胸腺嘧啶低能量VUV光解离路径的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算研究了胸腺嘧啶的光解离反应路径, 通过改变光子能量得到不同的质谱信号, 光子能量在12.0 eV时主要的碎片有m/z=98 (C₄H₆N₂₄O⁺)、97 (C₄H₅N₂O⁺)、84 (C₃H₄N₂O⁺或C<     

草酸铕颗粒微米层状颗粒的合成及其光学性能

在室温条件下, 以柠檬酸钠为辅助剂, 通过简单沉淀法合成了草酸铕Eu₂(C₂O₄)₃·10H₂O微米层状颗粒. 应用X射线衍射、X射线电子能谱、场发射扫描电子显微镜、光致发光光谱对Eu₂(C₂O₄)₃·10H₂O结构与性能进行了表征. 讨论了草酸铕微米层状颗粒可能的形成机理.     

异亮氨酸的真空紫外光电离和光离解

利用同步辐射光电离质谱结合理论计算, 研究了异亮氨酸的真空紫外光诱导电离解离．在光子能量为13 eV的质谱中探测到了m/z=86、75、74、69、57、46、45、44、41、30、28、18的碎片离子．对于异亮氨酸的主要碎片离子为：C₅H₁₂N⁺ (m/z=86)、C₂H₅NO₄⁺ (m/z=75)、C₅H₉⁺ (m/z=69)、C₄H₉⁺(m/z=57)和CH₄N⁺(m/z=30)．由光电离效率曲线得到出现势分别为：8.84±0.07、9.25±0.06、10.20±0.12、9.25±0.10、11.05±0.07 eV．结合量化理论计算(B3LYP/6-31++G(d,p)),详细给出了它们可能的生成路径．这些解离通道包括简单的键断裂反应和涉及中间体、过渡态的反应,实验值和理论计算的离子出现能或势垒一致．     

苯和苯胺在深紫外光照射下的电离和解离

本文利用自主研制的反射式飞行时间质谱仪结合177.3 nm深紫外激光研究了苯和苯胺分子的光电离与光解离过程. 质谱实验发现苯在177.3 nm皮秒激光作用下发生高效电离并观测到不对称C-C键解离形成的以C₄H₃⁺为主的较小碎片峰. 相比之下，苯胺的深紫外光电离中主要产生一个C₅H₆^+·离子自由基和一个较小丰度的C₆H₆^+·碎片，分别对应于CNH分子和NH自由基的去除. 结合第一性原理计算，诠释了苯和苯胺这两个仅有一个氨基差异的分子光解离路径，揭示苯和苯胺分子中氢原子转移对于C-C或C-N键断裂的关键重要作用.     

甲基环己烷在9∽15.5 eV能量区的真空紫外光电离研究

利用具有同步辐射源的反射式飞行时间质谱仪，研究甲基环己烷的真空紫外光电离和光解离. 观测到母体离子C₇H₁₄⁺和碎片离子C₇H₁₃⁺，C₆H₁₁⁺，C₆H₁₀⁺，C₅H₁₀⁺，C₅H₉⁺，C₄H₈⁺，C₄H₇⁺和C₃H₅⁺的光电离效率曲线. 测定甲基环己烷的电离能为9.80±0.03 eV，通过光电离效率曲线确定其碎片离子的出现势. 在B3LYP/6-31G(d)水平上对过渡态、中间体和产物离子的优化结构进行表征，并使用G3B3方法计算其能量. 提出主要碎片离子的形成通道. 分子内氢迁移和碳开环是甲基环己烷裂解途径中最重要的过程.     

环戊酮光电离解离的实验和理论研究

本文介绍了真空紫外光电离质谱结合理论计算研究环戊酮单分子的光电离解离过程. 在9.0∽15.5 eV能量范围内,测量了环戊酮离子及其碎片离子的光电离效率曲线. 通过光电离效率曲线,将环戊酮分子的电离能确定为9.23±0.03 eV,并确认碎片离子为：C₅H₇O⁺,C₄H₅O⁺,C₄H₈⁺,C₃H₃O⁺,C₄H₆⁺,C₂H₄O⁺,C₃H₆⁺,C₃H₅⁺,C₃H₄⁺,C₃H₃⁺,C₂H₅⁺, C₂H₄⁺. 利用量子化学计算方法,在ωB97X-D/6-31+G(d,p)理论水平基础上,提出了C₅H₈O⁺的解离机制. 通过对环戊酮解离路径的分析,发现开环和氢迁移过程为环戊酮离子解离的主要路径.     

酪胺和多巴胺VUV光电离/解离的实验和理论研究

利用同步辐射真空紫外光电离质谱和理论计算对中性酪胺和多巴胺分子的光诱导解离过程进行研究．在较低光子能量下,通过近阈光电离仅得到母体离子信号．当增加光子能量到11.7 eV甚至更高时,从酪胺和多巴胺分别得到四个清晰可辨的碎片离子信号．另外通过测量母体离子的光电离效率曲线,酪胺和多巴胺分子的电离能分别为7.98和7.67 eV(实验误差为±0.05 eV)．结合理论计算建立这两个分子的详细碎裂路径,包括相似的胺乙基消除路径．其中碎片C₇H₈O₂^+·(m/z=124)和C₇H₈O^+·(m/z=108)的生成认为来自McLafferty重排,该过程经历分子内的γ氢迁移诱导的β开裂反应． 另外,C7-C8键直接开裂可以生成CH₂NH₂⁺(m/z=30)碎片离子,并且该过程和McLafferty重排为主要的裂解路径.     

PHOTO ACOUSTIC MEASUREMENTS OF WATER VAPOR ABSORPTION COEFFICIENT IN UV SPECTRAL REGION

Data on the absorption coefficient of H₂O in binary mixture with N₂ in UV region of spectra are presented. With the use of the high sensitivity photoacoustic spectrometer, the following values of the absorption coefficient were found: 2.3×10^-9cm^-1·Pa^-1(λ=255 nm), 0.9×10^-9 cm^-1·Pa^-1(λ=271 nm), and 1.6×10^-9cm^-1 ·Pa^-1(λ=289 nm).     

分子团簇表面吸附敏化ZnO纳米线的第一性原理研究

ZnO纳米线作为新型太阳能电池结构的重要组成部件之一, 其导电能力直接影响到太阳能电池的性能. 采用密度泛函理论平面波超软赝势方法, 计算并分析了C₂H₆O(乙醇)、 C₆H₅FS(4-氟苯硫酚)、 C₇HF₇S(4-(三氟甲基L)-2, 3, 5, 6-四氟硫代苯酚) 等小分子吸附的六边形结构\langle0001angle ZNWs (ZnO 纳米线) 的几何结构、 吸附能和电子结构. 首先, 通过几何优化得到了不同基团吸附的ZNWs的稳定结构, 同时吸附能计算结果表明C₇HF₇S吸附的体系结构最为稳定, 且吸附呈现放热反应; 其次, 为研究表面敏化对导电性能的影响, 计算了不同小分子基团吸附下的能带结构和态密度, 并利用能带理论分析了表面吸附敏化对禁带宽度的调控机理, 结果分析表明小分子表面吸附敏化对ZNWs的电学性能有一定的影响, 其中C₇H₇FS和C₆H₅FS分子均发生了不同程度的电荷转移.     

异补骨脂素热解实验和理论研究

利用同步辐射真空紫外光电离质谱技术,在不同光子能量下,研究了异补骨脂素(C₁₁H₆O₃)的低压热解,探测了不同温度下异补骨脂素的热解产物及其与前驱体的比例. 实验结果表明,异补骨脂素的主要热解产物是CO及其依次消去CO的产物(C₁₀H₆O₂和C₉H₆O). 利用密度泛函理论计算异补骨脂素的解离途径,并利用过渡态理论计算了竞争通道的反应速率常数. 通过实验和理论的结合,确定了异补骨脂素主要解离路径和相应产物的分子结构.     

Raman spectroscopic study of the arsenite mineral vajdakite [(Mo6+O2)2(H2O)2As3+2O5]·H2O

Raman spectra of vajdakite, [(Mo⁶⁺O₂)₂(H₂O)₂As O₅]·H₂O, were studied and interpreted in terms of the structure of the mineral. The Raman spectra were compared with the published infrared spectrum of vajdakite. The presence of dimolybdenyl and diarsenite units and of hydrogen bonded water molecules was inferred from the Raman spectra which supported the known and published crystal structure of vajdakite. Mo O and O H···O bond lengths were calculated from the Raman spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Weakly interacting molecular clusters of CO with H2O,SO2, and NO+

Intermolecular interactions in three dimers, CO···H₂O, CO···SO₂, and CO···NO⁺, were studied at the CCSD(T) level of theory, using a series of the augmented correlation consistent polarised basis sets. Interaction energy and its components as well as vibrational spectra for local minima were computed using both harmonic and anharmonic approximations. While CO···H₂O and CO···SO₂ are weakly bound with the binding energies ?7.4 and ?6.4 kJ/mol, CO···NO⁺ is much more stable with the binding energy of ?32.8 kJ/mol corresponding to ΔG = ?4.7 kJ/mol at 254 K.     

The Studies of Enhanced Fluorescence in the Two Novel Ternary Rare-Earth Complex Systems

Two novel ternary rare-earth complexes SmL₅·L^’·(ClO₄)₂·7H₂O and EuL₅·L^’·(ClO₄)₂·6H₂O (the first ligand L = C₆H₅COCH₂SOCH₂COC₆H₅, the second ligand L^’ = C₆H₄OHCOO⁻) were synthesized and characterized by element analysis, molar conductivity, coordination titration analysis, IR, TG-DSC, ¹HNMR and UV spectra. The detailed luminescence studies on the rare-earth complexes showed that the ternary rare-earth complexes presented stronger fluorescence intensities, longer lifetimes, and higher fluorescence quantum efficiencies than the binary rare-earth materials. After the introduction of the second ligand salicylic acid group, the relative emission intensities and fluorescence lifetimes of the ternary complexes LnL₅·L^’·(ClO₄)₂·nH₂O (Ln = Sm, Eu; n = 7, 6) enhanced more obviously than the binary complexes LnL₅·(ClO₄)₃·2H₂O. This indicated that the presence of both organic ligand bis(benzoylmethyl) sulfoxide and the second ligand salicylic acid could sensitize fluorescence intensities of rare-earth ions, and the introduction of salicylic acid group was a benefit for the fluorescence properties of the ternary rare-earth complexes. The fluorescence spectra, fluorescence lifetime and phosphorescence spectra were also discussed.     

Raman spectroscopic study of the uranyl sulphate mineral jáchymovite (UO2)8(SO4)(OH)14· 13H2O

Raman spectra of jáchymovite, (UO₂)₈(SO₄)(OH)₁₄·13H₂O, were studied, complemented with infrared spectra, and compared with published Raman and infrared spectra of uranopilite, [(UO₂)₆(SO₄)O₂(OH)₆(H₂O)₆]·6H₂O. Bands related to the stretching and bending vibrations of (UO₂)²⁺, (SO₄)²⁻, (OH)⁻ and water molecules were assigned. U O bond lengths in uranyl and O H· · ·O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman spectroscopy of hydrogen‐arsenate group (AsO3OH) in solid‐state compounds: cobalt mineral phase burgessite Co2(H2O)4[AsO3OH]2·H2O

Raman spectrum of burgessite, Co₂(H₂O)₄[AsO₃OH]₂· H₂O, was studied, interpreted and compared with its infrared spectrum. The stretching and bending vibrations of (AsO₃) and As‐OH units, as well as the stretching, bending and libration modes of water molecules and hydroxyl ions were assigned. The range of O H···O hydrogen bond lengths was inferred from the Raman and infrared spectra of burgessite. The presence of (AsO₃OH)²⁻ units in the crystal structure of burgessite was proved, which is in agreement with its recently solved crystal structure. Raman and infrared spectra of erythrite inferred from the RRUFF database are used for comparison. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman spectroscopic study of the uranyl mineral metauranospinite Ca[(UO2)(AsO4)]2·8H2O

Raman spectra of metauranospinite Ca[(UO₂)(AsO₄)]₂·8H₂O complemented with infrared spectra were studied. Observed bands were assigned to the stretching and bending vibrations of (UO₂)²⁺ and (AsO₄)³⁻ units and of water molecules. U O bond lengths in uranyl and O H···O hydrogen bond lengths were calculated from the Raman and infrared spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Phonons and electronic transitions in the Raman spectra of FeCl2·2H2O and isomorphic compounds

The Raman spectra in FeCl₂ · 2H₂O (FC2) and the isomorphic compounds FeCl₂ · 2D₂O (FC2D), MnCl₂ · 2H₂O (MC2) and CoCl₂ · 2H₂O (CC2) were observed at 2 K to obtain the frequencies of all 12 optical phonons of even symmetry at the zone center. The lowest of these phonons is known to be coupled resonantly to the magnons below T_N. This coupling and other important magnetic properties of the iron salts are determined by the influence of the crystal field. The electronic transitions of the Fe²⁺-ion in a crystal field are identified after a thorough assignment of the phonon lines in the four isomorphic compounds to symmetry types, using back-scattering and 90°-scattering techniques.     

The catalytic effects of H2CO3, CH3COOH,HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH

The addition reaction of CH₂OO + H₂O → CH₂(OH)OOH without and with X (X = H₂CO₃, CH₃COOH and HCOOH) and H₂O was studied at CCSD(T)/6-311+ G(3df,2dp)//B3LYP/6-311+G(2d,2p) level of theory. Our results show that X can catalyse CH₂OO + H₂O → CH₂(OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH₂OO···H₂O is favourable one. Water-assisted CH₂OO + H₂O → CH₂(OH)OOH can occur by H₂O moiety of (H₂O)₂ or the whole (H₂O)₂ forming cyclic structure with CH₂OO, where the latter form is more favourable. Because the concentration of H₂CO₃ is unknown, the influence of CH₃COOH, HCOOH and H₂O were calculated within 0–30 km altitude of the Earth's atmosphere. The results calculated within 0–5 km altitude show that H₂O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%–77.26% and 0.04%–1.76%. Within 5–30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%–98.28%. However, compared with the reaction of CH₂OO + HCOOH, the rate of CH₂OO···H₂O + HCOOH is much slower.     

Raman spectra of crystalline double sulphates

Raman spectra of single crystals of K₂M(SO₄)₂ · 6 H₂O where M=Mg, Zn, Ni or Co have been recorded for the first time usingλ 2537 as the exciting radiation. The corresponding five single sulphates have also been studied. Interesting results concerning the substitution of magnesium, zinc, nickel or cobalt in the double sulphate lattice on the sulphate frequencies are observed. The lattice spectra of these double sulphates are analysed group theoretically and discussed in relation to the lattice spectra of the corresponding individual sulphates. Certain new results concerning the Raman spectra of the individual sulphates have also been obtained and in the case of CoSO₄ · 7 H₂O the spectrum has been recorded for the first time.     

Synthesis and Luminescence Properties of Two Novel Lanthanide (III) Perchlorate Complexes with Bis(benzoylmethyl) Sulfoxide and Benzoic Acid

Two novel ternary rare earth complexes of Tb(III) and Dy(III) perchlorates with bis(benzoylmethyl) sulfoxide (L) and benzoic acid (L′) had been synthesized and characterized by elemental analysis, coordination titration analysis, molar conductivity, IR, TG-DSC, ¹HNMR and UV spectra. The results indicated that the composition of these complexes was REL₅L′(ClO₄)₂·nH₂O (RE= Tb(III), Dy(III); L=C₆H₅COCH₂SOCH₂COC₆H₅, L′=C₆H₅COO; n = 6,8). The fluorescence spectra illustrated that the ternary rare earth complexes presented stronger fluorescence intensities, longer lifetimes and higher fluorescence quantum efficiencies than the binary rare earth complexes REL₅·(ClO₄)₃·2H₂O. After the introduction of the second ligand benzoic acid group, the relative fluorescence emission intensities and fluorescence lifetimes of the ternary complexes REL₅L′(ClO₄)₂·nH₂O (RE= Tb(III), Dy(III)) enhanced more obviously than the binary complexes. This indicated that the presence of both organic ligands bis(benzoylmethyl) sulfoxide and the second ligand benzoic acid could sensitize fluorescence intensities of rare earth ions, and the introduction of benzoic acid group was resulted in the enhancement of the fluorescence properties of the ternary rare earth complexes. The phosphorescence spectra were also discussed.