Cu台阶面多层弛豫的第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法对Cu(311),(511),(331)和(221)四个高指数台阶表面的弛豫结构和弛豫后表面各层的电子特性进行了系统研究.发现四个台阶面的层间弛豫规律依次为-+-…,--+-…,--+-…和---+-…,与其平台-阶梯n(hkl)×(uvw)的表示法2(100)×(111),3(100)×(111),3(111)×(111)和4(111)×(111)中的原子排数n相关,即     

Effect of alloy disorder and structural defects on excitonic properties in (100)- and (311)-Oriented InGaAs/GaAs quantum wells

The properties of excitonic states in pseudomorphic, (100)- and (311)-oriented In_0.2Ga_0.8As/GaAs quantum well (QW) structures are investigated. Strained QW's with different states of strain and segregation were grown by molecular beam epitaxy. No growth interruption was carried out at the interfaces. This approach allows us to reduce the segregation effects in samples having (311)A orientation. As a result, quite sharp gaussian shaped excitonic transitions with line width of about 0.8 meV have been demonstrated. We find significant differences in the optical properties, growth kinetic and defect formation of samples for the three orientations. The alloy disorder is smaller in the (311)A orientations than in the (311)B and (100) ones. An anomalous broadening of the excitonic line width is observed in case of samples having (311)B orientation and is accounted for structural defects other than those produced by alloy disorder. Surface wells are used in conjunction with In surface segregation and evaporation effects. Different activation energies for the indium desorption from the (311)A and B surfaces are obtained. We state that the different alloy and defect states are originated in the different strain relaxation mechanism and surface reaction kinetic in the three non equivalent (311) and (100) surfaces.     

Tight—binding calculation of the electronic states of bulk—terminated GaAs（311）A and B surfaces

We have carried out theoretical investigations on the electronic structure of GaAs(311)A and GaAs(311)B surfaces. The bulk electronic structure of GaAs has been described by the second-neighbour tight-binding formalism and the surface electronic structure was evaluated via an analytic Green function method. First, we present the surface band structure together with the projected bulk band of both Ga-terminated and As-terminated for GaAs(311)A and GaAs(311)B surfaces, respectively. In each case, the number of surface states is determined, and the localized surface features and orbital properties of these surface states along Γ-Y-S-X-Γ high symmetry lines of the surface Brillouin zone are discussed. For the Ga-terminated GaAs(311)A (1×1) surface, we have tested two possible structure models, i.e. "the bridge site" and "the hollow site" models. In comparison with the angle-resolved photoelectron spectroscopy studied recently, the results have shown that the surface electronic states of the hollow site model are in good agreement with the experiments, whereas those of the bridge site model are not. So we have concluded that the hollow site model is favourable for the Ga-terminated GaAs(311) (1×1) surface and the bridge site model should be excluded.     

1H NMR relaxation investigation of herbicides interacting with photosystem II preparations fromSpinacia oleracea L.

The interaction of three common herbicides, paraquat, acifluorfen and alachlor, with spinach chloroplast photosystem II (PS II) was investigated by measuring¹H nuclear magnetic resonance spin-lattice relaxation rates, transient nuclear Overhauser effect (NOE) and NOE spectroscopy (NOESY) spectra. Binding to PS II was detected by (i) the enhancement of single-selective relaxation rates and (ii) the decrease in the optimal mixing time providing maximal cross-peak intensity in NOESY spectra. Titration of relaxation enhancements was used to calculate the dissociation constants (K _d) from the bound state for paraquat (K _d = 292 ± 71 μM⁻¹) and acifluorfen (K _d = 311 ± 58 μM⁻¹). A similarK _d was apparent for alachlor. Double-selective relaxation rates allowed the isolation of dipolar relaxation terms between selected proton pairs wherefrom dynamic features of the bound state were evaluated. In all cases the motional correlation time of bound herbicide (τ_c = 0.1−0.4 ns at 300 K) was found two orders of magnitude slower than in the free-solution state. In the case of alachlor the E and Z isomers were observed to bind differently to PS II and a change in conformation could be hypothesized.     

Random walk to and interaction with an impurity

A random walker tagged with a spin may conveniently be studied by small amounts of paramagnetic impurities which significantly affect the spin relaxation at concentrations as low as a few parts per million. Examples are found in nuclear magnetic resonance (NMR) and muon spin rotation (SR). At low temperature relaxation is determined by the time for the walker to reach an impurity, and thus the impurity acts like a simple trap. Details of the interaction with the impurity are important at higher temperatures, and the relaxation rate is shown to go through a maximum because of this. Special features associated with many returns to the origin, particularly important in one-dimensional walks, and the difference between incoherent (rapidly fluctuating paramagnetic spin) and coherent (stationary paramagnetic spin) returns are discussed.Presented at the Symposium on Random Walks, Gaithersburg, MD, June 1982.This work performed at Sandia National Laboratories supported by the U.S. Department of Energy under contract No. DE-AC04-76DP000789.     

Multilayer relaxation of Rh(311)

The multilayer relaxation of the Rh(311) surface was investigated by means of LEED structure determination both for vertical and surface parallel (registry) relaxations. Excellent agreement between experimental and calculated spectra could be achieved mirrored by a minimum Pendry R-factor R = 0.174. The first three layer spacings are oscillatorily relaxed by Δd₁₂/d₀ = −14.5 ± 1.8%, Δd₂₃/d₀ = +4.9 ±2.0% and Δd₃₄/d₀ = −1.0 ±2.0%. There seems to be a coherent registry shift of the fir Δs = 0.03 ± 0.07 Å which, however, is within the error limits of the structure determination. Moreover, an energy dependent inner potential is detected. The results are discussed in comparison to equivalent surfaces of other materials as well as for the less open surfaces of rhodium.     

Nuclear spin-lattice relaxation in the triply rotating frame and ultraslow molecular motions in solids

A method for measuring nuclear magnetic spin-lattice relaxation in solids in the effective field H_e3 acting in the triply rotating frame (TRF) is described. The method advances the previously described techniques whereby nuclear magnetic resonance and relaxation in the rotating (RF) and doubly rotating frames (DRF) are measured directly. In the present work, the RF and DRF are employed for suppressing the secular part of nuclear dipole-dipole (DD) interactions in the first two orders. As a result, the higher-order DD interactions (four- and five-particle ones) were separated, and their contribution to the nuclear spin-lattice relaxation in the TRF was studied experimentally. The experiments were carried out on protons in polycrystalline benzene. With the introduced technique, an overall spin-lattice relaxation decay in the TRF was recorded continuously during a single radio-frequency pulse with a length not exceeding 1 s. The contribution of multiproton nonsecular DD interactions to the proton spin-lattice relaxation in the TRF was observed selectively as a pronounced local minimum in the temperature dependence of the relaxation timeT _1ϱϱϱ. This contribution corresponds to ultraslow motion of benzene molecules with a rate about γH_e3 ≈ 2π · (10¹-10³) s^-1 and is determined quantitatively by specific correlation functions corresponding to the multiparticle nonsecular DD interactions of protons. The prospects of using this method for studying ultraslow atomic and molecular dynamics in solids are discussed.     

First-principles investigation of the surface structures of Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces

Multilayer relaxation at high-index Cu(n, n−1, 0) (n=2, 3 and 4) stepped surfaces was determined by the first-principles pseudopotential plane wave (PPPW) method. For those surfaces that have n and n−1 atom-rows in terrace and subterrace, respectively, the topmost 2n−2 interlayer spacings contract, while the 2n−1st interlayer spacing expands. There is no similar rule found for the relaxations parallel to the surfaces. Compared with the bulk terminated structure, a thin compact layer, which consisted of the topmost 2n−1 atom layers and separated slightly from the underneath atom layers, makes the surface more flat after relaxation. The bond-lengths between the step edge (first layer) atom and its nearest-neighbors do not depend on the surface termination, but only on the local coordination.     

Hyperfine-interaction studies of surfaces

Applications of hyperfine-interaction techniques, like NMR, PAC and Mößbauer spectroscopy, to well-characterized surfaces are discussed and the present knowledge of surface hyperfine fields is reviewed. Measurements of nuclear spin relaxation permit to extract the local density of electron states at the Fermi level of adsorbed alkali atoms. From the observed electric-field-gradient properties surface probe sites and diffusion processes can be inferred; the experimentally determined magnetic hyperfine fields give access to the electron-spin behaviour at magnetic surfaces.     

Cu表面弛豫和自扩散机制的修正嵌入原子法模拟

利用角度修正的嵌入原子方法研究了Cu（100），（110），（111）和（311）等8个面的弛豫，得到了与实验符合较好的结果．然后研究了Cu（100）面上的自扩散机制，得到了与实验和局域密度近似计算相符合的结论．还计算了（110）和（111）面的扩散势垒     

Al表面的多层弛豫——修正嵌入原子势的应用

利用修正的嵌入原子方法计算了Al低指数面（100），（110），（111）和高指数面（210），（211），（310），（311），（331）的多层弛豫，所得到的结果都与实验及第一原理计算结果符合得很好．尤其是这种半经验方法给出了与实验结果相符的Al（100）和（111）表面最外层向外膨胀的理论结果，并提出这种膨胀主要是由于最外层与第二层的键中s态电子增加而p态电子减少引起的． 关键词：     

Molecular motions in chloramphenicol studied by35Cl nuclear quadrupole and1H nuclear magnetic resonance spectroscopy

The³⁵Cl nuclear quadrupole resonance (NQR) frequency (v_Q), nuclear quadrupole spinlattice relaxation time (T_1Q),¹H nuclear magnetic resonance second moment (M₂) and nuclear magnetic spin-lattice relaxation timeT ₁) were measured for polycrystalline chloramphenicol (drug) as a function of temperature. Hindered rotation of the CHC1₂ group and the phenyl ring was detected, the relevant activation energies were determined. The rotations are discussed in detail.     

Molecular properties with dual basis set methods

The dual basis set approach has proven to be very successful for accurately estimating total energies with large basis sets. This study extends the applications of this technique to the calculation of molecular properties, including energy derivatives with respect to nuclear positions and to an external electric field. All energy derivatives have been calculated numerically via finite-differences. Molecular gradients and Hessians as well as dipole moments and polarizabilites have been calculated at the HF and MP2 levels using two alternative versions of the dual basis set method. The accuracy of these approaches is discussed in the context of quality of basis sets used in calculations. It is shown that even quite poor results obtained with the 6-311G basis set are significantly improved in dual basis set calculations with the 6-311G(d,p) and 6-311G(3df,3dp) basis sets.     

Relaxation and electronic states of Au(100), (110) and (111) surfaces

Using a first-principles method based on density functional theory, we investigate the surface relaxation and electronic states of Au(100), (110) and (111) surfaces. The calculated results show that the relaxations of the (100) and (110) surfaces of the metal are inward relaxations. However, the Au(111) surface shows an ‘anomalous’ outward relaxation, although several previous theoretical studies have predicted inward relaxations that are contrary to the experimental measurements. Electronic densities of states and the respective charge density distribution along the Z-axis of the relaxed surfaces are analyzed, and the origin of inward and outward relaxation is discussed in detail.     

Quantum dynamics of ultracold Na+ Na2 collisions

Ultracold collisions between spin-polarized Na atoms and vibrationally excited Na2 molecules are investigated theoretically, using a reactive scattering formalism (including atom exchange). Calculations are carried out on both pairwise additive and nonadditive potential energy surfaces for the quartet electronic state. The Wigner threshold laws are followed for energies below 10(-5) K. Vibrational relaxation processes dominate elastic processes for temperatures below 10(-3)-10(-4) K. For temperatures below 10(-5) K, the rate coefficients for vibrational relaxation (v=1-->0) are 4.8x10(-11) and 5.2x10(-10) cm(3) s(-1) for the additive and nonadditive potentials, respectively. The large difference emphasizes the importance of using accurate potential energy surfaces for such calculations.     

Chromium(III) complexes as intermolecular probes

Metal ion complexes provide flexible paramagnetic centers that may be used to define intermolecular contacts in a variety of solution phase environments because both the charge and electronic relaxation properties of the complex may be varied. For most complex ions, there are several proton equilibria that may change the effective charge on the complex as a function of pH which in turn affects the efficacy of application for defining the electrostatic surfaces of co-solute molecules. We report here spectrophotometric and nuclear spin relaxation studies on aqueous solutions of chromium(III) complexes of EDTA, DTPA, and bis-amides of both. The effective charges available from these paramagnetic centers range from -3 to +1 and we report the pH ranges over which the effective charge is defined with confidence for application in magnetic relaxation experiments.     

Fe(5D/3D)+CH2(1A1)→FeC+H2的理论研究

采用密度泛函理论(DFT)中的UB3LYP方法在6-311 G(2d,2p)水平上研究了五重态和三重态的Fe与单重态CH2反应的机理,在UB3LYP结构优化的基础上用耦合簇理论方法UCCSD(T)在相同水平下对各驻点进行了单点能校正.结果表明,该反应在三重态和五重态上的势能面非常相似,都经过两个过渡态(TS1、TS2)和三个中间体(FeCH2、HFeCH、H2FeC),五重态和三重态势能面在形成中间体FeCH2前发生交叉,整个反应沿三重态路径进行,最后得到三重态的FeC和H2.该反应是一个四步反应,其中由HFeCH到H2FeC的反应步骤为整个反应的速率控制步骤,反应的活化能为176.3 kJ/mol.     

Low-frequency spin fluctuations in Skyrmions confined by wires: measurements of local nuclear spin relaxation

We investigate low-frequency electron spin dynamics in a quantum Hall system with wire confinement by nuclear spin relaxation measurements. We developed a technique to measure the local nuclear spin relaxation rate T(1)(-1). T(1)(-1) is enhanced on both sides of the local filling factor ν(wire)=1, reflecting low-frequency fluctuations of electron spins associated with Skyrmions inside the wire. As the wire width is decreased, the fast nuclear spin relaxation is suppressed in a certain range of Skyrmion density. This suggests that the multi-Skyrmion state is modified and the low-frequency spin fluctuations are suppressed by the wire confinement.     

Theoretical and antimicrobial activity study for ethyl{4-[3-(1H-imidazole-1-yl)propyl]-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl}acetate

Ethyl{4-[3-(1H-imidazole-1-yl)propyl]-3-methyl-5-oxo-4,5-dihydro-1H-1,2,4-triazol-1-yl}-acetate (I) was synthesized as described in the literature and studied by proton and carbon-13 nuclear magnetic resonance, Fourier transform infrared spectroscopic techniques. Theoretical calculations were performed by the density functional method with 6-311G(d,p) and 6-311++G(d,p) basis sets. Structural parameters of compound I, vibrational frequencies, and chemical shift values were determined. The antimicrobial activity of compound I was tested for seven standard bacteria; Staphylococcus aureus, Escherichia coli, Salmonella typhimurium, Yersinia enterocolitica, Listeria monocytogenes, Shigella flexneri, Pseudomonas aeruginosa, and one standard fungi isolate by microdilution broth assay with Alamar Blue Dye. The in vitro results show that compound I has antimicrobial activity against to two standard bacteria, Shigella flexneri and Listeria monocytogenes. And also, the antifungal activity was not detected against selected fungi isolate, Candida tropicalis.     

不同密度氢吸附金刚石(100)表面的微观结构

利用基于广义梯度近似的密度泛函理论,计算了金刚石(100)表面不同氢吸附密度的平衡态几何结构和态密度.结果表明对于2×1构型,在平行和垂直表面两个方向上发生弛豫,而1×1构型仅在垂直表面方向上发生弛豫.另外,清洁2×1,2×1 ∶0.5H和1×1 ∶1.5H表面,带隙中存在空表面态;而对于1×1 ∶2H和2×1 ∶H两种表面结构,空表面态上移进入导带,带隙中不存在表面态.结合电荷密度分布,探讨了金刚石(100)不同构型和氢吸附密度表面的表面态诱发机理. 关键词： 氢吸附 金刚石 弛豫 表面态