Structure and bonding of water on Pt(111)

We address the adsorption of water on Pt(111) using x-ray absorption, x-ray emission, and x-ray photoelectron spectroscopy along with calculations in the framework of density functional theory. Using the direct relationship between the electronic structure and adsorbate geometry, we show that in the first layer all the molecules bind directly to the surface and to each other through the in-layer H bonds without dissociation, creating a nearly flat overlayer. The water molecules are adsorbed through alternating metal-oxygen (M-O) and metal-hydrogen (M-HO) bonds.     

Molecular structure of alcohol-water mixtures

We use x-ray emission spectroscopy to elucidate the molecular structure of liquid methanol, water, and methanol-water solutions. We find that molecules in the pure liquid methanol predominantly persist as hydrogen-bonded chains and rings with six and/or eight molecules of equal abundance. For water-methanol solutions we find evidence of incomplete mixing at the microscopic level. Our results provide a new explanation for a smaller entropy increase in the solution due to water molecules bridging methanol chains to form rings.     

X-ray Raman spectroscopic study of water in the condensed phases

Oxygen K-edge x-ray absorption spectra of high-density amorphous (HDA) ice, low-density amorphous ice Ic, ice Ih, normal and deuterated liquid water were measured with the synchrotron x-ray Raman scattering method under almost identical experimental conditions by in situ heating of an HDA ice sample. The distinct preedge structure previously reported in water was observed in all the spectra. The results show that core-hole excitations are localized and not strongly affected by the local environment. Therefore, the existence of the preedge feature is not a concise indicator of the magnitude of local disorder within the hydrogen bonded network. The intensity of the near-edge absorption shifts into the postedge region when the hydrogen bond network becomes more ordered. This observation is interpreted as an enhancement of Wannier over Frenkel excitations in an ordered crystal.     

Direct observation of high-temperature polaronic behavior in colossal magnetoresistive manganites

The temperature dependence of the electronic and atomic structure of the colossal magnetoresistive oxides La1-xSrxMnO3 (x=0.3, 0.4) has been studied using core and valence level photoemission, x-ray absorption and emission, and extended x-ray absorption fine structure spectroscopy. A dramatic and reversible change of the electronic structure is observed on crossing the Curie temperature, including charge localization on and spin-moment increase of Mn, together with Jahn-Teller distortions, both signatures of polaron formation. Our data are also consistent with a phase-separation scenario.     

Properties of liquid silicon observed by time-resolved x-ray absorption spectroscopy

Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.     

Electrons and hydrogen-bond connectivity in liquid water

The network connectivity in liquid water is revised in terms of electronic signatures of hydrogen bonds (HBs) instead of geometric criteria, in view of recent x-ray absorption studies. The analysis is based on ab initio molecular-dynamics simulations at ambient conditions. Even if instantaneous threadlike structures are observed in the electronic network, they continuously reshape in oscillations reminiscent of the and modes in ice (tau approximately 170 fs). However, two water molecules initially joined by a HB remain effectively bound over many periods regardless of its electronic signature.     

Structural ordering in a silica glass matrix under Mn ion implantation

Mn(+)-implanted, amorphous SiO(2) samples were synthesized using pulsed-ion implantation without thermal annealing. The crystal and electronic structures have been studied using x-ray diffraction and synchrotron-based soft x-ray absorption and emission spectroscopy at the Si and Mn L(2,3) edges. We find a combination of small MnO clusters and Si crystallites at shallow depths while tetrahedral Mn coordination is found deeper in the host target. Through a combination of techniques, we find that the implantation process simultaneously decreases the long-range order in the near-surface region and increases order deeper in the SiO(2) host. Our results suggest Mn substitution into Si sites at deep levels catalyzes the formation of α-quartz, providing insight into the complex interactions that determine the local structure around the impurities as well as the overall changes to the crystallinity of implanted SiO(2).     

基于新型超低频拉曼光谱的液态水分子高温研究

液态水是地球上大多数生化过程的化学支柱,对生物的新陈代谢是必不可少的。因此,它是一个跨科学领域的关键课题。水的理化特性被认为是氢键衍生结构的结果。然而,目前还很难在实验上定量地将水分子的理化特性与氢键结构联系起来形成完整的液态水分子结构理论。拉曼光谱因其快速、无损等优点成为表征液态水分子结构及其变化规律的主要手段。目前,水分子的拉曼光谱主要研究的是其高频振动模。然而,液态水较宽的低频拉曼模是氢键及其局部结构效应的结果,包含高频峰无法表征的特征信息,而超低频拉曼特征峰仍能在高温下揭示水分子（超）结构的许多关键细节。因此,在实验上实现对水分子的新型高温超低频拉曼光谱（5～200 cm-1频率区域）,探测得到理论预测的全部四种平动特征模,包括弯曲模（51.7 cm-1）、扭转模（81.4 cm-1）、对称（154.0 cm-1）和不对称拉伸模（188.6 cm-1）,并在225.2 cm-1处额外发现了平动-旋转耦合特征模。所有特征模都被精确指认。高温超低频拉曼光谱实验发现,首先在特征峰频率上,由于高温下氢键断裂导致水分子间的平均结构关联长度（SLG）迅速缩短,当温度从0 ℃升高到400 ℃,所有四种超低频特征模的频率都随温度升高而大幅蓝移。其次在特征峰强度上,拉伸模的强度在100和200 ℃间出现明显降低。而弯曲模的强度随着拉伸模频率从高频率到低频率依次升高,这是理论研究从未涉及的。最后在斯托克斯/反斯托克斯比值（R_S/AS）上,温度在150～170 ℃时（压强约为2 kbar）,R_S/AS迅速从1.1增加到1.3;当温度高于170 ℃时,R_S/AS随温度线性变化。综上所述,通过对水分子各共振模的频率蓝移、强度变化,以及斯托克斯/反斯托克斯比值等特征进行细致研究,得到温度对水分子结构,尤其是氢键衍生特性的影响。该新型高温超低频拉曼光谱方法,填补了部分理论空白,为深入全面地理解水分子结构提供了重要的实验依据。     

How carbon monoxide adsorbs in different sites

The interplay between the electronic and the geometric structure of adsorbates is of fundamental importance for the understanding of many surface phenomena. Using x-ray emission spectroscopy and ab initio cluster calculations, this issue has been investigated in unprecedented detail for CO adsorption in different adsorption sites. The investigation establishes pi bonding and sigma repulsion, both increasing with the number of coordinated metal atoms. The two contributions partly compensate each other, leading to only small differences in adsorption energies for the different adsorption sites despite very large variations in the electronic structure.     

Isotope and temperature effects in liquid water probed by x-ray absorption and resonant x-ray emission spectroscopy

High-resolution x-ray absorption and emission spectra of liquid water exhibit a strong isotope effect. Further, the emission spectra show a splitting of the 1b1 emission line, a weak temperature effect, and a pronounced excitation-energy dependence. They can be described as a superposition of two independent contributions. By comparing with gas phase, ice, and NaOH/NaOD, we propose that the two components are governed by the initial state hydrogen bonding configuration and ultrafast dissociation on the time scale of the O 1s core hole decay.     

Electronic properties of hydrogen storage materials with photon-in/photon-out soft-X-ray spectroscopy

The applications of resonant soft X-ray emission spectroscopy on a variety of carbon systems have yielded characteristic fingerprints. With high-resolution monochromatized synchrotron radiation excitation, resonant inelastic X-ray scattering has emerged as a new source of information about electronic structure and excitation dynamics. Photon-in/photon-out soft-X-ray spectroscopy is used to study the electronic properties of fundamental materials, nanostructure, and complex hydrides and will offer potential in-depth understanding of chemisorption and/or physisorption mechanisms of hydrogen adsorption/desorption capacity and kinetics.     

Specific features of the electronic band structure and x-ray spectra of boron nitride in sphalerite and wurtzite modifications

The electronic band structure of boron nitride compounds with crystal lattices of the sphalerite (c-BN) and wurtzite (w-BN) types is calculated by the local coherent potential method in the cluster muffin-tin approximation within the framework of the multiple scattering theory. The local partial densities of 2p states for boron and nitrogen in c-BN and w-BN modifications are compared with the experimental boron and nitrogen K x-ray emission spectra and band-structure calculations. A comparison of the total densities of states in c-BN and w-BN with the x-ray photoelectron spectra and the band calculations has revealed both similarities and differences in the electronic structures of these modifications. The fine structure in the vicinity of the valence band top of boron nitride in different crystal modifications is theoretically calculated for the first time. The specific features of the electronic structure and the x-ray spectra of boron nitride in different modifications are discussed.     

Time resolved spectroscopy with femtosecond soft-x-ray pulses

The most challenging application of time resolved spectroscopy is to directly observe the structural and electronic dynamics. Here we present the combination of x-ray absorption spectroscopy with laser driven x-ray sources, offering atomic spatial and temporal resolution. Our new approaches for optimization of laser driven x-ray sources resulted in the demonstration of spatially coherent sub-20 fs x-ray pulses in a range up to several keV. We excited polycrystalline silicon with an ultrashort laser pulse and characterized the collective motion of atoms with time resolved x-ray absorption spectroscopy at a temporal resolution of less than 20 fs. Finally, we have shown the feasibility of probing the dynamics of the electronic structure of silicon and carbon with near edge x-ray absorption spectroscopy.     

Nature of the high-pressure transition in Fe2O3 hematite

We present a new method to separate the crystallographic and electronic phase transitions in hematite using x-ray emission spectroscopy and x-ray diffraction. Our observations, based on the behavior of a metastable high-pressure phase in the stability domain of the low-pressure phase, show that the electronic transition is preempted by the crystallographic transition. The former occurs only afterwards in the high-pressure phase, possibly as a result of a Mott transition. The idea that the electronic transition drives the transition in hematite is therefore invalidated. Such methods should help elucidate the mechanics and the driving forces behind a number of first-order high-pressure phase transitions.     

Metal-induced gap states at well defined alkali-halide/metal interfaces

In order to search for states specific to insulator/metal interfaces, we have studied epitaxially grown interfaces with element-selective near edge x-ray absorption fine structure. An extra peak is observed below the bulk edge onset for LiCl films on Cu and Ag substrates. The nature of chemical bonds as probed by x-ray photoemission spectroscopy and Auger electron spectroscopy remains unchanged, so we regard this as evidence for metal-induced gap states (MIGS) formed by the proximity to a metal, rather than local bonds at the interface. The dependence on the film thickness shows that the MIGS are as thin as one monolayer. An ab initio electronic structure calculation supports the existence of the MIGS that are strongly localized at the interface.     

Extended X-Ray absorption fine structure from hydrogen atoms in water

We report the first quantitative measurement of extended x-ray absorption fine structure (EXAFS) from hydrogen atoms. A single oscillation is observed from gaseous water consistent with the location of the covalently bonded hydrogen in H 2O. The experimental phase and amplitude of the oscillation are in excellent agreement with curved wave multiple scattering calculations for isolated water molecules. With this determination of the O-H scattering phase shift we have quantified the covalent hydrogen bond distance (0.95+/-0.03 A) in liquid water, thus demonstrating that hydrogen EXAFS can become a valuable complement to existing structural methods in chemistry and biology.     

Effect of pressure on magnetoelastic coupling in 3d metal alloys studied with x-ray absorption spectroscopy

Using x-ray absorption spectroscopy, we have studied the effect of pressure on femtometer-scale bond strain due to anisotropic magnetostriction in a thin FeCo film. At 7 GPa local magnetostrictive strain is found to be larger than at ambient, in agreement with spin-polarized ab initio electronic structure calculations, but contrary to the expected effect of compression on bond stiffness. The availability of high pressure data on local magnetostrictive strain opens new capabilities for validating theoretical predictions and can lead to the development of materials with the desired properties.     

液态水微观结构研究的新进展

液态水有很多奇异特性.近年来,对液态水以何种微观结构形式存在的问题争议激烈.文章介绍了当前对水的微观结构的一些研究及其进展,讨论了液态水中的氢键模式与水的结构关系,进而用一个简化模型探讨了氢键的取向性与强弱性对水的异常行为的作用.