Adsorbate interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate studied by CW and Pulsed electron spin resonance

The interactions of Cu(II) in Cu(II)-exchanged K-L gallosilicate with adsorbates containing coordinative nitrogens in ammonia, pyridine, aniline, acetonitrile and hydrazine, and with the adsorbates carbon monoxide, benzene, propanol and dimethyl sulfoxide are investigated by electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopies. These results are compared with those in Cu(II)-exchanged K-L aluminosilicate and the differences are discussed. Adsorption of ammonia produces a complex containing four molecules of ammonia based on resolved nitrogen superhyperfine interaction. Upon equilibrium with pyridine, Cu(II) forms a complex containing four molecules of pyridine in CuK-L gallosilicate and a complex containing only three molecules of pyridine in CuK-L aluminosilicate based on resolved nitrogen superhyperfine. Upon adsorption of aniline and acetonitrile, Cu(II) forms complexes containing two molecules of each in CuK-L gallosilicate based on resolved nitrogen superhyperfine. However, no resolved nitrogen superhyperfine between hydrazine and Cu(II) is seen. Adsorption of carbon monoxide, benzene, propanol and dimethyl sulfoxide causes changes in the ESR spectrum of Cu(II), indicating migration of Cu(II) into cation positions in the main channels where adsorbate coordination can occur. Cu(II) forms complexes with one molecule of benzene and two molecules of propanol based on ESEM data in both K-L gallosilicate and K-L aluminosilicate. However, Cu(II) interacts directly with one dimethyl sulfoxide in K-L aluminosilicate but only indirectly at a longer distance with one dimethyl sulfoxide in K-L gallosilicate based on ESEM data.     

Superhyperfine structure of the ESR spectrum of the Cu+2 ion in the ZnWO4 lattice

When present in the ZnWO₄ lattice in quantities of less than 0.005%, the Cu⁺² ion exhibits an ESR spectrum with a superhyperfine structure of the ligand type at liquid-helium temperature. This is due to the interaction of the 3d⁹ electrons of the Cu⁺² ion with the nuclear magnetic moments of the W¹⁸³ isotopes (14.4%) lying along the z axis; the superhyperfine interaction constant is equal to 7.4±0.4 G. On increasing the concentration of the Cu⁺² ions the superhyperfine structure of the spectrum no longer appears. Calculations of the intensities of the spectral components agree satisfactorily with experimental data.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 56–59, September, 1974.     

Modelling of multifrequency ESR spectra of Fe3+ ions in crystalline and amorphous materials: A Simplified approach to determine statistical distributions of spin-spin coupling parameters

Focussed on the understanding of the complex Fe³⁺ electron spin resonance (ESR) spectra in crystalline and amorphous systems, the simulation program ESR-MAKRO-1 was developed, which allows the calculation of powder spectra of paramagnetic centers with 1/2 ≤S ≤7/2. For the reproduction of the ESR spectra of amorphous systems Gaussian distributions of the zero-field-splitting parameters of second and fourth order (D, E, a, F) were implemented into the program. Applications of ESR-MAKRO-l are given both for crystalline powders and for glassy systems. A stepwise analysis of the ESR spectra, allowing an approach to Fe³⁺ ESR spectra of amorphous matrices and showing the influence ofD, E, a, andF as well as their distributions, is given.     

Method for calculating small-angle neutron scattering spectra using all-atom molecular dynamics trajectories

A method for calculating small-angle neutron scattering (SANS) spectra based on data obtained using the method of the all-atom molecular dynamics of biomacromolecular structures is considered. When interpreting the SANS data, this approach makes it possible to take into account the fact that the structure of biomacromolecules in a solution is not a static object. This method is implemented in the form of a module for the GROMACS software package and will be available in version 4.6 of this popular program package for simulating biomacromolecular-structure dynamics.     

EPR study of ordered Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-based aerogel

Samples of oriented aerogel based on aluminum oxide are studied by the electron paramagnetic resonance (EPR) technique under steady-state and pulse conditions. At least two types of paramagnetic centers interacting with Al nuclei on the surface of aerogel are revealed. Their spectra are characterized by the presence or absence of superhyperfine structure in the EPR spectra, respectively. The X-ray irradiation at room temperature gives rise to the formation of additional long-lived paramagnetic centers of the second kind. Their characteristic decay times for the “fast” and “slow” processes are determined. The interaction of induced paramagnetic centers with protons located on the surface of aerogel is revealed.     

以VO2+为自旋探针的配位共聚催化剂分子筛载体的ESR研究

以VO²⁺为自旋探针,观察了VO²⁺负载的分子筛载体的微环境,在计算机上模拟了复杂的多中心的实验ESR谱,发现VO²⁺在载体上的分散状况不仅取决于制备条件,也和分子筛的种类有关。利用这种方法,可得探针在载体上所处微环境的信息,进而可用于指导配位聚合催化剂载体的选择。     

Two-Dimensional CW-ESR Correlation Spectroscopy

In the present paper, a new method called two-dimensional continuous-wave electron spin resonance (2-D CW-ESR) correlation spectroscopy is introduced. This method is based on mathematical analysis of ESR data obtained from common CW-ESR spectra. It is different from conventional 2-D ESR, which is built on multiple-pulse sequences. Synchronous and asynchronous 2-D CW-ESR correlation spectra defined by two independent magnetic field variable axes are generated by a correlation analysis of dynamic fluctuations of ESR signals induced by an external perturbation. The basic property of 2-D ESR correlation spectra is described. Several examples are investigated and discussed on applications of 2-D ESR correlation spectra in the spin self-trapping of 2-methyl-2-nitrosopropane (MNP), the mixture of spin adducts generated by self-trapping of MNP and 5,5-dimethyl-1-pyrroline N-oxide, and the coordination reaction of benzo-15-crown-5 with cupric ion in boron trifluoride-ether solution. The potential applications of this new 2-D CW-ESR method are discussed. Authors' address: Yong Li, Department of Chemistry, Tsinghua University, Beijing 100084, China     

Ab initio calculation of hyperfine and superhyperfine interactions for shallow donors in semiconductors

For the shallow group V donors in Si we show that the hyperfine interaction for the donor nucleus and the superhyperfine interactions for the first five shells of Si ligands can be quite accurately calculated using the local spin-density approximation of the density-functional theory. We treat the impurity problem in a Green's function approach. Since we have to truncate the long-ranged part of the defect potential, we do not obtain a localized gap state. Instead we identify the resonance above the conduction band with the paramagnetic defect state. We show that the hf and shf interactions thus obtained are at least as accurate as those obtained from one-electron theories with fitting parameters. Application of this first principles method to other shallow donors could be an essential help in defect identification.     

ESR investigation of structure and dynamics of paramagnetic centres in lime mortars from Budinjak,Croatia

This study presents the preliminary results of investigation of the types and dynamics of paramagnetic centres in lime mortars from Sveta Petka church in Budinjak, Croatia, using Electron Spin Resonance (ESR) spectroscopy. The excavation in Budinjak discovered a very unique four lobed plan object Sveta Petka, with no additional finds or reliable historical records about the time of its construction. The lime mortars from the church were chosen for analysis in order to characterize the building material and to verify the site chronology by dating them. Lime mortar is valuable but problematic material for luminescence and radiocarbon dating. This type of material has not been dated before using ESR; therefore, careful studies are required to identify the useful paramagnetic centres. The ESR approach suggested in this work concentrates on a calcium carbonate signal. All samples were γ-irradiated in ⁶⁰C bomb with the doses of 1, 10, 20, 50, 80 and 100 kGy. In all spectra signals from Fe³⁺ and Mn²⁺ ions have been observed. Paramagnetic centres which give the ESR signals may be interpreted as CO₂^?, CO₃^?, CO₃^3?, HCO₃^2?, SO₂^?, SO₃^?, PO₂^? and PO₃^2? species. However, all spectra are complex and signals are interfering; therefore, computer resolution enhancement method will be needed in further research. The changes in ESR signals amplitude measured at magnetic field range about 3440–3450 G were analysed versus the dose of irradiation, using Mn²⁺ signals as a reference. Exponential growth of the curve and saturation for doses above 20 kGy were observed; therefore, irradiation with smaller doses is required. These preliminary studies will be helpful in future attempts of dating lime mortars by ESR method.     

Linewidth Analysis of Spin Labels in Liquids: I. Theory and Data Analysis

We present a method of simulating the EPR spectra of spin labels in liquids using direct convolution of hyperfine splitting with Lorentzian linewidths. The aim is to simulate the experimental lineshape by considering all spectrometer characteristics as well as inhomogeneous and homogeneous linewidth effects. A major advance in this method is the correction for the broadening produced by Zeeman modulation commonly used to obtain EPR signals; this allows experimenters much more freedom to optimize their experimental conditions for the best signal-to-noise ratio. Microwave power broadening (saturation) effects on the EPR lines are significant even at very low observer levels. Successful simulation requires that all contributions from unresolved hyperfine splittings be explicitly included. Inhomogeneous broadening is dealt with by including all spins that interact with the electron (as a set of superhyperfine interactions); there is no "effective Gaussian" to substitute for the correct superhyperfine interactions. The effects of spin exchange on the linewidth and lineshape can be observed and must be taken into account in order to extract the fundamental linewidths.     

二维相关光谱探测荧光能量转移现象

以EuCl₃和NdCl₃混合水溶液为研究对象,按正交浓度序列以浓度为外部扰动构建紫外可见-荧光二维相关光谱。在混合溶液的二维相关光谱中,观察到了Eu3+的荧光发射谱峰与Nd^{3+的吸收谱峰之间存在交叉峰。交叉峰的出现表明Eu3+和Nd3+的荧光发射与吸收之间存在能量传递。二维相关光谱中交叉峰的产生并非由于溶剂水分子与溶质(Eu3+或Nd3+)之间相互作用;若以单一溶质的EuCl₃和NdCl₃的水溶液构造模拟的“混合溶液”的拟合光谱构建二维紫外可见-荧光相关光谱,由于Eu3+和Nd3+在空间上相互分离,无相互作用发生,交叉峰并不存在。二维相关光谱的交叉峰可为从光谱学角度探测复杂体系能量传递及其相关机制提供一条新思路。}     

Discovery of a self-trapped-electron center in α-TeO 2

Electron spin resonance (ESR) studies show that electron irradiation of an f -TeO 2 single crystal followed by 330-nm UV illumination at ～10 v K generates a new spin-1/2 paramagnetic center having C 2 symmetry, like the Te lattice sites, that is attributed to a self-trapped charge on a Te. Identification is facilitated by a strong hyperfine interaction with 125 Te at a central Te site and weaker 125 Te superhyperfine interactions with three different equivalent pairs of neighboring Te cations. The irradiations also produce the diamagnetic V_{O}^{\times} center and the paramagnetic V_{O}^{\bullet} and V_{O}^{\prime} centers. From measurements of concentration changes of the paramagnetic centers due to thermal annealing of the new center it is deduced that the self-trapped charge is a self-trapped electron. It is designated as a \hbox{TeO}_{2}^{\prime} center. This assignment is consistent with its low thermal stability since it anneals quickly at temperatures above 40 v K. ESR characteristics of this new center are described.     

Optically detected magnetic resonance of a relaxed excited state of atomic hydrogen centres in KCl and RbCl doped with I-

The ESR spectrum of relaxed excited state (RES) of inerstitial hydrogen centres in the “mixed” configuration with 3 Cl^- and 1 I^- ions next could be measured via the magnetic circular dichroism of the UV absorption bands. The g factor and I superhyperfine interactions of the RES and the ground state are practically the same, whereas the proton hyperfine interaction in the RES is reduced by ～ $\text{1}\text{3}$. The RES is a spin quartet charge transfer state with a very large zero field splitting.     

Electron transfer at lanthanum endohedral fullerenes

The aim of this contribution is to study lanthanum containing fullerenes produced and treated under different conditions. The work was done using solid soot extract giving poorly resolved ESR spectra or separated lanthanofullerenes in solution showing well resolved ESR spectra. ESR experiments in connection with the mass spectrometry give information on the electronic states due to the electron transfer from the endohedral metal to the fullerene cage and the influence of oxygen on endohedral lanthanofullerene. The analysis of ESR spectra indicates the presence of up to nine octets of lanthanum containing fullerenes. These species have different stabilities. Furthermore, a very narrow single ESR line in the lanthanofullerene spectrum was detected having a linewidth ΔB=0.008 mT and ag-factor 2.0025. The electron transfer to the endohedral La@C₈₂ molecule studied by voltammetry and electrochemicalin situ ESR experiments is described. The interaction of the lanthanofullerene with oxygen in solution is also studied. In different solvents the influence of oxygen on line broadening in the ESR spectra of La@C₈₂ was observed.     

General formulae for hyperfine structure and endor frequencies

General expressions for hyperfine (superhyperfine) structure and ENDOR frequencies are derived. It is only assumed that the hyperfine (superhyperfine) interaction is much smaller than the electronic spin transition energy but the electronic spin-Hamiltonian may be of arbitrary form. To obtain the ENDOR frequencies one need only know the electron spin matrix elements. These influence the direction and magnitude of the effective magnetic field which act on the nucleus.     

四种哌啶系氮氧自由基的ESR特性研究Ⅲ.pH效应和去氧效应

本文研究不同PH和去氧对数种哌啶系氮氧自由基在溶液中的ESR波谱的影响。其中两种水溶性自由基在PH为3-12的缓冲液内,有较高稳定性。对固态自由基,去氧并不影响其ESR特性,但在自由基溶液中,溶剂极性对如何显现去氧效应起着决定性的作用。在低极性溶液中,去氧使波谱显著变窄及增强,¹⁴N超精细三峰分裂的完善程度大大提高;而在水溶液中,去氧效应甚小。     

多相氧载体CoO-MgO和氧分子作用的ESR研究

用ESK研究多相氧载体CoO-MgO表面上氧的吸附作用,发现在77-150K温度范围内表面Co²⁺离子和O₂的结合是可逆的,吸附产生Co³⁺-O₂^-自由基加合物有超精细结构的ESR谱;当温度增加,吸附态O₂^-自由基发生转移并稳定在Mg²⁺离子上形成Mg²⁺-O₂^-自由基,文中着重讨论Co³⁺-O₂^-自由基的电子结构和成键本质,认为自由基是通过自旋成对的方式形成的,由于σ-л键作用引起的自旋极化以及由于电子离域作用而引起的偶极作用与ESR制的超精细结构线产生有关。     

Superhyperfine interaction in the trigonal center BaF2: Gd3+ and the lattice distortion analysis in the vicinity of the impurity ion

The constants of the superhyperfine interaction of Gd³⁺ with the ¹⁹F nuclear spins in the first four coordination shells were determined from the ENDOR spectra of a trigonal BaF₂: Gd³⁺ center. These data were used for analysis of the crystalline lattice distortions in the vicinity of the impurity ion. It was found that the largest displacements of fluorine nuclei occurred in the vicinity of the ion compensator and the impurity ion. To calculate the anion positions within the first coordinate shell, whose electron-nuclear interaction with Gd³⁺ depends considerably on chemical bonds in the Gd³⁺F ₈ ^? complex, an empirical model is used for the isotropic constants of the superhyperfine interaction of Gd³⁺ with fluorine nuclei in cubic centers, with allowance made for the impurity ion polarization.     

The application of artificial neural networks to the inversion of the positron lifetime spectrum

A new method of processing positron annihilation lifetime spectra is proposed.It is based on an artificial neural network(ANN)-back propagation network(BPN).By using data from simulated positron lifetime spectra which are generated by a simulation program and tested by other analysis programs,the BPN can be trained to extract lifetime and intensity from a positron annihilation lifetime spectrum as an input.In principle,the method has the potential to unfold an unknown number of lifetimes and their intensities from a measured spectrum.So far,only a proof-of-principle type preliminary investigation was made by unfolding three or four discrete lifetimes.The present study aims to design the network.Besides,the performance of this method requires both the accurate design of the BPN structure and a long training time.In addition,the performance of the method in practical applications is dependent on the quality of the simulation model.However,the chances of satisfying the above criteria appear to be high.When appropriately developed,a trained network could be a very efficient alternative to the existing methods,with a very short identification time.We have used the artificial neural network codes to analyze data such as the positron lifetime spectra for single crystal materials and monocrystalline silicon.Some meaningful results are obtained.     

Electron-paramagnetic-resonance of ZnTe:Ga and ZnTe:Sn

Photosensitive EPR measurements ofS-state centers of gallium and tin in ZnTe single crystals are reported. In addition to large hyperfine interaction with the impurity nuclei the spectra show partially resolved superhyperfine structures arising from three shells of tellurium ligands. Both HF and SHF splittings decrease with increasing temperature. The samples exhibitp-type photoconductivity with the same spectral sensitivity observed with the generation and depletion of the EPR-spectrum.