD). The reactants investigated in this study are zirconium tetrachloride (ZrCl₄) and water (H₂O). Exchange reaction mechanisms for the two reaction half-cycles were investigated. For the first half-reaction, reaction of gaseous ZrCl₄ with the hydroxylated SiO₂ surface was studied. Upon adsorption, ZrCl₄ forms a stable intermediate complex with the surface SiO₂–OH^* site, followed by formation of SiO₂–O–Zr–Cl^* surface sites and HCl. For the second half-reaction, reaction of H₂O on SiO₂–O–Zr–Cl^* surface sites was investigated. The reaction pathway is analogous to that of the first half-reaction; water first forms a stable intermediate complex followed by evolution of HCl through combination of a Cl atom from the surface site and an H atom from H₂O. The results reveal that the stable intermediate complexes formed in both half-reactions can lead to a slow film growth rate unless process parameters are adjusted to lower the stability of the complex. The energetics of the two half-reactions are similar to those of ZrO₂ ALD on ZrO₂ and as well as the energetics of ZrO₂ ALD on hydroxylated silicon. The energetics of the growth reactions with two surface hydroxyl sites are also described.     

新型燃煤发电-CO2捕获-供热一体化系统

本文在深入分析燃煤电站CO₂捕获和汽水系统热平衡的基础上,提出一种新型燃煤发电-CO₂捕获-供热一体化系统。该系统通过汽水流程、碳捕获流程及地暖供热流程的有效集成,实现了系统中、低温余热的高效利用,降低了碳捕获对电厂效率的影响。分析结果显示,本文提出的一体化系统,在CO₂回收率90%时,供电效率可达31.32%,供电效率降低8.96%,而传统化学吸收法碳捕获电站效率惩罚普遍在10～12个百分点或更高。同时,该系统可供热350 MW,全厂（火用）效率达34.49%,全厂热效率高达55.88%;该系统以较少的能耗代价实现高效供电、供热与CO₂减排,为燃煤发电机组碳减排提供了独特的学术思路与技术方案。     

Observation of hydrogen induced intermediate borides in PrFeB based alloys by Mössbauer effect spectroscopy

In the present work, a quantitative analysis of the phase compositions by Mössbauer effect spectroscopy of solid and conventional hydrogen disproportionated Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys was carried out. Significant amounts of intermediate borides t-Fe₃B and Pr(Fe, Co)₁₂B₆ were detected after solid hydrogen disproportionation treatment in Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys, respectively. After conventional hydrogenation–disproportionation–desorption–recombination treatment these phases were not detected and in no case residual Pr₂Fe₁₄B-phase was found. It was observed that the amount of intermediate borides after disproportionation can be correlated with the degree of texture after recombination at various temperatures.     

kiow.to Search for 'p1 State of CC at BEPC-The Electromagnetic Transition Ψ' -+Ψ('p1) + 2Y1

Decay rate of the process Ψ'→Ψ(¹P₁)+2γ is calculated with all possible intermediate states included in the context of potential model. Out calculation shows that the branching ratio for this channel is about 10^-5.For a total production of 2×10Ψ' particles, it is possible to find out Ψ' (¹P₁) at BEPC through searching for 3γ signals.     

Substrate-induced freezing of alkane monolayers adsorbed on Au(1 1 1) dependant on the alkane/gold misfit

The molecular structure of the interfaces between pure C_nH_2n+2 (n=10, 12, 14, 16) and Au(1 1 1) surface has been studied by scanning tunneling microscopy. At 291 K, self-organized monolayers with a lamella structure are formed with these alkanes. The ordered monolayers are melting at temperature higher by 46, 28, 15, 5 K than the melting point of bulk C_nH_2n+2 crystals with n=10, 12, 14, 16, respectively. Two kinds of melting process were observed: (i) a direct solid/liquid phase transition within the monolayer for C₁₀H₂₂, C₁₂H₂₆ and C₁₄H₃₀ molecules, (ii) an intermediate phase for C₁₆H₃₄ molecules. This mesophase corresponds to a two-dimensional liquid crystal formed by molecules moving along their axis and along Au1 1 0. These results agree well with calculations using a geometric model taking in account the misfit between the CH₂–CH₂–CH₂ period along alkyl chain and the gold lattice along 1 1 0 direction.     

Pseudo-copper Ni–Zn alloy catalysts for carbon dioxide reduction to C2 products

Electrocatalytic CO₂ reduction reaction (CO2RR) to obtain C₂ products has drawn widespread attentions. Copper-based materials are the most reported catalysts for CO₂ reduction to C₂ products. Design of high-efficiency pseudo-copper catalysts according to the key characteristics of copper (Cu) is an important strategy to understand the reaction mechanism of C₂ products. In this work, density function theory (DFT) calculations are used to predict nickel–zinc (NiZn) alloy catalysts with the criteria similar structure and intermediate adsorption property to Cu catalyst. The calculated tops of 3d states of NiZn3(001) catalysts are the same as Cu(100), which is the key parameter affecting the adsorption of intermediate products. As a result, NiZn3(001) exhibits similar adsorption properties with Cu(100) on the crucial intermediates *CO₂, *CO and *H. Moreover, we further studied CO formation, CO hydrogenation and C–C coupling process on Ni–Zn alloys. The free energy profile of C₂ products formation shows that the energy barrier of C₂ products formation on NiZn3(001) is even lower than Cu(100). These results indicate that NiZn3 alloy as pseudo-copper catalyst can exhibit a higher catalytic activity and selectivity of C₂ products during CO₂RR. This work proposes a feasible pseudo-copper catalyst and provides guidance to design high-efficiency catalysts for CO₂RR to C₂ or multi-carbon products.