电子自旋极化谱的计算机模拟

简要介绍了电子自旋极化(CIDEP)极化的基本原理．利用时间分辨电子自旋共振测量得到的CIDEP谱线，建立合适的计算模型。并用Quic kBasic语言编写相应的程序，实现了对激光光解自由基CIDEP谱图的计算机模拟．     

自旋相关自由基对电子极化机理的理论计算

利用自由基对自旋哈密顿，考虑自由基对自旋三重态中的态与自旋单重态的相互作用，理论上计算了自旋相关自由基对的能级及其波函数，并从密度矩阵运动计算了动态电子极化跃迁的度。     

不同共轭桥的氮氧双自由基分子NLO性质的DFT研究

采用密度泛函理论(DFT)UB3LYP/6-31G(d,p)方法对不同共轭桥的氮氧双自由基分子4个体系的非线性光学(NLO)系数进行了计算.结果表明:所有体系单重态为稳定的基态,与自旋极化规则一致;4个体系的极化率在单重态时较大,三重态时较小;体系a,b和c在单重态与三重态的二阶超极化率与极化率规律相同,而具有垂直稳定构型的体系d,由于强的反铁磁性耦合体现出三重态时具有较大的二阶超极化率.     

氮氧自由基对苯甲酮三重激发态猝灭反应的TR-EPR研究

利用TR-EPR技术并结合瞬态吸收光谱方法研究了乙二醇(EG)均相溶液中稳态自由基TEMPO对光诱导苯甲酮三重激发态3BP*的猝灭反应,分析了其中的光化学反应中间体,讨论光解自由基的CIDEP机理,测量了TEMPO对3BP*的猝灭速率常数.结果表明,EG均相溶液中BP*与溶剂分子EG之间存在氢原子转移反应,生成苯甲酮中性自由基BPH·和乙二醇羰自由基Egl[-H]·.E+E/A的CIDEP信号说明TM机理是体系CIDEP的主要机理.另外,TEMPO对3BP*也有明显的猝灭作用,猝灭速率常数为1.40×107L.mol-1·s-1.     

自旋三重态超导

超导体中的库珀对通常是由一对自旋相反总自旋为零(自旋单态)的电子组成.然而,在某些特殊情况下,超导体中的库珀对可以是自旋三重态,这类超导体被称之为自旋三重态超导体.自旋三重态超导是非常罕见的量子现象,在已经发现的上万种超导体中,仅有几个超导体可能具有三重态配对.近几年,随着拓扑物态研究的深入,三重态超导体因为可能是拓扑超导的载体而越来越多地引起关注.本文简要地总结了几类可能的自旋三重态超导体的物理性质.     

均相溶液与微复相体系中光解自由基的CIDEP研究

本文总结了利用自己研制的高时间分辨率电子自旋共振波谱仪，在研究均相溶液与微复相体系中光解自由基的化学诱导动态电子极化（ＣＩＤＥＰ）方面所做的主要工作首先介绍了高时间分辨电子自旋共振波谱仪的原理与结构，然后报道对多种敏化剂分子的ＣＩＤＥＰ研究。在乙二醇均相溶液中，苯醌、蒽醌、萘醌等为三重态极化的中性自由基。在表面活性剂ＴＸ－１００胶束体系中，获得了这些分子的负离子极化自由基。研究了含硫酸溶液中极化的     

微复相体系中光解二苯甲酮羰基的CIDEP研究

本文用高时间分辨自旋共振（ＴＲＥＳＲ）波谱仪器．研究了几种微复相体系中光解二苯甲酮（ＢＰ）自由基的化学诱导动态电子自旋极化（ＣＩＤＥＰ），在ＡＥＯ９／异丙醇／Ｃ３Ｈ１８的层状液晶体系中观察到自旋相关自由对极化．二苯甲酮的异丙醇溶液经３０８ｎｍ激光照射...     

非常规超导体的核磁共振研究新进展

核磁共振作为一种重要的谱学研究手段,在非常规超导体的机理研究中发挥了极其重要的作用.近年来随着新型非常规超导材料的发现,对应的核磁共振研究也有了许多新的进展,这些工作对非常规超导电性的机理研究起到了积极的推动作用.本文将就核磁共振技术在奇宇称超导体、铜基高温超导体和笼目结构超导体这三类超导材料中的若干最新研究进展进行一个有针对性的概述和梳理.在奇宇称超导体研究方面,将重点介绍铬基超导家族A₂Cr₃As₃中铁磁量子临界点顺磁侧的超导相图的研究和自旋三重态超导的实验证据,非中心超导体YPtBi中反铁磁自旋涨落及非常规的自旋单态和自旋三重态混合的超导态的发现.在铜氧化物超导体和笼目结构超导体研究方面,将重点介绍YBa₂Cu₃O_y中强磁场诱导的电荷密度波序出现3倍晶胞(λ=3b)公度性的微观实验证据,笼目结构超导体CsV₃Sb₅中电荷密度波序和电子关联随压力的演化.希望本文对后续超导电性的机理研究、材料探索及实际应用能起...     

四苯基铁卟啉双氧加合物的密度泛函理论研究

采用密度泛函理论方法计算了自旋多重度为1、3、5的四苯基铁卟啉双氧加合物(FeTPPO2)的几何构型及电子性质。考察了四苯基铁卟啉对分子氧的活化。研究发现,FeTPPO2能量随自旋多重度升高而降低。五重态FeTPPO2的能量最低,但其铁卟啉对分子氧的活化效果最差。FeTPPO2中Oa—Ob键键长随自旋多重度变化的规律为三重态>单重态>五重态,说明三重态FeTPPO2中分子氧活化最明显。Fe—Oa键键长和Oa—Ob键键长呈负相关关系。电荷布居分析表明,FeTPPO2中分子氧活化程度与分子氧上所带负电荷多少有关,所带负电荷越多,分子氧活化越明显。分析自旋密度得知,三重态FeTPPO2中分子氧为单线态分子氧。三重态和五重态FeTPPO2中,铁离子均向分子氧转移了β电子,有利于铁氧键的形成。     

磁交换作用对铁磁/dx2-y2+idxy混合波超导结隧道谱的影响

考虑到铁磁层中的磁交换作用和界面势垒的散射效应,利用推广的Blonder-Tinkham-Klapwijk散射理论,计算了铁磁/dx2y2 idxy混合波超导结中的准粒子输运系数和自旋极化的隧道谱.研究表明:(1)铁磁/dx2-y2 idxy混合波超导结中自旋极化的隧道谱能较好地解释La2/3Ba1/3MnO3/DyBa2Cu3O7隧道结中观察到的零偏压电导凹陷的实验结果;(2)在△2/△1=1的情况下,磁交换作用和界面势垒散射可压低峰值,且导致隧道谱逐渐演化出四个电导峰;(3)虚的Andreev 反射过程对铁磁/dx2-y2 idxy混合波超导结的隧道谱有显著影响.     

Intraprotein radical transfer during photoactivation of DNA photolyase

Amino-acid radicals play key roles in many enzymatic reactions. Catalysis often involves transfer of a radical character within the protein, as in class I ribonucleotide reductase where radical transfer occurs over 35 A, from a tyrosyl radical to a cysteine. It is currently debated whether this kind of long-range transfer occurs by electron transfer, followed by proton release to create a neutral radical, or by H-atom transfer, that is, simultaneous transfer of electrons and protons. The latter mechanism avoids the energetic cost of charge formation in the low dielectric protein, but it is less robust to structural changes than is electron transfer. Available experimental data do not clearly discriminate between these proposals. We have studied the mechanism of photoactivation (light-induced reduction of the flavin adenine dinucleotide cofactor) of Escherichia coli DNA photolyase using time-resolved absorption spectroscopy. Here we show that the excited flavin adenine dinucleotide radical abstracts an electron from a nearby tryptophan in 30 ps. After subsequent electron transfer along a chain of three tryptophans, the most remote tryptophan (as a cation radical) releases a proton to the solvent in about 300 ns, showing that electron transfer occurs before proton dissociation. A similar process may take place in photolyase-like blue-light receptors.     

<Emphasis Type="Italic">In situ</Emphasis> generation and detection of methyl radical by voltammetry

The chemistry of free radicals is one of the advanced subjects of fundamental sciences such as biomedicine, environment protection, new energy sources and new material. The detection technique of free radicals is an essential tool for studying free radicals. Methyl radical is one of the representatives of alkyl radicals and the studies on it attract more attention. The current approaches to obtaining methyl radical are based on pulse radiolysis of organic substances that contain the methyl gro…     

Chemical compass model of avian magnetoreception

Approximately 50 species, including birds, mammals, reptiles, amphibians, fish, crustaceans and insects, are known to use the Earth's magnetic field for orientation and navigation. Birds in particular have been intensively studied, but the biophysical mechanisms that underlie the avian magnetic compass are still poorly understood. One proposal, based on magnetically sensitive free radical reactions, is gaining support despite the fact that no chemical reaction in vitro has been shown to respond to magnetic fields as weak as the Earth's ( approximately 50 muT) or to be sensitive to the direction of such a field. Here we use spectroscopic observation of a carotenoid-porphyrin-fullerene model system to demonstrate that the lifetime of a photochemically formed radical pair is changed by application of < or =50 microT magnetic fields, and to measure the anisotropic chemical response that is essential for its operation as a chemical compass sensor. These experiments establish the feasibility of chemical magnetoreception and give insight into the structural and dynamic design features required for optimal detection of the direction of the Earth's magnetic field.     

重质有机资源热解过程中的自由基化学

热解是煤炭、油页岩、重油、生物质以及有机废物等重质有机资源生产燃料和化学品过程中的重要步骤，不仅存在于非催化过程，也存在于催化过程。热解工艺有很多种，但其化学反应主体是自由基机理。针对文献在自由基机理这个宽泛概念下缺乏对自由基反应内涵的认识的现状，作者团队自2007年起开展了对煤、油页岩、重油、生物质等热解过程中的自由基行为研究，明确了文献中的一些不确切推论，形成了系统性认识，逐步建立了热解过程中的自由基化学体系。本文将介绍这些研究的主要进展，包括活性自由基与稳定自由基的确定、赋存状态及在热解过程中的作用、稳定自由基与缩聚反应和积炭的关系、催化剂积炭的形态与稳定自由基的关系、自由基诱导热解与反应调控等等。     

氢键链中质子和电子的协同转移

提出氢键链中电荷转移的一种机制。电子被质子子晶格的反孤子缺陷所俘获。钟罩型电子波函数局域在质子子晶格的压缩区。氢键链中的质子和电子以电孤子－反孤子对束缚态的形式协同转移。     

An allylic ketyl radical intermediate in clostridial amino-acid fermentation

The human pathogenic bacterium Clostridium difficile thrives by the fermentation of l-leucine to ammonia, CO(2), 3-methylbutanoate and 4-methylpentanoate under anaerobic conditions. The reductive branch to 4-methylpentanoate proceeds by means of the dehydration of (R)-2-hydroxy-4-methylpentanoyl-CoA to 4-methylpent-2-enoyl-CoA, which is chemically the most demanding step. Ketyl radicals have been proposed to mediate this reaction catalysed by an iron-sulphur-cluster-containing dehydratase, which requires activation by ATP-dependent electron transfer from a second iron-sulphur protein functionally similar to the iron protein of nitrogenase. Here we identify a kinetically competent product-related allylic ketyl radical bound to the enzyme by electron paramagnetic resonance spectroscopy employing isotope-labelled (R)-2-hydroxy-4-methylpentanoyl-CoA species. We also found that the enzyme generated the stabilized pentadienoyl ketyl radical from the substrate analogue 2-hydroxypent-4-enoyl-CoA, supporting the proposed mechanism. Our results imply that also other 2-hydroxyacyl-CoA dehydratases and the related benzoyl-CoA reductases-present in anaerobically living bacteria-employ ketyl radical intermediates. The absence of radical generators such as coenzyme B12, S-adenosylmethionine or oxygen makes these enzymes unprecedented in biochemistry.     

均匀电场中Dirac方程的严格解和真空中正负电子对的产生率

基于在一均匀恒定电场中Dirac方程的严格解,本文导出了真空中正负电子对产生率的一个解析表达式,用抛物圆柱函数表示.此表达式在弱场极限下与熟知的结果一致.     

VSEPR法对分子几何构型的判断

本文重点分析了孤对电子对分子构型的影响,从而确定分子的几何构型;另外还介绍孤对电子对分子键角的影响。