Electronic structure and catalytic behavior of tungsten carbide

Tungsten carbide has been shown to be an effective catalyst for a number of reactions that are readily catalyzed by platinum, but not at all by tungsten, and it was speculated that this behavior is due to changes in the electron distribution when carbon is added to tungsten. A test of this hypothesis, made by measuring the valence band x-ray photoelectron spectrum of tungsten carbide and comparing it with the spectra of tungsten and platinum, shows that, near the Fermi level, the electronic density of states of tungsten carbide more nearly resembles that of platinum than that of tungsten.     

Hydrated electron dynamics: from clusters to bulk

The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 eaq-(s(dagger)) internal conversion lifetime.     

Direct spectroscopic detection of a zwitterionic excited state

Two electrons in two weakly coupled orbitals give rise to two states (diradical) with electrons residing in separate orbitals and two states (zwitterionic) with both electrons paired in one orbital or the other. This two-electron, two-orbital state manifold has eluded experimental confirmation because the zwitterionic states have been difficult to locate. Two-photon excitation of fluorescence from Mo(2)CI(4)(PMe(3))(4) (D2d) has been measured with linearly and circularly polarized light. From the polarization ratio and the energy of the observed transition, the 2(1)A(1) (delta*delta*) excited state has been located and characterized. In conjunction with the one-photon allowed (1)B(2) (deltadelta*) excited state, the zwitterionic state manifold for the quadruply bonded metal-metal class of compounds is thus established.     

Characterization of excess electrons in water-cluster anions by quantum simulations

Water-cluster anions can serve as a bridge to understand the transition from gaseous species to the bulk hydrated electron. However, debate continues regarding how the excess electron is bound in (H2O)-n, as an interior, bulklike, or surface electronic state. To address the uncertainty, the properties of (H2O)-n clusters with 20 to 200 water molecules have been evaluated by mixed quantum-classical simulations. The theory reproduces every observed energetic, spectral, and structural trend with cluster size that is seen in experimental photoelectron and optical absorption spectra. More important, surface states and interior states each manifest a characteristic signature in the simulation data. The results strongly support assignment of surface-bound electronic states to the water-cluster anions in published experimental studies thus far.     

Wet electrons at the H2O/TiO2(110) surface

At interfaces of metal oxide and water, partially hydrated or "wet-electron" states represent the lowest energy pathway for electron transfer. We studied the photoinduced electron transfer at the H2O/TiO2(110) interface by means of time-resolved two-photon photoemission spectroscopy and electronic structure theory. At approximately 1-monolayer coverage of water on partially hydroxylated TiO2 surfaces, we found an unoccupied electronic state 2.4 electron volts above the Fermi level. Density functional theory shows this to be a wet-electron state analogous to that reported in water clusters and which is distinct from hydrated electrons observed on water-covered metal surfaces. The decay of electrons from the wet-electron state to the conduction band of TiO2 occurs in 相似文献   

纳米纤维素表面烷基化特性的研究

用表面烷基化的方法降低纳米纤维素表面的亲水性,并通过傅里叶红外光谱、X 射线衍射、X 射线光电子能 谱、扫描电子显微镜及能谱分析对烷基化后的纳米纤维素进行了测定。结果表明:KH鄄570 和纳米纤维素之间发生 了偶联反应,随着偶联剂浓度的升高,纳米纤维素的结晶度先下降后上升;硅醇或部分缩合的硅醇包覆在纳米纤维 素的表面,从而使烷基化纤维素的碳氧比下降;烷基化能使纳米纤维素表面的羟基量减少,降低了纳米纤维素表面 的亲水性;硅烷偶联剂与纳米纤维素发生了偶联反应,且反应程度一致,纳米纤维素表面烷基化均一。      

The transition state of the f + h2 reaction

The transition state region of the F + H(2) reaction has been studied by photoelectron spectroscopy of FH(2)(-). New para and normal FH(2)(-)photoelectron spectra have been measured in refined experiments and are compared here with exact three-dimensional quantum reactive scattering simulations that use an accurate new ab initio potential energy surface for F + H(2). The detailed agreement that is obtained between this fully ab initio theory and experiment is unprecedented for the F + H(2) reaction and suggests that the transition state region of the F + H(2) potential energy surface has finally been understood quantitatively.     

Correlations between ground and excited state spectra of a quantum Dot

The ground and excited state spectra of a semiconductor quantum dot with successive electron occupancy were studied with linear and nonlinear magnetoconductance measurements. A direct correlation was observed between the mth excited state of the N-electron system and the ground state of the (N + m)-electron system for m up to 4. The results are consistent with a single-particle picture in which a fixed spectrum of energy levels is successively filled, except for a notable absence of spin degeneracy. Further departures from the single-particle picture due to electron-electron interaction were also observed. Magnetoconductance fluctuations of ground states show anticrossings where wave function characteristics are exchanged between adjacent levels.     

Resonating valence-bond ground state in a phenalenyl-based neutral radical conductor

An organic material composed of neutral free radicals based on the spirobiphenalenyl system exhibits a room temperature conductivity of 0.3 siemens per centimeter and a high-symmetry crystal structure. It displays the temperature-independent Pauli paramagnetism characteristic of a metal with a magnetic susceptibility that implies a density of states at the Fermi level of 15.5 states per electron volt per mole. Extended Hückel calculations indicate that the solid is a three-dimensional organic metal with a band width of approximately 0.5 electron volts. However, the compound shows activated conductivity (activation energy, 0.054 electron volts) and an optical energy gap of 0.34 electron volts. We argue that these apparently contradictory properties are best resolved in terms of the resonating valence-bond ground state originally suggested by Pauling, but with the modifications introduced by Anderson.     

Pseudogaps and extrinsic losses in photoemission experiments on poorly conducting solids

A photoelectron emitted from a conducting solid may suffer a substantial energy change through ohmic losses that can drastically alter the line shape on the millielectron volt scale that is now observable through improved resolution. Almost all of this energy loss occurs after the electron leaves the solid. These losses are expected to be important in isotropic materials with relatively low conductivity, such as certain colossal magnetoresistance manganates, and in very electrically anisotropic materials, such as one-dimensional conductors, and may also affect interpretation of photoemission in superconductors with high transition temperatures. The electric field of the photoelectron can penetrate the solid, and extrinsic losses of this type can mimic pseudogap effects and other peculiar features of photoemission in cubic manganates, as illustrated for La0.67Ca0.33MnO3.     

SF~n（n=-1,0,＋1）分子离子基态Murell-Sorbie势能函数的计算

基于Gaussian03软件包,利用密度泛函理论的B3P68方法,选用多种基组对SFn(n=-1,0,+1)分子离子基态进行几何优化和频率计算.优选出6-311g(3df),6-311++g(3df),D95++(3df)基组,进一步对SF分子和SF+,SF-分子离子基态进行单点能扫描计算.采用最小二乘法拟合得到SFn(n=-1,0,+1)分子离子基态的Murell-Sorbie势能函数.首次给出SFn(n=-1,0,+1)分子离子基态力常数(Re),完善了光谱参数(Be,αe,ωe,ωexe)的理论值,为SFn(n=-1,0,+1)分子离子基态的后期研究提供重要的参考.     

Frequency metrology in quantum degenerate helium: direct measurement of the 2 3S1 --> 2 1S0 transition

Precision spectroscopy of simple atomic systems has refined our understanding of the fundamental laws of quantum physics. In particular, helium spectroscopy has played a crucial role in describing two-electron interactions, determining the fine-structure constant and extracting the size of the helium nucleus. Here we present a measurement of the doubly forbidden 1557-nanometer transition connecting the two metastable states of helium (the lowest energy triplet state 2 (3)S(1) and first excited singlet state 2 (1)S(0)), for which quantum electrodynamic and nuclear size effects are very strong. This transition is weaker by 14 orders of magnitude than the most predominantly measured transition in helium. Ultracold, submicrokelvin, fermionic (3)He and bosonic (4)He atoms are used to obtain a precision of 8 × 10(-12), providing a stringent test of two-electron quantum electrodynamic theory and of nuclear few-body theory.     

具有内部交易的多头交易博弈

进行了8种坡度下单个三维山体的模型风洞试验，讨论了山体各位置脉动风速谱的变化规律，以及坡度对脉动风速谱的影响.结果表明：背风面山脚0.8 h高度以下位置，脉动风速功率谱与来流风速谱相比，功率谱峰值明显增大，峰值频率向高频移动，单峰特征明显，频带变窄.除此以外的背风面其他位置、迎风面以及山顶位置的脉动风速功率谱与来流风速谱基本一致.提出了山体背风面脉动风速能量由来流湍流能量和山体尾流涡旋能量构成的思想，将来流脉动风速谱与涡旋谱进行分离，并根据试验数据拟合，提出了保守的涡旋谱的计算公式.根据不同坡度山体的试验，得出了0.5为涡旋产生与否的临界坡度.     

Structural and Electronic Role of Lead in (PbBi)2Sr2CaCu2O8 Superconductors by STM

The structural and electronic effects of lead substitution in the high-temperature superconducting materials Pb(x)Bi(2-x)Sr(2)CaCu(2)O(8) have been characterized by scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Large-area STM images of the Bi(Pb)-O layers show that lead substitution distorts and disorders the one-dimensional superlattice found in these materials. Atomic-resolution images indicate that extra oxygen atoms are present in the Bi(Pb)-O layers. STS data show that the electronic structure of the Bi(Pb)-O layers is insensitive to lead substitution within +/-0.5 electron volt of the Fermi level; however, a systematic decrease in the density of states is observed at approximately 1 electron volt above the Fermi level. Because the superconducting transition temperatures are independent of x(Pb) (x 相似文献   

肌注氟苯尼考在鸭疫里氏杆菌感染鸭体内的药动学特征

【目的】研究并比较肌注氟苯尼考在2周龄健康和鸭疫里氏杆菌感染鸭体内的药代动力学特征。【方法】240只鸭随机分为2组,各120只鸭,其中一组用鸭疫里氏杆菌腿部感染,分别以30 mg·kg~(-1)体重单剂量肌内注射氟苯尼考,采血点为给药前和给药后5、10、15、20、30、45 min和1、1.5、2、4、8、10、14 h。采用高效液相色谱法(HPLC)测定血浆氟苯尼考的浓度,采用紫外检测器检测,检测波长为223 nm,流动相为乙腈和水,其体积比为26和74,流速为1 m L·min-1,色谱柱为Agilent C18(4.6 mm×150 mm,5μm),进样量为20μL。药动学分析软件Win Nonlin 5.2.1以非房室模型拟合处理血药浓度-时间数据,计算相关的药动学参数,并用统计学软件SPSS17.0对药动学参数进行t检验统计学分析。【结果】氟苯尼考在健康鸭体内的峰浓度(Cmax)为(22.88±3.11)μg·m L-1,表观分布容积(Vd/F)为(2.39±0.81)L·kg~(-1),体清除率(ClB/F)为(0.64±0.11)L·h-1·kg~(-1),消除半衰期(t1/2β)为(2.57±0.51)h和药时曲线下面积(AUC)为(47.28±7.87)μg·m L-1·h;氟苯尼考在感染鸭体内的峰浓度(Cmax)为(19.77±1.82)μg·m L-1,表观分布容积(Vd/F)为(2.44±0.46)L·kg~(-1),体清除率(ClB/F)为(0.63±0.08)L·h-1·kg~(-1),消除半衰期(t1/2β)为(2.74±0.54)h和药时曲线下面积(AUC)为(48.11±6.62)μg·m L-1·h。统计分析氟苯尼考在健康鸭和感染鸭的药动学参数,结果表明,除了Cmax差异显著(P0.05),其他参数差异均不显著(P0.05)。【结论】两者的主要药动学参数相比较,感染鸭体内的Cmax显著低于(P0.05)健康鸭体内的C_(max),其他参数无显著性差异。氟苯尼考以30 mg·kg~(-1)体重肌内注射在健康和感染鸭体内具有吸收迅速,峰浓度高,体内分布广泛,消除较快的特点。     

Electron solvation in finite systems: femtosecond dynamics of iodide. (Water)n anion clusters

Electron solvation dynamics in photoexcited anion clusters of I-(D2O)n=4-6 and I-(H2O)4-6 were probed by using femtosecond photoelectron spectroscopy (FPES). An ultrafast pump pulse excited the anion to the cluster analog of the charge-transfer-to-solvent state seen for I- in aqueous solution. Evolution of this state was monitored by time-resolved photoelectron spectroscopy using an ultrafast probe pulse. The excited n = 4 clusters showed simple population decay, but in the n = 5 and 6 clusters the solvent molecules rearranged to stabilize and localize the excess electron, showing characteristics associated with electron solvation dynamics in bulk water. Comparison of the FPES of I-(D2O)n with I-(H2O)n indicates more rapid solvation in the H2O clusters.     

A Rotationally Resolved Fluorescence Excitation Spectrum of all-trans-1,4-Diphenyl-1,3-butadiene

Band 1 in the jet-cooled one-photon S(1) <-- S(0) fluorescence excitation spectrum of all-trans-1,4-diphenyl-1,3-butadiene has been rotationally resolved with a molecular beam laser spectrometer. Both the orientation of the optical transition moment and the rotational constants of the two vibronic levels have been measured. The molecule shows no evidence of being significantly distorted from a C(24) geometry when it is low in the vibrational manifolds of either of the two electronic states.     

Quantum point contact switches

Switching behavior between electron tunneling and ballistic transport states was induced by repeatedly bringing a sharpened nickel wire into contact with a gold surface. The high-conductivity ballistic state had a quantized conductance of 0.977 +/- 0.015 (2e(2)/h). Switching was accomplished by moving the electrodes with a piezoelectric actuator over a distance of 2 angstroms. The two electrodes and the actuator form a three-terminal device that is demonstrated to be a reliable digital and analog switch; it shows good discrimination between high and low states and possesses the important property of power gain. The conductance channel is most likely only one atom wide and possibly consists of a single atom.     

Quantum-well states as fabry-Perot modes in a thin-film electron interferometer

Angle-resolved photoemission from atomically uniform silver films on iron (100) shows quantum-well states for absolutely determined film thicknesses ranging from 1 to approximately 100 monolayers. These states can be understood in terms of Fabry-Perot modes in an electron interferometer. A quantitative line shape analysis over the entire two orders of magnitude of thickness range yields an accurate measurement of the band structure, quasiparticle lifetime, electron reflectivity, and phase shift. Effects of confinement energy gap, reflection loss, and surface scattering caused by controlled roughness are demonstrated.     

A paramagnetic bonding mechanism for diatomics in strong magnetic fields

Elementary chemistry distinguishes two kinds of strong bonds between atoms in molecules: the covalent bond, where bonding arises from valence electron pairs shared between neighboring atoms, and the ionic bond, where transfer of electrons from one atom to another leads to Coulombic attraction between the resulting ions. We present a third, distinct bonding mechanism: perpendicular paramagnetic bonding, generated by the stabilization of antibonding orbitals in their perpendicular orientation relative to an external magnetic field. In strong fields such as those present in the atmospheres of white dwarfs (on the order of 10(5) teslas) and other stellar objects, our calculations suggest that this mechanism underlies the strong bonding of H(2) in the (3)Σ(u)(+)(1σ(g)1σ(u)*) triplet state and of He(2) in the (1)Σ(g)(+)(1σ(g)(2)1σ(u)(*2)) singlet state, as well as their preferred perpendicular orientation in the external field.