多核芳烃正离子自由基的ENDOR和EPR研究

用EPR和ENDOR方法检测傅氏烷基化反应(Friedel-Crufts reaction)中所生成的多核芳烃正离子自由基:1,4,5,8-四甲基惠、9,10-二氘代-1,4,5,8-四甲基蒽、2,6,9,10-四甲基蒽、2,6-二甲基-9,10-二(对甲苯基)蒽、3,6,11,14-四甲基二苯并(a,c)三亚苯正离子自由基,测定了它们的超精细偶合常数并提出了其生成机理。     

乙烯和乙炔基在Ni(110)表面上吸附结构的研究

采用平面波赝势方法，利用基于从头计算的软件包，对乙烯和乙炔基在Ni(110)表面上吸附的问题进行了计算. 在低覆盖度时，孤立的乙烯分子的吸附能比密集时高，乙烯分子的C-C 轴大致沿衬底的Ni原子链方向(即沿［110］晶向)，C-C轴与衬底Ni(110)表面有12°的倾斜角，乙烯分子的C—C键的键长为 0.147nm. 乙烯分子中接近顶位的C原子与衬底中距离最近的Ni原子为0.199nm. 在高覆盖度时，乙烯分子在Ni(110)表面上形成c(2×4)再构，每个表面二维元胞中有两个乙烯分子，每个乙烯分子的吸附位置与低覆盖度时相似，而C—C键长比低覆盖度时要短. 乙炔基是乙烯在Ni(110)表面上分解的产物. 关于乙炔基的计算结果表明：乙炔基的两个C原子的间距为0.131nm，比乙烯分子中C原子的间距更短. 与乙烯分子相比，乙炔基的吸附位置更靠近顶位. H原子与吸附在顶位上的C原子相连接，C—H键也大致沿衬底的Ni原子链方向，与Ni表面呈45°的倾斜角. 关键词： 乙烯和乙炔基 平面波赝势方法 吸附几何结构     

手性和构型的识别Ⅰ.开链氮氧化物的ESR研究

我们将微波电子自族共振仪的吸收谐振腔为光化学反应器.在其各种流体及温度的范围内讨论其光化学效应.作者所用的模型乃是有机烷基-亚硝酸类在醇类的动力研究,许多不同的双氢氧烷基及烷氧基-烷基与一氧化氮所结合的自由基均由光分解而产生不同的电子自旋共振光谱.最有兴趣的是产生对映结构的双氢氧乙烷基与一氧化氮所结合的异构物自由基,它们的几何形态可用分子振动理论及共价键理论来解析.自标准化学键长及化学键角度,这些烷氧基-烷基与一氧化氛所结合的自由基还存在很强的氢键,这些将会在科学上,如生物化学、生物学及医学上的氧化及还原反应有相当重要的位置.     

新疆肉苁蓉多糖清除活性氧自由基

研究了肉苁蓉多糖体外抗氧化活性。以抗坏血酸为对照,以类Fenton反应产生羟自由基,多巴胺自氧化反应产生超氧阴离子自由基,次氯酸钠与过氧化氢反应产生单线态氧、二苯代苦味肼基自由基为实验模型,采用紫外-可见分光光度法和化学发光分析法,首次测定新疆肉苁蓉多糖对超氧阴离子自由基、羟自由基、DPPH.自由基（二苯代苦味肼基自由基）、单线态氧的清除作用。结果表明：新疆肉苁蓉多糖对上述自由基均有明显清除作用,且清除作用与多糖浓度呈正相关性。     

含二噻吩乙烯的非线性光学开关分子的新设计方案研究

本文提出了一种利用二噻吩乙烯来设计光致二阶非线性光学开关分子的新方案.与传统设计方案不同之处在于,新方案中,二噻吩乙烯主要作为一个得失电子能力可以改变的基团处于化合物的端基上.通过设计一组结构简单的模型化合物,并利用密度泛函理论计算它们的一阶超极化率β,我们实验了新方案的效果.计算结果表明,使用适当的取代基,能使设计的分子的光异构体之间的β比值达到10倍左右,差值超过100×10-30esu,使得这组模型化合物的二阶非线性光学开关能力不逊色于一些遵循传统设计方案的复杂金属有机化合物.     

含二噻吩乙烯的非线性光学开关分子的新设计方案研究

本文提出了一种利用二噻吩乙烯来设计光致二阶非线性光学开关分子的新方案. 与传统设计方案不同之处在于,新方案中,二噻吩乙烯主要作为一个得失电子能力可以改变的基团处于化合物的端基上. 通过设计一组结构简单的模型化合物,并利用密度泛函理论计算它们的一阶超极化率β,我们实验了新方案的效果. 计算结果表明,使用适当的取代基,能使设计的分子的光异构体之间的β比值达到10倍左右,差值超过100×10-30 esu,使得这组模型化合物的二阶非线性光学开关能力不逊色于一些遵循传统设计方案的复杂金属有机化合物.     

N-溴代琥珀酰亚胺光解夺氢反应的ESR研究

本文用自旋捕捉剂亚硝基叔丁烷(MNP)和2,3,5,6-四甲基亚硝基苯与ESR相结合分别研究了N-溴代琥珀酰亚胺(NBS)光解反应产生的自由基,以及NBS与醇、取代芳烃及烷烃进行光解夺氢反应生成的活泼自由基中间体,结果表明:1.在紫外光用下,NBS分子中的N-Br键发生均裂,产生N-中心自由基并为MNP所捕获.2.对于醇及烷烃,NBS光解产生的Br能夺取叔碳原子上的氢,分别形成叔碳自由基HOR和R,并被ND所捕获.3.与烷烃及醇不同的是:Br不仅能夺取烷基取代苯分子中叔碳原子上的氢,而且还能夺取仲碳原子上的氢,分别形成自由基PhCR₂及PhCHR.     

EPR and DFT Study of the Polycyclic Aromatic Radical Cations from Friedel-Crafts Alkylation Reactions

利用电子顺磁共振和电子核双共振技术在间二甲苯与氯代烷烃和对二甲苯与氯代烷烃进行付-克烷基化反应体系中分别检测到二个多核芳烃正离子自由基信号．研究结果表明,所观察到顺磁共振信号分别来自于2,6-二甲基蒽正离子和1,4,5,8-四甲基蒽自由基的贡献．提出了这二个自由基的生成是在付-克烷基化反应中生成的氯代芳基在AlCl3存在下发生Scholl缩合反应生成多核芳烃,后者发生单电子氧化转变为相应的多核芳烃正离子自由基。利用密度泛函理论计算了这两个自由基的超精细偶合常数,与实验值符合相当满意,从理论上支持了对实验超精细谱线的归属．     

外电场作用下乙酸乙烯酯的分子结构和激发态

采用密度泛函B3LYP方法在6-31G(d)基组水平上,计算了乙酸乙烯酯分子在不同外电场(0.000 a.u.~0.030 a.u.)作用下的基态几何结构、电偶极距、电荷分布及分子总能量,然后利用杂化CIS-DFT方法在相同基组下研究了外电场对乙酸乙烯酯分子前8个激发态的激发能、波长和振子强度的影响.结果表明,分子的几何结构、电荷分布与外电场的大小呈现强烈的依赖关系.随着外电场的不断增加,分子的总能量逐渐减小,偶极距逐渐增大,激发能随电场的增加总体上呈减小的趋势,表明在外电场作用下,乙酸乙烯酯分子易于激发,激发态波长随电场的增加总体上呈增大的趋势,且电子跃迁光谱都集中在紫外区.     

HC_(2n)O~+(n=3-6)正离子的红外光解离光谱以及理论计算研究（英文）

本文利用脉冲激光溅射-超声分子束载带离子源在气相中产生了HC_(2n)O~+(n=3～6)正离子.通过对贴附CO的络合物离子的红外光解离光谱实验获得了HC_(2n)O~+正离子在1600～3500 cm~(-1)范围内的红外光谱.通过比较实验光谱和理论模拟光谱确定了HC_(2n)O~+正离子具有端接氢和氧的直线型碳链衍生物结构,基态为三重态,单重态比三重基态能量高10～15 kcal/mol.成键分析表明HC_(2n)O~+中的碳链具有连烯的结构特征.     

Constraints on proton structure from precision atomic-physics measurements

Ground-state hyperfine splittings in hydrogen and muonium are very well measured. Their difference, after correcting for magnetic moment and reduced mass effects, is due solely to proton structure-the large QED contributions for a pointlike nucleus essentially cancel. The rescaled hyperfine difference depends on the Zemach radius, a fundamental measure of the proton, computed as an integral over a product of electric and magnetic proton form factors. The determination of the Zemach radius, (1.019+/-0.016) fm, from atomic physics tightly constrains fits to accelerator measurements of proton form factors. Conversely, we can use muonium data to extract an experimental value for QED corrections to hydrogenic hyperfine data. There is a significant discrepancy between measurement and theory, in the same direction as a corresponding discrepancy in positronium.     

E.P.R. of free radicals in an adamantane matrix

Benzyl radicals and the isoelectronic azabenzyl radicals were prepared in an adamantane matrix and their isotropic E.P.R. spectra observed and analysed. The proton hyperfine splittings were assigned by specific deuteration and by analogy with the benzyl radical. The spin density distribution is strongly affected by non-symmetrical nitrogen substitution, but is only weakly affected by symmetrical substitution. INDO calculations on the radicals predict only small deviations from the benzyl radical spin density distribution for all of the azabenzyl radicals. However, the trends in the experimental values can be rationalized in terms of the electronegativity difference between carbon and nitrogen and its effect on the molecular orbitals of benzyl radical. Furthermore the observed trend in the g values not only lends support to this view of the structure but also allows estimation of the approximate energy of the first nπ* excited states.     

Nitroxide radicals

The proton hyperfine constants have been measured, using N.M.R., for a series of sterically hindered alkyl aryl nitroxides. Computer reconstructions of the electron resonance spectra show that the coupling constants obtained from the pure radical are very similar to those obtained from the electron resonance spectra of dilute solutions. Comparison of methyl and proton splittings in identical positions suggests that the radicals are σ in character although the molecular-orbital calculations are unable to distinguish between σ or π radicals.     

氮氧自由基中的多光子化学反应(Ⅰ)

在不同光源照射下,作者利用乙基亚硝基有机化合物在乙醇溶剂下,产生双光子的化学反应,用电子自旋共振吸收谐振腔为反应器.在不同的流速下,生成3种同分异构自由基.其结构由电子自旋共振光谱确定、微观的氢键跳动频率由不同波形的氮核超精细偶合常数的变化而确定、利用Charm软件计算,确定β-氢超精细偶合常数的意义及其几何形状.     

An INDO study of the hyperfine coupling constants and equilibrium geometries of some tetra-atomic radicals

Equilibrium geometries and isotropic hyperfine coupling constants have been estimated for the series of radicals CH _n F_3-n , CH _n Cl_3-n , CCl _n F_3-n and S₁H _n F_3-n using the INDO method. The theoretical hyperfine splittings agree well with experimental values including the unusually large proton splittings of 34·6 G and 89·9 G recently reported for SiH₂F and SiHF₂.     

Hyperfine interactions as clues to the structure of elementary particles

The history of hyperfine interactions in hadron physics is reviewed. The recent treatment of hyperfine splittings in meson spectroscopy by Frank and O'Donnell is generalized and applied to baryons as well as mesons by the use of techniques developed for treating hyperfine interactions in atomic physics. New relations between meson and baryon mass splittings are obtained following from the assumption that mesons and baryons are made of the same quarks and have the same color hyperfine interactions at the quark level, with corrections due to color factors and differences between baryon and meson wave functions. Work supported by the U.S. Department of Energy, Division of High Energy Physics, Contract W-31-109-ENG-38 and by the Minerva Foundation, Munich, Germany. 1985–86 Argonne Fellow on leave from the Wiezmann Institute of Science, Rehovot, Israel.     

Importance of quantum tunneling in vacancy-hydrogen complexes in diamond

Our ab initio calculations of the hyperfine parameters for negatively charged vacancy-hydrogen and nitrogen-vacancy-hydrogen complexes in diamond compare static defect models and models which account for the quantum tunneling behavior of hydrogen. The static models give rise to hyperfine splittings that are inconsistent with the experimental electron paramagnetic resonance data. In contrast, the hyperfine parameters for the quantum dynamical models are in agreement with the experimental observations. We show that the quantum motion of the proton is crucial to the prediction of symmetry and hyperfine constants for two simple defect centers in diamond. Static a priori methods fail for these systems.     

Liquid-phase EPR, ENDOR, and TRIPLE resonance studies on corrole and isocorrole cation radicals

The “Contracted Porphyrins” corrole and the recently synthesized isocorrole (as octaethyl derivatives) represent novel porphyrinoid macrocycles of biochemical interest. The radical cations of the free-bases of both corrole and its isomer are studied by EPR, ENDOR, and TRIPLE resonance in liquid solution to measure isotropic hyperfine couplings including signs. They yield detailed information of the electronic structure of the radical cations. The experimental findings are compared with results of all-valence-electrons self-consistent field molecular orbital calculations (RHF-INDO/SP). The comparison shows that the free-bases of corrole and isocorrole undergo protonation when oxidized to cation radicals in CH₂Cl₂ solution. Excellent agreement of the measured and calculated spin density distributions is achieved for the protonated dication radicals, which exhibit the C₂ symmetry observed for the hyperfine structure. The analysis of the hyperfine data discriminates against NH tautomerism as the sole source for an effective C₂ symmetry of the macrocycle.     

Extended analysis of the Ar VII spectrum in the vacuum ultraviolet region

The current status of the determination of corrections to the hyperfine splitting of the ground state in hydrogen is considered. Improved calculations are provided taking into account the most recent value for the proton charge radius. Comparing experimental data with predictions for the hyperfine splitting, the Zemach radius of the proton is deduced to be 1.045(16) fm. Employing exponential parametrizations for the electromagnetic form factors we determine the magnetic radius of the proton to be 0.778(29) fm. Both values are compared with the corresponding ones derived from the data obtained in electron-proton scattering experiments and the data extracted from a rescaled difference between the hyperfine splittings in hydrogen and muonium.     

Rubidium and proton ENDOR on ion pairs in solution

The E.S.R. spectrum of the o-dimesitoylbenzene anion-alkali cation radical shows unusually large isotropic alkali hyperfine splitting constants. We report a solution ENDOR study of this radical in which both alkali (^85,87Rb) and proton ENDOR spectra were recorded. Both the alkali and proton intensities showed a strong dependence on the metal ion nuclear spin quantum number of the E.S.R. line being saturated. This dependence is attributed to strong flip-flop cross-relaxation induced by modulation of the isotropic alkali hyperfine splitting. The powder E.S.R. spectrum of the complex reveals a small anisotropy of the Rb hyperfine splitting tensor. This indicates a small metal non-s-contribution to the half-filled molecular orbital, which is consistent with the observed relaxation behaviour and the small g shift. The intensity variations in the alkali and proton ENDOR spectra were used to determine the relative signs of all hyperfine splitting constants, and the absolute signs of the hyperfine splitting constants are deduced from a model of the structure of the complex.