Librational dynamics of nitroxide molecules in a molecular glass studied by echo-detected EPR

Nitroxides 2,2,6,6-tetramethyl-4-piperidone N-oxide (tempone), 3-carboxy-proxyl and potassium peroxylamine disulfonate (Fremy salt) in glycerol solution were studied in a wide temperature range near the glass transition temperatureT _g. The echo-detected (ED) electron paramagnetic resonance (EPR) lineshape reveals strong dependence on the time interval τ between the echo-forming microwave pulses which is readily explained by anisotropic phase relaxation. Employing a librational model of molecular motion and the Redfield relaxation theory, spectra were simulated for the τ’s varying in a large interval. The anisotropic relaxation rate increases with temperature increase and it is larger for nitroxide with a larger molecular size. The mean-squared amplitude of motion, obtained from reduced hyperfine splitting in continuous-wave EPR, near T_g linearly depends on temperature which is characteristic of harmonic solids. For tempone in a host crystal 2,2,4,4-tetramethyl-cyclobutan-1, 3-dione the anisotropic spin relaxation rate decreases with temperature increase so the found feature solely belongs to a glassy state. A new approach is proposed for modeling slow wobbling motion in a restricted angular space.     

The cooperative spin transition in [FexZn1 − x(ptz)6](BF4)2: II. Structural properties and calculation of the elastic interaction

The cooperativity of the thermal spin transition in the Fe(II) spincrossover compound [Fe(ptz)₆](BF₄)₂ (ptz = 1-propyltetrazole) and in isomorphous mixed crystals with the isostructural zinc complex is investigated. From powder X-ray measurements the lattice deformation (tensor ε) accompanying the spin transition is determined. For diluted mixed crystals with x < 0.44 the lattice deformation is directly related to the spin transition, whereas in concentrated mixed crystals with x > 0.44 a first order crystallographic phase transition (R3i → P1i) is observed on cooling, which is triggered by the spin transition and can be suppressed by cooling rapidly. The thermal spin transition is measured with UV/VIS optical absorption spectroscopy on mixed single crystals in the R3i structure. From this metal dilution experiment an interaction constant of 169 cm ^{? 1} for the cooperativity of the spin transition is determined. Furtheron, this interaction constant is calculated on the grounds of elasticity theory: The lattice deformation due to the spin transition is traced back to anisotropic elastic point defects, which directly interact with each other via their stress fields and indirectly via the surface of the elastic crystal by an image pressure. The elastic properties of the crystalline matrix are taken in the isotropic approximation. They are derived from the complete sets of anisotropic elastic constants of the pure iron and zinc compounds, which have been measured previously by Brillouin spectroscopy. The contribution of elastic energy calculated this way is ? 80% of the experimental value of the interaction constant, i.e. the cooperativity in crystalline spincrossover compounds is quantitatively of elastic nature.     

Singularities in the lineshape of a second-order perturbed quadrupolar nucleus. The magic-angle spinning case

For a nucleus with a half-integral spin and a strong quadrupole coupling, the central transition (from magnetic quantum number −1/2 to +1/2) in the spectrum shows a characteristic lineshape. By strong coupling, we mean an interaction strong enough so that second-order perturbation theory is needed, yet still sufficient. The spectrum of a static sample is well-known and the magic-angle-spinning (MAS spectrum) is different, but still can be calculated. The important features of both these spectra are singularities and steps in the lineshape, since these are the main tools in fitting the calculated spectrum to experimental data. A useful tool in this investigation is a plot of the frequency as a function of orientation over the surface of the unit sphere. These plots have maxima, minima and saddle points, and these correspond to the features of the spectrum. We used these plots to define both the positions and derive new formulae for the heights of the features and we now extend this to the magic-angle spinning case. For the first time, we identify the orientations corresponding to the features of the MAS spectra and derive formulae for the heights. We then compare the static and MAS cases and show the relationships between the features in the two spectra.     

溶液自由基ESR谱的计算机模拟

根据溶液自由基电子自旋共振(ESR)原理,用高级BASIC语言编写了溶液自由基谱的模拟程序。自由基的ESR能级用一级近似求解,谱线的线型采用洛仑兹和高斯型的混合线型函数,程序规定体系中核自旋量子数可从1/2到7/2,不等性核的数目最多可达10组,每组中等性核的数目原则上不受限制。通过二萘嵌苯阳离子自由基和硝基苯负离子自由基谱模拟二个例子加以说明,模拟结果是满意的。     

Highly anisotropic g-factor of two-dimensional hole systems

Coupling the spin degree of freedom to the anisotropic orbital motion of two-dimensional (2D) hole systems gives rise to a highly anisotropic Zeeman splitting with respect to different orientations of an in-plane magnetic field B relative to the crystal axes. This mechanism has no analog in the bulk band structure. We obtain good, qualitative agreement between theory and experimental data, taken in GaAs 2D hole systems grown on (113) substrates, showing the anisotropic depopulation of the upper spin subband as a function of in-plane B.     

Exchange and dipolar spin-spin interaction and rotational diffusion in saturation transfer EPR spectroscopy

Saturation transfer EPR spectroscopy (STEPR) provides a means for investigating weak spin-spin interaction between spin-labelled molecules because the spectral intensity is proportional to the effective spin-lattice relaxation time,T ₁ ^eff. Rate equations for the spin population defferences yield equivalent results for the dependence ofT ₁ ^eff on the physical (or chemical) and Heisenberg spin exchange rates and show thatT ₁ ^eff depends on the extent of redistribution of saturation throughout the anisotropic spin label powder lineshape. This approach yields a particularly simple formulation for the dependence of the STEPR lineshape on slow rotational diffusion. The effects of spin exchange are readily distinguished from those of slow rotational diffusion because of the insensitivity of the STEPR lineshape in the former case. The characteristic dependence of the STEPR spectral intensity on spin concentration allows determination of the exchange rate and can be used for studying slow translational diffusion, e.g. of spin-labelled proteins. Dipolar relaxation induced by paramagnetic ions gives a linear dependence of the reciprocal spin label STEPR intensity on metal ion concentration. STEPR measurements with spin-labelled lipid molecules in gel phase membranes in the presence of Ni²⁺ ions yield reliable distance information and provide calibrations for use with other systems.     

Substituent effect on electron affinity,gas‐phase basicity,and structure of monosubstituted propargyl radicals and their anions: a theoretical study

The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH₂ group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CH?C? CH₂?), 1.15 eV (CH?C? CHF?), 1.38 eV (CH?C? CHCl?), 1.48 eV (CH?C? CHBr?) for the isomers with terminal CH and 1.66 eV (CF?C? CH₂?), 1.70 eV (CCl?C? CH₂?), 1.86 eV (CBr?C? CH₂?) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CH?C? CH₂:^?), 371.6 kcal/mol (CH?C? CHF:^?), 365.1 kcal/mol (CH?C? CHCl:^?), 363.5 kcal/mol (CH?C? CHBr:^?) for the isomers with terminal CH and 362.6 kcal/mol (CF?C? CH₂:^?), 360.4 kcal/mol (CCl?C? CH₂:^?), 356.3 kcal/mol (CBr?C? CH₂:^?) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.     

XeO3和XeOF2与三种不同杂化方式N原子的Xe···N非共价作用的理论研究

本文采用密度泛函理论和二级微扰理论方法研究了XeO₃和XeOF₂与一系列不同杂化含氮给体配合物之间的相互作用. 含氮给体与XeO₃和XeOF₂之间的相互作用能在6.5∽19.9 kcal/mol之间. 相互作用强弱顺序为sp³>sp²>sp,且XeO₃比XeOF₂高. 约化密度梯度图证明,对于sp²和sp³杂化的给体,空间位阻效应在相互作用中起着一定的影响. 能量成分分析发现,Xe···N作用主要的吸引部分是静电相互作用. 在XeO₃配合物中,极化能的占比大于色散,而在XeOF₂配合物中则相反. 除表面静电势(V_s)外,其他5个相互作用参数之间的线性相关系数均较大.     

Mesoscopic mixing of spin orientation phases in particles with Ising ions: Holmium: Yttrium iron garnets in strong magnetic fields

The paper presents a theoretical analysis of macroscopic quantum tunneling phenomena in small particles of a cubic ferromagnet of the Ho_xY_3?xFe₅O₁₂ type with strongly anisotropic (Ising) impurity ions present in a low concentration x ? 1 in the region of strong magnetic fields, at which many orientation phase transitions related to the competition of external and exchange field actions on the spin subsystem are observed. The theory of path integrals for the magnetic subsystem was used to calculate the instanton contributions to interphase tunneling amplitudes in the vicinity of first-order transitions for three principal orientations of an external magnetic field in a cubic crystal. It was shown that low-energy barriers separating angular phases could result in anomalously large mesoscopic volumes at which macroscopic spin tunneling effects could appear in the energy spectra of particles. The special features of spectral splitting caused by the mixing of azimuthally degenerate angular phases and phases with different polar angles of magnetization orientation were revealed.     

Ni^2＋：CsMgCl3的光学吸收谱和EPR的研究

应用三角晶场中d^2(d^8)电子组态包括静电相互作用和自旋－轨道耦合作用的强场能量矩阵,采用完全对角化方法,精确地计算了具有D3d对称的Ni^2 :CsMgCl3的光学吸收谱和EPR谱,理论结果与实验值符合得很好。     

The orientational relaxation of methane molecules in the solid phase II at low temperatures

A model for the dynamics of the coupling between the orientations of the ordered CH₄ molecules in phase II of solid methane at low temperatures is proposed. The model is equivalent to the dynamics of disordered solid hydrogen. The effective interaction strength is determined by the overlap of the librational ground states in the molecular field potential and vanishes in the classical limit. An approximate expression for the effective interaction strength is derived, showing an exponential dependence on the uncertainty of orientation in the librational ground states. This parameter is estimated from the experimental values of the tunnel energies. The second moments of the spectral densities of several anisotropic operators are evaluated in the infinite temperature limit. The resulting gaussian approximations for the spectra are applied in a derivation of the spin lattice relaxation time. The calculated values of the spin lattice relaxation time are compared to experiment.     

PbTe/PbSrTe半导体非对称量子阱中的Rashba效应

窄带隙半导体异质结构的自旋效应最近受到了国际上的很大关注.Ⅳ-Ⅵ族半导体具有各向异性和多能谷的特征,因此可以预期Rashba自旋效应在不同取向的Ⅳ-Ⅵ族半导体量子阱结构中存在显著差异.计算了多个取向的Pb_1-ySr_yTe/PbTe/Pb_1-xSr_xTe非对称量子阱中的Rashba分裂能,结果表明［100］取向的PbTe量子阱的Rashba分裂能在阱宽为5.0nm时 关键词： Ⅳ-Ⅵ族半导体 非对称量子阱 Rashba效应 自旋-轨道耦合分裂     

MnFe2O4晶体的基态能级和零场分裂参量

由不可约张量理论构成一个3d4/3d6离子三角(C3V)对称的晶体场和自旋-轨道相互作用哈密顿矩阵,由这个晶体场和自旋-轨道相互作用哈密顿矩阵被完全对角化后能够求出MnFe2O4晶体中的Fe2+离子的电子顺磁共振零场分裂参量D和F-a,计算了低自旋态(3L态)对电子顺磁共振零场分裂参量(D,F-a)的贡献.结果显示低自旋3L态对电子顺磁共振的零场分裂参量的贡献是较强的.理论计算的结果与实验值是相符的.     

Can tetra‐tert‐butylethylene be formed by ion–ion recombination or ion–molecule reaction of two di‐tert‐butylcarbene units?—a DFT study

The reaction channels of di‐tert‐butylcarbene ( 2 ), its radical anion, ( 3 ) and its radical cation ( 4 ) were investigated theoretically by using DFT/B3LYP with 6‐31+G(d) basis set and 6‐311+G(2d,p) for single point energy calculations. Conversion of the neutral carbene 2 to the charged species 3 and 4 results in significant geometric changes. In cation 4 two different types of C? (CH₃)₃ bonds are observed: one elongated sigma bond called “axial” with 1.61 Å and two normal sigma bonds with a bond length of 1.55 Å. Species 2 and 4 have an electron deficient carbon center; therefore, migration of CH₃ and H is observed from adjacent tert‐butyl groups with low activation energies in the range of 6–9 kcal/mol like similar Wagner–Meerwein rearrangements in the neopentyl‐cation system. Neutral carbene 2 shows C? H insertion to give a cyclopropane derivative with an activation energy of 6.1 kcal/mol in agreement with former calculations. Contrary to species 2 and 4 , the radical anion 3 has an electron rich carbon center which results in much higher calculated activation energies of 26.3 and 42.1 kcal/mol for H and CH₃ migrations, respectively. NBO charge distribution indicates that the hydrogen migrates as a proton. The central issue of this work is the question: how can tetra‐tert‐butylethylene ( 1 ) be prepared from reaction of either species 2 , 3 , or 4 as precursors? The ion–ion reaction between 3 and 4 to give alkene 1 with a calculated reaction enthalpy of 203.5 kcal/mol is extremely exothermic. This high energy decomposes alkene 1 after its formation into two molecules of carbene 2 spontaneously. Ion–molecule reaction of radical anion 3 with the neutral carbene 2 is a much better choice: via a proper oriented charge–transfer complex the radical anion of tetra‐tert‐butylethylene (11) is formed. The electron affinity of 1 was calculated to be negligible. Copyright © 2010 John Wiley & Sons, Ltd.     

Molecular simulation investigations on the coating of Al-alloy surface by nano-SiO2-epoxy composite

To improve corrosion protections, a better understanding of the coating behavior and therefore the interaction properties between the inhibitor and the surface is a vital factor. Density functional theory (DFT) simulations were used to explore the adsorption properties of the pure epoxy and nano-SiO₂-epoxy composites on the Al₂Cu surface. The interaction energies and transferred charges of adsorbed composites on the Al₂Cu surface and their optimized structures with various interacting orientations are investigated. It is found that nano-SiO₂-epoxy adsorb more strongly on Al₂Cu substrate in comparison with the epoxy matrix with interaction energies of ˗228.084 kcal/mol and ˗35.341 kcal/mol, respectively. The validity of our computational methods was evaluated by experiments as well as high-level quantum chemistry method. The atom-in-molecules analysis with DFT indicates that the interaction nature is typical for electrostatics. The stability of the adsorption behavior of composites on the surface was also explored by DFT-based molecular dynamics simulation.     

Structural and electronic effects in acetone adsorption over TiO<Subscript>2</Subscript> anatase clusters as the first stage of photocatalytic oxidation

Photocatalytic oxidation is used for air purification from low concentrations of organic compounds and microbiological objects. Adsorption is the first stage of photocatalytic oxidation, and adsorption constant value has direct linear influence onto the rate of oxidation at low concentration according to the Langmuir-Hinshelwood equation. The present computational investigation has been undertaken with the goal to estimate the effect of nanoparticle size in the range of 1–1.5 nm, extent of hydroxylation, surface acidity, and nanoparticle shape on adsorption of acetone over TiO₂ anatase particle facets, edges, and vertices. The anatase nanoparticles were represented by three cluster models—two of cubic shape and one of decahedral shape with exposed surfaces (001), (100), and (101). Adsorption energy was calculated with density functional tight binding (DFTB) semiempirical method and varied from ? 0.67 to ? 25.79 kcal/mol for different sites of the clusters depending on facet types and location on a facet. Mean unweighted adsorption energy of acetone increased from ? 4.49 to ? 8.16 kcal/mol for (001) facet and from ? 11.05 to ? 12.97 kcal/mol for (100) facet when the cubic cluster size increased from 3 × 3 × 1 to 4 × 4 × 1 elementary cells. For decahedral cluster, mean adsorption energy on (001) facet was ? 9.87 kcal/mol and ? 14.44 kcal/mol on (101) facets. The largest adsorption energy ? 25.60 and ? 25.79 kcal/mol was observed on grove Ti atoms on (100) facet of the largest cubic cluster and vertex atoms in decahedral cluster, respectively. Dissociative adsorption of one and two water molecules on (001) facet increased acetone adsorption energy from ? 4.02 to ? 8.20 and to ? 18.50 kcal/mol. A marked electronic effect on adsorption energy was observed for two adjacent sites on (001) facet with a similar structure but adsorption energy ? 16.40 and ? 1.40 kcal/mol. Influence of acetone adsorption on clusters’ band gap, photogenerated thermalized electron and hole location, and C=O vibration wavenumber is also reported.     

Interaction of O2, CO2, CO,C2H4 and C2H4O with Ag(110)

The interaction of O₂, CO₂, CO, C₂H₄ AND C₂H₄O with Ag(110) has been studied by low energy electron diffraction (LEED), temperature programmed desorption (TPD) and electron energy loss spectroscopy (EELS). For adsorbed oxygen the EELS and TPD signals are measured as a function of coverage (θ). Up to θ = 0.25 the EELS signal is proportional to coverage; above 0.25 evidence is found for dipole-dipole interaction as the EELS signal is no longer proportional to coverage. The TPD signal is not directly proportional to the oxygen coverage, which is explained by diffusion of part of the adsorbed oxygen into the bulk. Oxygen has been adsorbed both at pressures of less than 10^-4 Pa in an ultrahigh vacuum chamber and at pressures up to 10³ Pa in a preparation chamber. After desorption at 10³ Pa a new type of weakly bound subsurface oxygen is identified, which can be transferred to the surface by heating the crystal to 470 K. CO₂ is not adsorbed as such on clean silver at 300 K. However, it is adsorbed in the form of a carbonate ion if the surface is first exposed to oxygen. If the crystal is heated this complex decomposes into O_ad and CO₂ with an activation energy of 27 kcal/mol(1 kcal = 4.187 kJ). Up to an oxygen coverage of 0.25 one CO₂ molecule is adsorbed per two oxygen atoms on the surface. At higher oxygen coverages the amount of CO₂ adsorbed becomes smaller. CO readily reacts with O_ad at room temperature to form CO₂. This reaction has been used to measure the number of O atoms present on the surface at 300 K relative to the amount of CO₂ that is adsorbed at 300 K by the formation of a carbonate ion. Weakly bound subsurface oxygen does not react with CO at 300 K. Adsorption of C₂H₄O at 110 K is promoted by the presence of atomic oxygen. The activation energy for desorption of C₂H₄O from clean silver is ～ 9 kcal/mol, whereas on the oxygen-precovered surface two states are found with activation energies of 8.5 and 12.5 kcal/mol. The results are discussed in terms of the mechanism of ethylene epoxidation over unpromoted and unmoderated silver.     

Angular dependent linewidths for a spin probe dissolved in a liquid crystal

A spin probe dissolved in the mesophase of a nematic or smectic liquid crystal behaves, in many ways, as if it were encorporated in a uniaxial single crystal. For example the positions of the lines in the electron resonance spectrum of the probe depend on the orientation of the liquid crystal with respect to the magnetic field. In addition the widths of the spectral lines might also be expected to be angular dependent. The form of this angular dependence is readily calculated provided the dominant spin relaxation process results from molecular reorientation with respect to the director in the mesophase. In this paper we develop a theory for the angular dependence of the linewidths and show how it could be used, with some advantage, to investigate molecular reorientation in a macroscopically anisotropic system. The observed angular dependence of the linewidths for a nitroxide spin probe dissolved in the mesophase of a smectic A liquid crystal confirms certain aspects of the theory.     

Hyperfine anomaly arising from the nuclear spin-forbidden transition,and absolute sign determination of the zero-field splitting constant

It has been found in the triplet E.S.R. spectra of radical pairs in irradiated potassium deuterium fumarate that the hyperfine structure of the two transitions, M _s = 1?0 and M _s = 0?+1, are entirely different. This anomaly has been interpreted in terms of the forbidden transition arising from the mixing of the nuclear spin states by the anisotropic hyperfine interaction. The theory has been developed for multiplet electron spin systems and includes the nuclear Zeeman interaction which is often neglected. The theoretical predictions are in good agreement with the observed separations and intensities of the anomalous hyperfine lines. In addition, it has been found that since the forbidden lines of the electron spin multiplet system with S ≥ 1 appear strongly only in transitions which include some specific electronic spin states, the anomalous features of the spectra make it possible to determine the absolute sign of the zero-field or hyperfine splitting constant, if the sign for one of them is known. Using this principle, attempts have been made to determine the absolute sign of the zero-field splitting constant for a number of triplet E.S.R. spectra which exhibit a hyperfine anomaly arising from the proposed mechanism.