Diffraction Photoelectron Research Articles

Click preparation of multiple-thioether bridged cyclodextrin chiral materials for efficient enantioseparation in high-performance liquid chromatography.

A highly efficient covalent immobilization procedure is considered as an essential tool for obtaining stable and reliable cyclodextrin (CD) chiral stationary phases (CSPs). This work reports the "thiolene" click immobilization of heptakis(6-mercapto-6-deoxy)-β-CD-CSP onto alkene functional silica to afford novel multiple-thioether bridged CD CSPs by controlling the surface CD concentration. Solid-state NMR, FTIR, TGA and X-ray photoelectron diffraction spectroscopy (XPS) results proved the successful preparation of the desired CSPs with different surface CD loadings. The surface CD concentrations were calculated to be 0.49 and 0.68 μmol m-2 according to the elemental analysis results. More than 60 chiral enantiomers including isoxazolines, chiral lactides, chiral ketones, dansyl amino acids, small molecule acids and alkalis as well as some flavonoids were resolved or partially separated in the reversed-phase HPLC mode. Compared with the previously prepared single thiolene bridged CD-CSP, the current multiple-thioether CD-CSP afforded much better enantioseparation ability due to the existence of the thiol moiety and a confined structure.

Imaging intramolecular hydrogen migration with time- and momentum-resolved photoelectron diffraction.

Imaging ultrafast hydrogen migration with few- or sub-femtosecond time resolution is a challenge for ultrafast spectroscopy due to the lightness and small scattering cross-section of the moving hydrogen atom. Here we propose time- and momentum-resolved photoelectron diffraction (TMR-PED) as a way to overcome limitations of existing methodologies and illustrate its performance in the ethanol molecule. By combining different theoretical methods, namely molecular dynamics and electron scattering methods, we show that TMR-PED, along with a judicious choice of the reference frame for multi-coincidence detection, allows for direct imaging of single and double hydrogen migration in doubly-charged ethanol with both few-fs and Å resolutions, all the way from its birth to the very end. It also provides hints of proton extraction following H2 roaming. The signature of hydrogen dynamics shows up in polarization-averaged molecular-frame photoelectron angular distributions (PA-MFPADs) as moving features that allow for a straightforward visualization in space.

Hard X-ray Photoelectron Diffraction Applied to the System Pyrite (FeS2) for Direct Atom Imaging by means of Chemical Sensitive Photoelectron Holography : proof of principle study

Hard X-ray Photoelectron Diffraction Applied to the System Pyrite (FeS₂) for Direct Atom Imaging by means of Chemical Sensitive Photoelectron Holography : proof of principle study

Surface relaxation and rumpling of Sn-doped β−Ga2O3(010)

We have studied the surface structure of single-crystal, wide-gap semiconductor $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}(010)$ using x-ray photoelectron diffraction (XPD), low-energy electron diffraction (LEED), and x-ray photoelectron spectroscopy (XPS). The XPS measurements show typical spectra for stoichiometric ${\mathrm{Ga}}_{2}{\mathrm{O}}_{3}(010)$. Annealing in vacuum produced a sharp ($1\ifmmode\times\else\texttimes\fi{}1$) LEED pattern, characteristic of the monoclinic structure. The XPD angular anisotropies were collected for the Ga $2{p}_{3/2}$ and O $1s$ core levels. Surface interlayer relaxation up to 8% of the bulk interplanar distance and 0.11--0.14 $\AA{}$ rumpling are observed at the $\ensuremath{\beta}\text{\ensuremath{-}}{\mathrm{Ga}}_{2}{\mathrm{O}}_{3}(010)$ surface. At the surface, the oxygen atoms shift toward the vacuum with respect to the gallium atoms. The rumpling decreases to zero and and the interplanar distance reaches the bulk value of 1.52 $\AA{}$ by the sixth atomic layer. The surface structure agrees with that predicted by first-principles density functional theory calculations which, in addition, suggest a significant band gap narrowing of $\ensuremath{\approx}1$ eV in the surface layer, due to surface states spatially localized on surface oxygen atoms of ${\mathrm{O}}_{\mathrm{II}}$ type.

Selecting ‘convenient observers’ to probe the atomic structure of CVD graphene on Ir(111) via photoelectron diffraction

CVD graphene grown on metallic substrates presents, in several cases, a long-range periodic structure due to a lattice mismatch between the graphene and the substrate. For instance, graphene grown on Ir(111), displays a corrugated supercell with distinct adsorption sites due to a variation of its local electronic structure. This type of surface reconstruction represents a challenging problem for a detailed atomic surface structure determination for experimental and theoretical techniques. In this work, we revisited the surface structure determination of graphene on Ir(111) by using the unique advantage of surface and chemical selectivity of synchrotron-based photoelectron diffraction. We take advantage of the Ir 4f photoemission surface state and use its diffraction signal as a probe to investigate the atomic arrangement of the graphene topping layer. We determine the average height and the overall corrugation of the graphene layer, which are respectively equal to 3.40 ± 0.11 Å and 0.45 ± 0.03 Å. Furthermore, we explore the graphene topography in the vicinity of its high-symmetry adsorption sites and show that the experimental data can be described by three reduced systems simplifying the moiré supercell multiple scattering analysis.

Photoelectron diffraction for probing valency and magnetism of 4f -based materials: A view on valence-fluctuating EuIr2Si2

We present and discuss the methodology for modeling $4f$ photoemission spectra, $4f$ photoelectron diffraction (PED) patterns, and magnetic dichroism effects for rare-earth-based materials. Using PED and magnetic dichroism in photoemission, we explore the electronic and magnetic properties of the near-surface region of the valence-fluctuating material ${\mathrm{EuIr}}_{2}{\mathrm{Si}}_{2}$. For the Eu-terminated surface, we found that the topmost Eu layer is divalent and exhibits a ferromagnetic order below 10 K. The valency of the next Eu layer, that is the fifth atomic layer, is about 2.8 at low temperature that is close to the valency in the bulk. The properties of the Si-terminated surface are drastically different. The first subsurface Eu layer (fourth atomic layer below the surface) behaves divalently and orders ferromagnetically below 48 K. Experimental data indicate, however, that there is an admixture of trivalent Eu in this layer, resulting in its valency of about 2.1. The next deeper lying Eu layer (eighth atomic layer below the surface) behaves mixed valently, but the estimated valency of 2.4 is notably lower than the value in the bulk. The presented approach and obtained results create a background for further studies of exotic surface properties of $4f$-based materials, and allow us to derive information related to valency and magnetism of individual rare-earth layers in a rather extended area near the surface.

Atomic and Electronic Structure of a Multidomain GeTe Crystal.

Renewed interest in the ferroelectric semiconductor germanium telluride was recently triggered by the direct observation of a giant Rashba effect and a 30-year-old dream about a functional spin field-effect transistor. In this respect, all-electrical control of the spin texture in this material in combination with ferroelectric properties at the nanoscale would create advanced functionalities in spintronics and data information processing. Here, we investigate the atomic and electronic properties of GeTe bulk single crystals and their (111) surfaces. We succeeded in growing crystals possessing solely inversion domains of ∼10 nm thickness parallel to each other. Using HAADF-TEM we observe two types of domain boundaries, one of them being similar in structure to the van der Waals gap in layered materials. This structure is responsible for the formation of surface domains with preferential Te-termination (∼68%) as we determined using photoelectron diffraction and XPS. The lateral dimensions of the surface domains are in the range of ∼10-100 nm, and both Ge- and Te-terminations reveal no reconstruction. Using spin-ARPES we establish an intrinsic quantitative relationship between the spin polarization of pure bulk states and the relative contribution of different terminations, a result that is consistent with a reversal of the spin texture of the bulk Rashba bands for opposite configurations of the ferroelectric polarization within individual nanodomains. Our findings are important for potential applications of ferroelectric Rashba semiconductors in nonvolatile spintronic devices with advanced memory and computing capabilities at the nanoscale.

Electrochemical Aspects of a Nitrogen-Doped Pseudo-Graphitic Carbon Material: Resistance to Electrode Fouling by Air-Aging and Dopamine Electro-Oxidation

The nitrogen-doped form of GUITAR (pseudo-Graphite from the University of Idaho Thermalized Asphalt Reaction) was examined by X-ray photoelectron, Raman, and X-ray diffraction spectroscopies and cyclic voltammetry (CV). Electrochemical studies indicate that N-GUITAR exhibits significant resistance to fouling by adsorption and by passivation. Unlike other carbon materials, it maintains fast heterogenous electron transfer (HET) kinetics with Fe(CN)63−/4− with exposure to air. The CV peak potential separation (ΔEp) of 66 mV increased to 69 mV in 3 h vs. 67 to 221 mV for a highly oriented pyrolytic graphite (HOPG) electrode. Water contact angle measurements indicate that N-GUITAR was able to better maintain a hydrophilic state during the 3-h exposure, going from 55.8 to 70.4° while HOPG increased from 63.8 to 80.1°. This indicates that N-GUITAR better resisted adsorption of volatile organic compounds. CV studies of dopamine also indicate N-GUITAR is resistant to passivation. The ΔEp for the dopamine/o-dopaminoquinone couple is 83 mV indicating fast HET rates. This is reflected in the peak current ratios for the oxidation and reduction processes of 1.3 indicating that o-dopaminoquinone is not lost to passivation processes. This ratio along with the minimal signal attenuation is the best reported in literature.

Emitter-site specificity of hard x-ray photoelectron Kikuchi-diffraction

High-resolution full-field imaging of (kx, ky) photoelectron distributions (k-resolution 0.03 Å−1, angular resolution 0.03° at 6.7 keV) in a large field of view (up to 16 Å−1 dia.) allows to observe fine details in Kikuchi-type diffractograms. Alongside with the element specificity via core-level spectra, this method opens a new avenue to structural analysis using hard x-ray photoelectron diffraction (hXPD). Here we present a theoretical study of the emitter-site specificity by simulating hXPD patterns for arbitrary positions of emitter atoms in the unit cell. Using the Bloch wave approach to photoelectron diffraction from lattice planes, the diffraction patterns from a number of positions in the unit cell can be obtained simultaneously exploiting the reciprocity theorem. Simulations for dopant atoms and dopant multimers (dimers, trimers, clusters) in the Si lattice at various positions in the unit cell reveal a strong site-sensitivity in terms of dramatic changes in the diffraction patterns with emitter-atom position. The results are compared with measurements for Si hyperdoped with Te.

Time-resolved X-ray photoelectron diffraction using an angle-resolved time-of-flight electron analyzer

X-ray photoelectron diffraction (XPD) provides atomic resolution, element sensitive local structure information about the surfaces and interfaces of materials. In the work reported in this paper, a two-dimensional angle resolved time-of-flight (2DARTOF) system is used to perform time-resolved XPD experiments on epitaxial silicene. The two Si 2p peak components from the different atomic sites in the silicene layer allow extraction of the individual XPD patterns. Time-resolved measurements captured small angle shifts in the forward focusing peak, indicating laser-induced changes in the silicene structure. At 10 ns, the XPD patterns appear to relax back to the equilibrium state. This work demonstrates that 2DARTOF systems are well suitable for time-resolved XPD measurements.

“Storage-Discharge” Ethanol Cold Plasma for Synthesizing High Performance Pd/Al2O3 Catalysts

Atmospheric pressure cold plasma is an environmentally friendly and novel method to synthesize supported metal catalysts, which usually uses active hydrogen species to reduce metal ions. Ethanol is a hydrogen-rich renewable liquid hydrogen source, and it is more convenient to store and transport than H2. In this study, a “storage-discharge” ethanol cold plasma was used to prepare Pd/Al2O3-EP catalysts, and the obtained catalysts are used for CO oxidation. The complete oxidation of CO temperature (T100) over Pd/Al2O3-EP was 145 °C, which was comparable to the performance of Pd/Al2O3-HP that was synthesized by atmospheric pressure hydrogen cold plasma. Pd/Al2O3-EP-C obtained by calcining Pd/Al2O3-EP at 450 °C for 2 h in air atmosphere in order to remove residual carbon species showed much higher CO oxidation activity, and T100 was 130 °C. The Pd/Al2O3 catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron diffraction (XPS), Brunauer–Emmett–Teller (BET), and transmission electron microscopy (TEM), and the structure-performance relationship was analyzed. The results indicate that the “storage-discharge” ethanol cold plasma can reduce the Pd precursor ions into metallic Pd state, and the dissociation of ethanol forms lots of highly active chemisorbed oxygen species, which can enhance the performance of Pd/Al2O3-EP for CO oxidation. In contrast, Pd/Al2O3-EP-C shows much higher CO oxidation activity, which is mainly attributed to the removal of the residual carbon species, and the exposure of more Pd active sites and chemisorbed oxygen species. The “storage-discharge” ethanol cold plasma is a safe and efficient novel method for synthesizing supported Pd catalysts, and it has important potential for the preparation and application of supported metal catalysts.

Targeted research on the single role of lithium Bis(oxalate)borate in the film-forming process through a novel lithium salt-free electrolyte system

A blank comparison group of lithium salt-free electrolyte system, replacing the lithium salt of electrolyte with a redox shuttle agent, is constructed to give targeted research on the single role of lithium bis(oxalate)borate (LiBOB) salt, especially of bis(oxalate)borate anions (BOB−) in the film-forming process. By combining and comparing all available studies, such as attenuated total reflectance (IR-ATR), X-Ray photoelectron diffraction spectrum (XPS), electrochemical impedance spectrum (EIS), scanning electron microscopy (SEM) tests and quantum chemical calculation, the formation mechanism of the solid electrolyte interphase (SEI) film is proposed. Results reveal that the prior reduction of BOB− anions can postpone the reduction potential and hinder the decomposition rate of carbonate solvents, but promote the formation of a dense, conductive and effective SEI film. This work provides a novel way to investigate the film-forming mechanism and has guiding significance for revealing the effect of other kinds of lithium salts on the surface film formation.

Photoelectron Diffraction Imaging of a Molecular Breakup Using an X-Ray Free-Electron Laser

Author(s): Kastirke, G; Schoffler, MS; Weller, M; Rist, J; Boll, R; Anders, N; Baumann, TM; Eckart, S; Erk, B; De Fanis, A; Fehre, K; Gatton, A; Grundmann, S; Grychtol, P; Hartung, A; Hofmann, M; Ilchen, M; Janke, C; Kircher, M; Kunitski, M; Li, X; Mazza, T; Melzer, N; Montano, J; Music, V; Nalin, G; Ovcharenko, Y; Pier, A; Rennhack, N; Rivas, DE; Dorner, R; Rolles, D; Rudenko, A; Schmidt, P; Siebert, J; Strenger, N; Trabert, D; Vela-Perez, I; Wagner, R; Weber, T; Williams, JB; Ziolkowski, P; Schmidt, LPH; Czasch, A; Trinter, F; Meyer, M; Ueda, K; Demekhin, PV; Jahnke, T | Abstract: A central motivation for the development of x-ray free-electron lasers has been the prospect of time-resolved single-molecule imaging with atomic resolution. Here, we show that x-ray photoelectron diffraction - where a photoelectron emitted after x-ray absorption illuminates the molecular structure from within - can be used to image the increase of the internuclear distance during the x-ray-induced fragmentation of an O2 molecule. By measuring the molecular-frame photoelectron emission patterns for a two-photon sequential K-shell ionization in coincidence with the fragment ions, and by sorting the data as a function of the measured kinetic energy release, we can resolve the elongation of the molecular bond by approximately 1.2 a.u. within the duration of the x-ray pulse. The experiment paves the road toward time-resolved pump-probe photoelectron diffraction imaging at high-repetition-rate x-ray free-electron lasers.

Substitution of Titanium for Magnesium Ions at the Surface of Mg-Doped Rutile

The surface structure of Mg-doped rutile TiO2 (011) surfaces is determined by combining the core-level or valence band photoemission and photoelectron diffraction (PED) measurements with evolutiona...

The true corrugation of a h-BN nanomesh layer

Hexagonal boron nitride (h-BN) nanomesh, a two-dimensional insulating monolayer, grown on the (111) surface of rhodium exhibits an intriguing hexagonal corrugation pattern with a lattice constant of 3.2 nm. Despite numerous experimental and theoretical studies no quantitative agreement has been found on some details of the adsorption geometry such as the corrugation amplitude. The issue highlights the differences in chemical and electronic environment in the strongly bound pore regions and the weakly bound wire regions of the corrugated structure. For reliable results it is important to probe the structure with a method that is intrinsically sensitive to the position of the atomic cores rather than the electron density of states.In this work, we determine the corrugation of h-BN nanomesh from angle- and energy-resolved photoelectron diffraction measurements with chemical state resolution. By combining the results from angle and energy scans and comparing them to multiple-scattering simulations true adsorbate-substrate distance can be measured with high precision, avoiding pitfalls of apparent topography observed in scanning probe techniques. Our experimental results give accurate values for the peak-to-peak corrugation amplitude (0.80 Å), the bonding distance to the substrate (2.20 Å) and the buckling of the boron and nitrogen atoms in the strongly bound pore regions (0.07 Å).These results are important for the development of theoretical methods that involve a quantitative description of van der Waals systems as required for the understanding of the physics of two-dimensional sp2 layers.

Momentum-transfer model of valence-band photoelectron diffraction

Recent instrumental progress of valence-band photoemission in the X-ray range allows uncovering bulk- and surface-related electronic properties. Four-dimensional recording of energy and momentum-vector gives access to the complete spectral-density function. Systematic measurements for a number of transition metals between 15 eV-6 keV reveal unexpected strong intensity modulations due to photoelectron diffraction. Here, we present a graphical model that illustrates the role of momentum-conservation in Fermi’s Golden-Rule in an intuitive way. Intensity enhancement or reduction by factors >5 are confined to small energy- and momentum-intervals (widths 0.03 Å−1 and 200 meV). Laue-type diffraction involves the photon momentum and is intrinsic in the photoemission process, in accordance with Pendry’s final-state-model. At higher energies, Kikuchi-diffraction imprints additional modulations on valence-band-patterns and quasi-elastic background. The absence of photon-momentum transfer uncovers the extrinsic nature of Kikuchi-diffraction. For Re at 30 K and 3.4 keV the relative weight of the Kikuchi-branch is comparable to the Laue-branch, whereas at 6 keV the Kikuchi-branch prevails.

X-ray standing waves reveal lack of OH termination at hydroxylated ZnO(0001) surfaces

The vertical adsorption distances of the planar conjugated organic molecule 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) on hydroxylated ZnO(0001), determined with the x-ray standing wave technique (XSW), are at variance with adsorption geometries simulated with density functional theory for surface-structure models that consider terminating OH, whereas good agreement is found for PTCDI in direct contact with the topmost Zn layer. The consequential assignment of OH to subsurface sites is supported by additional, independent XSW and energy scanned photoelectron diffraction data and calls for a reconsideration of the prevalent surface models with important implications for the understanding of ZnO(0001) surfaces.

Combining three time-resolved photoemission techniques in a single instrument

A new article describes a versatile instrument that enables time-resolved momentum microscopy, time-resolved X-ray photoelectron spectroscopy and time-resolved X-ray photoelectron diffraction in a single experimental setup.

Ultrafast X-ray photoelectron diffraction in triatomic molecules by circularly polarized attosecond light pulses

We theoretically study ultrafast photoelectron diffraction in triatomic molecules with cyclic geometry by ultrafast circular soft X-ray attosecond pulses. Molecular frame photoelectron distributions show complex diffraction patterns, arising from molecular multiple center interference and circular charge migration. It is found that photoelectron diffraction patterns depend on the initial electronic state, encoding the information of molecular orbital symmetries. In a resonant coherent electron excitation process, time-resolved photoelectron diffraction patterns enables us to reconstruct the charge migration with highly spatiotemporal resolutions. We simulate and analyze the results from ab initio calculations of the single electron triangular hydrogen molecular ion H32+ which is used as a benchmark molecular system in combination with an ultrafast multi-center and multi-state photoionization model. This approach presents a general scheme which can be applied to explore circular charge migration from electron orbits and attosecond coherent electron dynamics in polyatomic systems by circular ultrafast laser pulses.

Time- and momentum-resolved photoemission studies using time-of-flight momentum microscopy at a free-electron laser

Time-resolved photoemission with ultrafast pump and probe pulses is an emerging technique with wide application potential. Real-time recording of nonequilibrium electronic processes, transient states in chemical reactions, or the interplay of electronic and structural dynamics offers fascinating opportunities for future research. Combining valence-band and core-level spectroscopy with photoelectron diffraction for electronic, chemical, and structural analyses requires few 10 fs soft X-ray pulses with some 10 meV spectral resolution, which are currently available at high repetition rate free-electron lasers. We have constructed and optimized a versatile setup commissioned at FLASH/PG2 that combines free-electron laser capabilities together with a multidimensional recording scheme for photoemission studies. We use a full-field imaging momentum microscope with time-of-flight energy recording as the detector for mapping of 3D band structures in (kx, ky, E) parameter space with unprecedented efficiency. Our instrument can image full surface Brillouin zones with up to 7 Å-1 diameter in a binding-energy range of several eV, resolving about 2.5 × 105 data voxels simultaneously. Using the ultrafast excited state dynamics in the van der Waals semiconductor WSe2 measured at photon energies of 36.5 eV and 109.5 eV, we demonstrate an experimental energy resolution of 130 meV, a momentum resolution of 0.06 Å-1, and a system response function of 150 fs.