晶体CsMgCl3:Ni2+的局部结构、光谱和EPR谱的理论研究

本文采用半自洽场(semi-SCF) 自由Ni2+的3d轨道波函数、点电荷-偶极子模型和Ni2+-6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgCl3:Ni2+晶体的局部结构参数,统一解释了CsMgCl3:Ni2+晶体的吸收光谱和EPR 谱.此外,还讨论了高阶微扰方法、参量拟合方法等问题.理论计算结果与实验值符合得很好.     

EPR spectra and structure of sodium sulfate borate glasses

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 2, pp. 242–248, February, 1991.     

EPR studies of technetium complexes in frozen solution

Analysis of the EPR spectra of Tc complexes in frozen solution has given information about the behaviour of these complexes not readily obtainable by other means. In particular, spectral simulations have enabled the determination of the quadrupole interaction parameter,Q, and thus to the evaluation of subtle electronic effects.     

EPR studies of X-ray irradiated dithiophosphate metal complexes

Different metal O,O’-disubstituted dithiophosphates have been studied by Electron Paramagnetic Resonance (EPR) spectroscopy after X-ray irradiation at 77K. Formation of different radicals has been recorded depending on the central metal atom and on the substituents in the ligands. Phosphorus-centered radicals with hyperfine constants of about 800 G were recorded after radiolysis of zinc and cadmium complexes. Their shape and EPR parameters lead to their identification as phosphoranyl radicals (RO)₂P (S)S^?. In these compounds two different types of coordination of the ligands have been found by X-ray analysis. One dithiophosphate group is coordinated to the metal atom forming a chelate four-membered ring, and another one is a bridging group. The formation of phosphorus-centered radicals is related to the presence of a bridging, or interchelating group. In other metal dithiophosphates, with only chelating groups present, such radicals were not found. In platinum, palladium and nickel dithiophosphates similar EPR signals with small hyperfine coupling were observed. They have been identified as carbon-centered radicals with one phosphorus in γ-position.     

The electronic structure and spectra of octacyanide complexes

The optical and electron spin resonance spectra of molybdenum and tungsten octacyanides have been measured and the results are interpreted by electrostatic crystal field theory using a point charge model of D _2d symmetry.     

Simulation studies of high-field EPR spectra of spin-labeled lipids in membranes

The high-field (i.e., 94 GHz) membrane EPR spectra of lipids spin labeled in their fatty acid chains have been simulated by using two limiting motional models. The aim was to identify the dynamic origin of the residual (g(xx) - g(yy)) anisotropy observed in the nonaxial EPR spectra of cholesterol-containing membranes. It is concluded that the residual spectral anisotropy arises from in-plane ordering of the lipid chains by cholesterol. The partial averaging of the (g(xx) - g(yy)) anisotropy was best described by restricted axial rotation with a frequency in the region of tau(-1)(R||) approximately 0.5-1 x 10(9) s(-1). Simulations for slower axial rotation of unrestricted amplitude produced less satisfactory fits. In phospholipid membranes not containing cholesterol, the nonaxial anisotropy is completely averaged in the fluid phase and substantially reduced even in the gel phase. The unrestricted axial rotation in the gel phase is of comparable frequency to that of the limited axial rotation in the liquid-ordered phase of membranes containing cholesterol. These results on in-plane ordering by cholesterol in the liquid-ordered phase could be significant for current proposals regarding domain formation in cellular membranes.     

X-ray photoelectron spectra and structure of iron polynuclear complexes

Iron trimethylacetate complexes with different ligands have been investigated by X-ray photoelectron spectroscopy (XPS). The Fe 2p, Fe 3p, C 1s, O 1s, and N 1s spectra obtained at successive replacement of the Fe-O coordination bonds with Fe-N bonds have been analyzed. A satellite component is found in the spectra of iron trimethylacetate complexes, which is indicative of the high-spin state of Fe^II and Fe^III iron atoms. The XPS data made it possible to determine the degree of covalence of the metal-ligand bonding and reveal two nonequivalent states for iron atoms.     

Ru(bpy)2dppx2+与核酸作用的光谱研究

合成７,８－二甲基二联吡啶并（３,２,ａ：２’,３’,ｃ）吩嗪,简称ｄｐｐｘ,并合成了Ｒｒ（ｂｐｙ）２ｄｐｐｘ＾２＋混配物,研究了混配物与ＤＮＡ作用的紫外－可见光谱与荧光光谱。在ｐＨ９．５时ＤＮＡ能使混配物的紫外可见光谱发生明显的减色效应,荧光光谱在５９９ｎｍ处（λｅｘ＝４７１ｎｍ）产生新的荧光峰,探讨了反应的机理。     

Hyperfine structure of submillimeter EPR spectra of non-Kramers lanthanide ions in crystals

The hyperfine structures of submillimeter EPR spectra of CsCdBr₃:Tm³⁺ and CaF₂:Dy²⁺ single crystals have been resolved and analyzed. The crystal field parameters and the magnetic hyperfine constants are obtained from fitting the envelopes of the simulated spectra to the measured signals. From the specific peculiarities of the hyperfine structure the energy of the interion interaction in the thulium dimers in CsCdBr₃ is determined. The isotopic shift of the crystal field splitting in energy patterns of dysprosium isotopes in CainF₂ is estimated.     

Infrared spectra and structure of molecular complexes of aromatic acids

FTIR spectra of pharmacologically active molecules of benzoic acid and its derivatives have been measured in CCl₄ solutions and in microcrystals. Features of the formation of intra-and intermolecular hydrogen bonds have been analyzed. Spectral attributes have been revealed that characterize the participation of a carboxyl group in different types of intermolecular interactions with the formation of cyclic, linear, and criss-cross dimers. Mechanisms of the intermolecular interactions are shown to be defined by the character of the substituents attached to the benzene ring in the para- and meta-positions relative to the carboxylic group.     

用光谱和EPR谱确定CsMgBr3:Ni2+的局域结构

本文采用半自洽场(semi-SCF)自由Ni2 的3d轨道波函数、点电荷—偶极子模型和Ni2 -6X-(X=F,Cl,Br,I)络合物的μ-κ-α模型,建立了结构参数与光谱、EPR谱之间的定量关系,利用完全对角化方法,由光谱和电子顺磁共振(EPR)谱,确定了CsMgBr3:Ni2 晶体在77K温度时的局域结构参数,统一解释了CsMgBr3:Ni2 晶体的局域结构、光谱和EPR谱。所得理论结果与实验值符合得很好。此外,还讨论了晶体局域结构发生畸变的原因。     

Superhyperfine structure in the EPR spectra and optical spectra of impurity f ions in dielectric crystals: A review

The results of observation and simulation of the superhyperfine (ligand hyperfine) structure (SHFS) of the electron paramagnetic resonance (EPR) spectra of rare-earth and uranium impurity ions in dielectric crystals have been systematized. The resolved SHFS of the EPR spectra of doped cubic crystals (with the fluorite and perovskite structures) has been observed for orientations of a constant magnetic field along the crystallographic axes. Most attention has been paid to tetragonal double fluorides LiRF₄ (R = Y, Lu, Tm), in which the SHFS of the EPR spectra has also been found for intermediate orientations of the magnetic field. For the LiYF₄: Nd³⁺ single crystal, the splitting of optical spectral lines due to the interaction of Nd³⁺ ions with nuclear magnetic moments of the nearest neighbor fluorine ions has been observed for the first time. The Van Vleck paramagnet LiTmF₄: U³⁺ is characterized by the SHFS with clearly distinguishable components due to the interaction of uranium ions both with nuclei of the fluorine ions and with enhanced magnetic moments of the thulium nuclei. The SHFS envelopes of the EPR spectra of Yb³⁺, Ce³⁺, Nd³⁺, and U³⁺ ions in LiYF₄ and LiLuF₄ crystals are well reproduced by numerical calculations based on the microscopic model using only three fitting parameters: the width of transitions between the electron-nuclear sublevels of the complex containing the paramagnetic ion and nuclei of the ligands and two constants of covalent bonding of the f electrons with 2s and 2p electrons of the nearest neighbor fluorine ions.     

Theoretical studies of the optical and EPR spectra for vanadyl ions in alkaline-earth aluminoborate glasses

The optical spectra and electron paramagnetic resonance (EPR) g and A factors of calcium aluminoborate glasses (CaAB) : VO²⁺ are calculated using a complete diagonalization (of the energy matrix) process (CDP). Good agreement between the theoretical values and experimental results indicates the effectiveness of the CDP method for theoretical studies of optical and EPR spectra of 3d¹ (or V⁴⁺) ions in glasses.     

EPR spectra of C60 anions

The broad and sharp EPR signals observed in spectra of C₆₀ and C ₆₀ ^3? are summarized and proposed assignments are discussed. The sharp signals in samples of C ₆₀ ^2? are reviewed.     

Molecular spectroscopic studies of charge transfer complexes of thiourea derivatives with benzoquinones

Charge transfer complexes of substituted-N-aryl-N-4-(-p-anisyl-5-arylazothiazolyl)thiourea with 2,3-dichloro-5,6-dicyanobenzoquinones (DDQ), chloranilic acid (CHLA), chloranil (CHL), bromanil (BRL) and iodanil (IDL) in methylene chloride were investigated spectrophotometrically to determine association constants (K), molar extinction coefficients (ε) and stoichiometric ratio. The effect of thermodynamic parameters (ΔG* and ΔH) on the stability of the complexes are discussed and the transition energy (E) of the CT complexes are reported. The solid CT complexes of the substituted-N-aryl-N-4-(-p-anisyl-5-arylazothiazolyl)thiourea with the above acceptors have been prepared and investigated by IR, electronic, ¹H NMR and ESR spectroscopy. Nonacidic acceptors yield complexes having π–π* and n–π* bonding. Acidic acceptors yield complexes having π–π* and proton transfer interaction. The formation of 1:2 (D:A) complexes is also ascertained.