反式-1,4,5,8-四硝基-1,4,5,8-四氮杂萘烷异构体热解机理与稳定性的理论研究

运用密度泛函理论和半经验分子轨道方法,对一系列高能杂环硝胺—反式-1,4,5,8-四硝基-1,4,5,8-四氮杂萘烷异构体的热解机理和稳定性进行了系统地计算研究。在B3LYP/6-31G**和PM3水平上,分别计算了标题物的化学键离解能(BDE)和热解反应活化能(Ea),并根据BDE和Ea数值考察了硝胺取代基对化合物稳定性和热解机理的影响;同时,还详细考察了BDE与Ea、化学键重叠布居数、前线轨道能级以及能隙之间的相关性。结果表明,由BDE、Ea和静态电子结构参数推断的标题物热稳定性和热解机理的结论基本是一致的,N-NO2键均裂是标题物的热解引发步骤,间位取代异构体较对位取代异构体稳定,而邻位取代的异构体稳定性最差。     

Isolating Reactions at the Picoliter Scale: Parallel Control of Reaction Kinetics at the Liquid–Liquid Interface

Miniaturized liquid–liquid interfacial reactors offer enhanced surface area and rapid confinement of compounds of opposite solubility, yet they are unable to provide in situ reaction monitoring at a molecular level at the interface. A picoreactor operative at the liquid–liquid interface is described, comprising plasmonic colloidosomes containing Ag octahedra strategically assembled at the water‐in‐decane emulsion interface. The plasmonic colloidosomes isolate ultrasmall amounts of solutions (<200 pL), allowing parallel monitoring of multiple reactions simultaneously. Using the surface‐enhanced Raman spectroscopy (SERS) technique, in situ monitoring of the interfacial protonation of dimethyl yellow (p‐dimethylaminoazobenzene (DY)) is performed, revealing an apparent rate constant of 0.09 min^?1 for the first‐order reaction. The presence of isomeric products with similar physical properties is resolved, which would otherwise be indiscernible by other analytical methods.     

苯甲酰基硫代苯甲酸-S-苯酯的双重磷光研究

在对不同取代的苯甲酰基硫代苯甲酸-S-苯酯的光物理性质进行研究时,发现其苯甲酰基在邻位时可观测到双磷光现象,本工作对这种现象的机理进行了研究,确定这种现象是由于溶剂的作用,使溶液中具有多种不同的构象体,不同异构体的磷光发射不同,其激发波长也不同,改变激发波长可观察到双重磷光现象。     

HPO3异构体结构与稳定性

使用密度泛函方法(B3LYP)和6-311 G(3df,3pd)基组计算得到了HPO3体系的9个异构体与11个过渡态,并用内禀反应坐标理论验证了异构体的异构化过程．结果表明,在HPO3体系中,只有热力学最稳定的平面型异构体HOFO2(E1),(cis,cis)构象的HOOPO(E3)和立体的具有Cs对称性的异构体HP(O)O2(E7)具有较高的动力学稳定性,理论预测结果与实验一致．另外2个立体的HOFO2连接方式的异构体(E2和E4)由于解离为HO(Ⅱ) OPO(^2A1)的解离能较低,因此不能稳定存在。     

Synthesis and characterization of ordered polyurethanes from nonsymmetric diisocyanate and ethylene glycol

An ordered polyurethane with a head‐to‐head (H‐H) or tail‐to‐tail (T‐T) content over 95% was prepared by polyaddition reaction of a nonsymmetric monomer, p‐isocyanatobenzyl isocyanate (1) with a symmetric monomer, ethylene glycol (2). The model reactions were studied in detail to demonstrate the feasibility of polymer formation. The polymerization was conducted in THF in the presence of triethylamine (TEA) at 0 °C by slow addition of a half amount of 2 to 1, followed by removing THF and then adding the rest of 2 in DMF at once at 30 °C in the presence of dibutyltin dilaurate (DBTL). The microstructure of the polymer obtained was investigated by ¹³C NMR spectroscopy, and it was found that the polymer had the expected structural regularity. The constitutional regularity of polymers influenced their thermal properties. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2106–2114, 2000     

S2O2分子稳定结构的密度泛函理论研究

采用密度泛函理论中的B3LYP方法,在6-311+G(3df)和Aug-cc-pVTZ水平上,研究了单态S2O2分子的各种可能的异构体及其相对稳定性。结果表明,具有C2v对称性的三角平面分叉异构体的热力学稳定性要高于目前实验上唯一被发现的具有C2v对称性的cis-OSSO异构体,同时trans-OSSO的稳定性与顺式异构体十分接近,这2种异构体应该可以在实验上被观察到。同时本文还讨论了3个最稳定构型的前线分子轨道和链型OSSO的内扭转势能。     

Improving Our Knowledge on the 229mThorium Isomer: Toward a Test Bench for Time Variations of Fundamental Constants

For more than four decades, the lowest excitation in the whole landscape of atomic nuclei, the low‐lying, isomeric state of ²²⁹Th, the so‐called thorium isomer, has challenged physicists of various disciplines. Being a solitaire with its uniquely low excitation energy of <10 eV, its predicted lifetime of a few hours results in an extremely sharp relative linewidth ΔE/E as low as 10^–20. While until recently the indication of its existence was based only on indirect evidence, its unique properties inspired a multitude of potential applications, like the use of the thorium isomer as a nuclear frequency standard, potentially able to outperform even the best atomic clocks and a sensitivity‐enhanced access to potential temporal variations of fundamental constants. The various proposals to exploit the unique properties of ^229mTh are presented herein, in particular focusing on its ability to serve as a test bench for time variations of fundamental constants like the fine structure constant.     

关于93Mo中21/2+晕阱的来源(英文)

本研究通过壳模型计算研究了N=51的同中子素91Zr、93Mo和95Ru中高自旋晕态21/2+的同核异能态现象。计算发现,低角动量的p_1/2轨道上的质子是仅在93Mo中存在21/2+晕阱的主要原因。同时,本工作还研究了N=52的同中子素92Zr、94Mo和96Ru中10₁+-12₁+能级结构的系统性,发现94Mo中的10₁+-12₁+能级间隙相对最小,考虑到与93Mo的17/2₁+-21/2₁+能级相似的组态,这一结果为93Mo中出现21/2+晕阱提供了补充性的论证。Isomerism of the high-spin yrast 21/2+ states of the N=51 isotones 91Zr, 93Mo and 95Ru has been investigated using the shell model calculations. It is found that the low-j πp_1/2 is responsible for the only yrast trap in 93Mo. In addition, the relatively smaller 10₁+-12₁+ level spacing in 94Mo has been found by investigating the systematics of the 10₁+-12₁+ level structures in the N=52 isotones 92Zr, 94Mo and 96Ru. This result provides a supplementary argument to the origin of the 21/2+ yrast trap in 93Mo from the viewpoint of the similarity between the configurations of 10₁+-12₁+ states in 94Mo and those of 17/2₁+-21/2₁+ states in 93Mo.     

环状氮氢化合物NnHn(n=3~5)的构象研究

应用密度泛函理论对10种环状氮氢化合物异构体进行了研究.利用自然键轨道理论(NBO)和分子中的原子理论(AIM)分析了这些异构体的成键特征、相对稳定性.N-N键长与键临界点的电荷密度存在反比关系.超共轭作用和立体排斥作用计算表明:立体排斥作用和超共轭作用在决定构象稳定性的方面均起了主要的作用.H原子的相对位置的差异影响了键-键立体排斥能的类型.     

Theoretical XANES spectra for C76 isomers

Two isolated pentagon rule satisfying isomers of C76 are optimized. And 1（D2） isomer is reconfirmed to be the relative more stable one. The X-ray absorption near-edge structure （XANES） spectra are theoretically characterized by the hybrid density functional theory （DFT） method in combination with the full core-hole potentials. Isomer identification of XANES spectra for Cr6 is found and XANES spectra dependence on local structure of fullerene is discussed.