Ultrafast interfacial proton-coupled electron transfer

The coupling of electron and nuclear motions in ultrafast charge transfer at molecule-semiconductor interfaces is central to many phenomena, including catalysis, photocatalysis, and molecular electronics. By using femtosecond laser excitation, we transferred electrons from a rutile titanium dioxide (110) surface into a CH3OH overlayer state that is 2.3 +/- 0.2 electron volts above the Fermi level. The redistributed charge was stabilized within 30 femtoseconds by the inertial motion of substrate ions (polaron formation) and, more slowly, by adsorbate molecules (solvation). According to a pronounced deuterium isotope effect (CH3OD), this motion of heavy atoms transforms the reverse charge transfer from a purely electronic process (nonadiabatic) to a correlated response of electrons and protons.     

Ion penetration of the water-Oil interface

Ions typically pass with difficulty from water into organic phases because of water's superior solvation power. This inhibits such processes as ion transport in batteries or in lipid bilayers of cells. Ion penetration across such an interface was studied with unusual structural control. Hydronium ions were soft-landed at 1 electron volt on cold films of 3-methylpentane ("oil") on a metal substrate. The field produced by these ions drove them through the films when warmed. Coadsorption of water (0.14 to 35 bilayers) inhibited the ion penetration by creating a solvation energy trap. A Born solvation model successfully predicted the trapping energies (0 to 38 kilojoules per mole).     

Linear response breakdown in solvation dynamics induced by atomic electron-transfer reactions

The linear response (LR) approximation, which predicts identical relaxation rates from all nonequilibrium initial conditions that relax to the same equilibrium state, underlies dominant models of how solvation influences chemical reactivity. We experimentally tested the validity of LR for the solvation that accompanies partial electron transfer to and from a monatomic solute in solution. We photochemically prepared the species with stoichiometry Na0 in liquid tetrahydrofuran by both adding an electron to Na+ and removing an electron from Na-. Because atoms lack nuclear degrees of freedom, ultrafast changes in the Na0 absorption spectrum reflected the solvation that began from our two initial nonequilibrium conditions. We found that the solvation of Na0 occurs more rapidly from Na+ than Na-, constituting a breakdown of LR. This indicates that Marcus theory would fail to describe electron-transfer processes for this and related chemical systems.     

Spatially Resolved Observation of Static Magnetic Flux States in YBa2Cu3O7-dgr Grain Boundary Josephson Junctions

With low-temperature scanning electron microscopy, the magnetic flux states in high critical temperature Josephson junctions have been imaged. The experiments were performed with YBa(2)Cu(3)O(7-delta) thin-film grain boundary Josephson junctions fabricated on [001] tilt SrTiO(3) bicrystals. For applied magnetic fields parallel to the grain boundary plane, which correspond to local maxima of the magnetic field dependence of the critical current, the images clearly show the corresponding magnetic flux states in the grain boundary junction. The spatial modulation of the Josephson current density by the external magnetic field is imaged directly with a spatial resolution of about 1 micrometer.     

Quantum solvation of carbonyl sulfide with helium atoms

High-resolution infrared and microwave spectra of He(N)-carbonyl sulfide (He(N)-OCS) clusters with N ranging from 2 to 8 have been detected and unambiguously assigned. The spectra show the formation of a solvation layer beginning with an equatorial "donut" of five helium atoms around the OCS molecule. The cluster moment of inertia increases as a function of N and overshoots the liquid droplet limit for N > 5, implying that even atoms in the first solvation shell are decoupled from the OCS rotation in helium nanodroplets. To the extent that this is due to superfluidity, the results directly explore the microscopic evolution of a phenomenon that is formally macroscopic in nature.     

Density fluctuations under confinement: when is a fluid not a fluid?

Knowing the behavior of a fluid in small volumes is essential for the understanding of a vast array of common problems in science, such as biological interactions, fracture propagation, and molecular tribology and adhesion, as well as pressure solvation and other geophysical processes. When a fluid is confined, its phase behavior is altered and excluded-volume effects become apparent. Pioneering measurements performed with the surface forces apparatus have revealed so-called structural or oscillatory solvation forces as well as the occurrence of a finite shear stress, which was interpreted as a solidification transition. Here, we report measurements obtained with an extended surface forces apparatus, which makes use of fast spectral correlation to gain insight into the behavior of a thin film of cyclohexane confined within attoliter volumes, with simultaneous measurement of film thickness and refractive index. With decreasing pore width, cyclohexane is found to undergo a drastic transition from a three-dimensional bulk fluid to a two-dimensional adsorbate with strikingly different properties. Long-range density fluctuations of unexpected magnitude are observed.     

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.     

Extreme ultraviolet observations from the voyager 2 encounter with saturn

Combined analysis of helium (584 angstroms) airglow and the atmospheric occultations of the star delta Scorpii imply a vertical mixing parameter in Saturn's upper atmosphere of K (eddy diffusion coefficient) approximately 8 x 10(7) square centimeters per second, an order of magnitude more vigorous than mixing in Jupiter's upper atmosphere. Atmospheric H(2) band absorption of starlight yields a preliminary temperature of 400 K in the exosphere and a temperature near the homopause of approximately 200 K. The energy source for the mid-latitude H(2) band emission still remains a puzzle. Certain auroral emissions can be fully explained in terms of electron impact on H(2), and auroral morphology suggests a link between the aurora and the Saturn kilometric radiation. Absolute optical depths have been determined for the entire C ring andparts of the A and B rings. A new eccentric ringlet has been detected in the C ring. The extreme ultraviolet reflectance of the rings is fairly uniform at 3.5 to 5 percent. Collisions may control the distribution of H in Titan's H torus, which has a total vertical extent of approximately 14 Saturn radii normal to the orbit plane.     

Subparticle ultrafast spectrum imaging in 4D electron microscopy

Single-particle imaging of structures has become a powerful methodology in nanoscience and molecular and cell biology. We report the development of subparticle imaging with space, time, and energy resolutions of nanometers, femtoseconds, and millielectron volts, respectively. By using scanning electron probes across optically excited nanoparticles and interfaces, we simultaneously constructed energy-time and space-time maps. Spectrum images were then obtained for the nanoscale dielectric fields, with the energy resolution set by the photon rather than the electron, as demonstrated here with two examples (silver nanoparticles and the metallic copper-vacuum interface). This development thus combines the high spatial resolution of electron microscopy with the high energy resolution of optical techniques and ultrafast temporal response, opening the door to various applications in elemental analysis as well as mapping of interfaces and plasmonics.     

The interface phase and the Schottky barrier for a crystalline dielectric on silicon

The barrier height for electron exchange at a dielectric-semiconductor interface has long been interpreted in terms of Schottky's theory with modifications from gap states induced in the semiconductor by the bulk termination. Rather, we show with the structure specifics of heteroepitaxy that the electrostatic boundary conditions can be set in a distinct interface phase that acts as a "Coulomb buffer." This Coulomb buffer is tunable and will functionalize the barrier-height concept itself.     

不同N、P源对红松根/土界面pH及磷有效性影响

用根垫法研究了不同形态N源与P源对红松苗木根/土界面pH及磷有效性的影响.结果表明，铵态N处理使根/土界面pH降低，硝态N处理使根/土界面pH升高.不同N源处理引起根/土界面pH变化的幅度受P源种类及距根面距离的影响，施加矿物P时，铵态N引起的根/土界面pH下降的幅度明显减小.不同P源处理时根/土界面有效P含量受N源种类的影响，铵态N处理时，加入易溶性P近根面处有效P含量显著增加，而加入难溶性P时仅距根面0～2 mm处有效P含量显著增加；硝态N处理时，仅在加入易溶性P时近根面处有效P含量显著增加，而加入难溶性P时，近根面处有效P含量与不加P处理时相近，表明铵态N处理引起的根系分泌质子是根/土界面处难溶性矿物P溶解的主要驱动力.根/土界面处P浓度与苗木叶中P浓度具有较好的相关性.      

Femtosecond dynamics of electron localization at interfaces

The dynamics of two-dimensional small-polaron formation at ultrathin alkane layers on a silver(111) surface have been studied with femtosecond time- and angle-resolved two-photon photoemission spectroscopy. Optical excitation creates interfacial electrons in quasi-free states for motion parallel to the interface. These initially delocalized electrons self-trap as small polarons in a localized state within a few hundred femtoseconds. The localized electrons then decay back to the metal within picoseconds by tunneling through the adlayer potential barrier. The energy dependence of the self-trapping rate has been measured and modeled with a theory analogous to electron transfer theory. This analysis determines the inter- and intramolecular vibrational modes of the overlayer responsible for self-trapping as well as the relaxation energy of the overlayer molecular lattice. These results for a model interface contribute to the fundamental picture of electron behavior in weakly bonded solids and can lead to better understanding of carrier dynamics in many different systems, including organic light-emitting diodes.     

Domain dynamics during ferroelectric switching

The utility of ferroelectric materials stems from the ability to nucleate and move polarized domains using an electric field. To understand the mechanisms of polarization switching, structural characterization at the nanoscale is required. We used aberration-corrected transmission electron microscopy to follow the kinetics and dynamics of ferroelectric switching at millisecond temporal and subangstrom spatial resolution in an epitaxial bilayer of an antiferromagnetic ferroelectric (BiFeO(3)) on a ferromagnetic electrode (La(0.7)Sr(0.3)MnO(3)). We observed localized nucleation events at the electrode interface, domain wall pinning on point defects, and the formation of ferroelectric domains localized to the ferroelectric and ferromagnetic interface. These results show how defects and interfaces impede full ferroelectric switching of a thin film.     

The force needed to move an atom on a surface

Manipulation of individual atoms and molecules by scanning probe microscopy offers the ability of controlled assembly at the single-atom scale. However, the driving forces behind atomic manipulation have not yet been measured. We used an atomic force microscope to measure the vertical and lateral forces exerted on individual adsorbed atoms or molecules by the probe tip. We found that the force that it takes to move an atom depends strongly on the adsorbate and the surface. Our results indicate that for moving metal atoms on metal surfaces, the lateral force component plays the dominant role. Furthermore, measuring spatial maps of the forces during manipulation yielded the full potential energy landscape of the tip-sample interaction.     

Phonons localized at step edges: a route to understanding forces at extended surface defects

Inelastic helium atom scattering has been used to measure the phonons on a stepped metallic crystalline surface, Ni(977). When the scattering plane is oriented parallel to the step edges and perpendicular to the terraces, two branches of step-induced phonons are observed. These branches are identified as transversely polarized, step-localized modes that propagate along the step edge. Analysis reveals significant anisotropy in the force field near the step edge, with all forces near the step edge being substantially smaller than in the bulk. Such measurements provide valuable information on metallic bonding and interface stability near extended surface defects.     

Experiments on the structure of an individual elementary particle

Research begun in the early 1970s on geonium is reviewed. Genoium is a man-made atom, created at liquid-helium temperature in ultrahigh vacuum from an individual electron in magnetic and electric trapping fields. For this atom the electron gyromagnetic ratio g = 2. 000 000 000 110(60) has been measured in microwave spectroscopy experiments after subtraction of quantum electrodynamics shifts. The g - g(Dirac) = 11 x 10(-11) excess over the value g(Dirac) = 2 for the theoretical Dirac point electron suggests for the electron of nature a corresponding excess radius R(e) - R(Dirac) over the Dirac radius R(Dirac) = 0 and a spatial structure. From a plot of measured g and R values for the near-Dirac particles electron, proton, triton, and helium-3 an electron radius R(e) approximately 10(-20) centimeter is extrapolated. In a speculation, the triton-proton-quark model has been extended to the electron, to a succession of subquarks, and finally to the "cosmon." Rapid decay of a cosmon-anticosmon pair created from the "nothing" state in a spontaneous quantum jump initiated the Big Bang.     

Vibrational promotion of electron transfer

By using laser methods to prepare specific quantum states of gas-phase nitric oxide molecules, we examined the role of vibrational motion in electron transfer to a molecule from a metal surface free from the complicating influence of solvation effects. The signature of the electron transfer process is a highly efficient multiquantum vibrational relaxation event, where the nitrogen oxide loses hundreds of kilojoules per mole of energy on a subpicosecond time scale. These results cannot be explained simply on the basis of Franck-Condon factors. The large-amplitude vibrational motion associated with molecules in high vibrational states strongly modulates the energetic driving force of the electron transfer reaction. These results show the importance of molecular vibration in promoting electron transfer reactions, a class of chemistry important to molecular electronics devices, solar energy conversion, and many biological processes.     

Direct observation of chemical bond dynamics on surfaces

The dynamics of chemisorbed species as they swing to-and-fro on their adsorption sites may be directly observed with electron-stimulated desorption. The observation of the thermal disorder in adsorbate chemical bond directions, through studies of the thermal excitation of librational modes, allows one to visualize the potential energy surfaces controlling the structure and dynamics of adsorbates on single crystal metal and semiconductor surfaces. This information may be useful in understanding surface diffusion as well as the spatial aspects of surface chemical reactions.     

Energy dependence of abstractive versus dissociative chemisorption of fluorine molecules on the silicon (111)-(7x7) surface

Scanning tunneling microscopy and monoenergetic molecular beams have been used to obtain real-space atomic images of the competition between abstractive and dissociative chemisorption. The size distribution of Si-F adsorbates on the Si(111)-(7x7) surface was examined as a function of the incident translational energy of the F(2) molecules. For F(2) molecules with 0.03 electron volt of incident energy, the dominant adsorbate sites were isolated Si-F species. As an F(2) molecule with low translational energy collides with the surface, abstraction occurs and only one of the F atoms chemisorbs; the other is ejected into the gas phase. For F(2) molecules with 0.27 electron volt of incident energy, many adjacent Si-F adsorbates (dimer sites) were observed because F(2) molecules with high translational energy collide with the surface and chemisorb dissociatively so that both F atoms react to form adjacent Si-F adsorbates. For halogens with very high incident energy (0.5-electron volt Br(2)), dissociative chemisorption is the dominant adsorption mechanism and dimer sites account for nearly all adsorbates.     

基于体素的森林地区机载LiDAR数据DTM提取

机载LiDAR是一种能够直接、快速获取被测目标三维空间信息的主动式遥感技术,被广泛用于获取高精度的数字地面模型,但是在植被比较密集、地势比较陡峭的森林地区,能够穿透植被到达地表的激光脚点数量较开阔区域少,对于提取精确的DTM有一定难度。该文提出一种继承式多分辨率体素滤波算法,从机载激光扫描数据中获取森林地区的DTM。该方法将激光点云数据划分为不同分辨率等级的体素,以体素为单位通过与邻域体素的高程加权均值比较,剔除植被点,保留地面点,从而获取森林地区的DTM。实验证明该滤波方法能够有效地提取森林地区的DTM。