Erratum: Bending Rigidity of 2D Silica [Phys. Rev. Lett. 120, 226101 (2018)].

This corrects the article DOI: 10.1103/PhysRevLett.120.226101.

Surface Action Spectroscopy: A Review and a Perspective on a New Technique to Study Vibrations at Surfaces.

A new vibrational spectroscopy method aimed at the investigation of solid surfaces in ultrahigh vacuum, called "Surface Action Spectroscopy (SAS)", is described and the first results are reviewed. This technique is based on ideas and experiments performed in the gas phase. A surface is exposed to a messenger species at low temperature. This messenger species is desorbed via absorption of tunable infrared light from a free-electron laser and the desorption rate of the messenger species is recorded via mass spectrometry. It is shown that the technique is extremely surface sensitive and we discuss the basic mechanisms of the technique. We show a feasibility study on a V2 O3 (0001) surface, where we know the surface structure. We then proceed to the example of iron oxide films to study the surface structure in parallel with calculations of the surface phonons, which allow us to confirm the surface structure of Fe3 O4 (111) to be Fetet terminated. It also provides evidence for the so-called biphase structure. To conclude, we discuss possibilities to apply the technique to interesting questions in model and real catalysis, since the technique may provide interesting information independent of long-range order of the sample.

Bending Rigidity of 2D Silica.

A chemically stable bilayers of SiO_{2} (2D silica) is a new, wide band gap 2D material. Up till now graphene has been the only 2D material where the bending rigidity has been measured. Here we present inelastic helium atom scattering data from 2D silica on Ru(0001) and extract the first bending rigidity, κ, measurements for a nonmonoatomic 2D material of definable thickness. We find a value of κ=8.8 eV±0.5 eV which is of the same order of magnitude as theoretical values in the literature for freestanding crystalline 2D silica.

Model systems in heterogeneous catalysis: towards the design and understanding of structure and electronic properties.

We discuss in this paper two case studies related to nano-particle catalyst systems. One concerns a model system for the Cr/SiO2 Phillips catalyst for ethylene polymerization and here we present XPS data to complement the previously published TPD, IRAS and reactivity studies to elucidate the electronic structure of the system in some detail. The second case study provides additional information on Au nano-particles supported on ultrathin MgO(100)/Ag(100) films where we had observed a specific activity of the particle's rim at the metal-oxide interface with respect to CO2 activation and oxalate formation, obviously connected to electron transfer through the MgO film from the metal substrate underneath. Here we present XPS and Auger data, which allows detailed analysis of the observed chemical shifts. This analysis corroborates previous findings deduced via STM.

[Religious beliefs and spirituality in medical residency : A survey among physicians in charge of training psychiatry and psychotherapy]. / Religiosität und Spiritualität in der Facharztweiterbildung : Eine Umfrage bei den Weiterbildungsermächtigten für Psychiatrie und Psychotherapie.

Religion and spirituality (R/S) as empirically measurable and treatment-relevant variables are growing in significance in psychiatry and psychotherapy worldwide. In a survey conducted among physicians in charge of psychiatric residency training in Germany respondents were asked about the integration of R/S in their curricula. Data suggest that subjects (n = 285) attach considerable importance to R/S and especially to existential issues. The importance of R/S in psychiatric training is essentially linked to the trainers' personal views of the world and the corporate culture of the training centers. A possible selection bias and the need to integrate R/S in psychiatric training on the basis of scientific evidence and ethical considerations are discussed.

Deep brain stimulation of the nucleus basalis of Meynert in Alzheimer's dementia.

Cholinergic neurons of the medial forebrain are considered important contributors to brain plasticity and neuromodulation. A reduction of cholinergic innervation can lead to pathophysiological changes of neurotransmission and is observed in Alzheimer's disease. Here we report on six patients with mild to moderate Alzheimer's disease (AD) treated with bilateral low-frequency deep brain stimulation (DBS) of the nucleus basalis of Meynert (NBM). During a four-week double-blind sham-controlled phase and a subsequent 11-month follow-up open label period, clinical outcome was assessed by neuropsychological examination using the Alzheimer's Disease Assessment Scale-cognitive subscale as the primary outcome measure. Electroencephalography and [(18)F]-fluoro-desoxyglucose positron emission tomography were, besides others, secondary endpoints. On the basis of stable or improved primary outcome parameters twelve months after surgery, four of the six patients were considered responders. No severe or non-transitional side effects related to the stimulation were observed. Taking into account all limitations of a pilot study, we conclude that DBS of the NBM is both technically feasible and well tolerated.

Supports and modified nano-particles for designing model catalysts.

In order to design catalytic materials, we need to understand the essential causes for material properties resulting from its composite nature. In this paper we discuss two, at first sight, diverse aspects: (a) the effect of the oxide-metal interface on metal nanoparticle properties and (b) the consequences of metal particle modification after activation on the selectivity of hydrogenation reactions. However, these two aspects are intimately linked. The metal nanoparticle's electronic structure changes at the interface as a catalyst is brought to different reaction temperatures due to morphological modifications in the metal and, as we will discuss, these changes in the chemistry lead to changes in the reaction path. As the morphology of the particle varies, facets of different orientations and sizes are exposed, which may lead to a change in the surface chemistry as well. We use two specific reactions to address these issues in some detail. To the best of our knowledge, the present paper reports the first observations of this kind for well-defined model systems. The changes in the electronic structure of Au nanoparticles due to their size and interaction with a supporting oxide are revealed as a function of temperature using CO2 activation as a probe. The presence of spectator species (oxopropyl), formed during an activation step of acrolein hydrogenation, strongly controls the selectivity of the reaction towards hydrogenation of the unsaturated C[double bond, length as m-dash]O bond vs. the C[double bond, length as m-dash]C bond on Pd(111) when compared with oxide-supported Pd nanoparticles.

A fresh look at an old nano-technology: catalysis.

The development of model catalyst systems for heterogeneous catalysis going beyond the metal single crystal approach, including phenomena involving the limited size of metal nanoparticles supported on oxide surfaces, as well as the electronic interaction through the oxide-metal interface, is exemplified on the basis of two case studies from the laboratory of the authors. In the first case study the reactivity of supported Pd nanoparticles is studied in comparison with Pd single crystals. The influence of carbon contaminants on the hydrogenation reaction of unsaturated hydrocarbons is discussed. Carbon contaminants are identified as a key parameter in those reactions as they control the surface and sub-surface concentration of hydrogen on and in the particles. In the second case study, scanning probe techniques are used to determine electronic and structural properties of supported Au particles as a function of the number of Au atoms in the particle. It is demonstrated how charge transfer between the support and the particle determines the shape of nanoparticles and a concept is developed that uses charge transfer control through dopants in the support to understand and design catalytically active materials.

Ultrathin oxide films on metal supports: structure-reactivity relations.

Well-ordered, thin oxide films have drawn some attention in recent years as suitable oxide supports for modeling highly dispersed metal catalysts at the atomic scale. It turned out, however, that ultrathin oxide films may exhibit interesting catalytic properties in their own right. In this review, we discuss phenomena specifically connected to ultrathin oxide films to explain and understand the physicochemical basis of their reactivity in oxidation reactions. Two sets of systems are discussed, i.e., transition metal oxide films grown on metal substrates and native oxide films formed upon oxidation of metal surfaces.

Adsorption energetics of CO on supported Pd nanoparticles as a function of particle size by single crystal microcalorimetry.

The heat of adsorption and sticking probability of CO on well-defined Pd nanoparticles were measured as a function of particle size using single crystal adsorption microcalorimetry. Pd particles of different average sizes ranging from 120 to 4900 atoms per particle (or from 1.8 to 8 nm) and Pd(111) were used that were supported on a model in situ grown Fe(3)O(4)/Pt(111) oxide film. To precisely quantify the adsorption energies, the reflectivities of the investigated model surfaces were measured as a function of the thickness of the Fe(3)O(4) oxide layer and the amount of deposited Pd. A substantial decrease of the binding energy of CO was found with decreasing particle size. Initial heat of adsorption obtained on the virtually adsorbate-free surface was observed to be reduced by about 20-40 kJ mol(-1) on the smallest 1.8 nm sized Pd particles as compared to the larger Pd clusters and the extended Pd(111) single crystal surface. This effect is discussed in terms of the size-dependent properties of the Pd nanoparticles. The CO adsorption kinetics indicates a strong enhancement of the adsorbate flux onto the metal particles due to a capture zone effect, which involves trapping of adsorbates on the support and diffusion to metal clusters. The CO adsorption rate was found to be enhanced by a factor of ∼8 for the smallest 1.8 nm sized particles and by ∼1.4 for the particles of 7-8 nm size.

Morphological and chemical influences on alumina-supported palladium catalysts active for the gas phase hydrogenation of crotonaldehyde.

A series of five alumina-supported palladium catalysts have previously been prepared and characterised by a combination of CO chemisorption and infrared spectroscopy. The reactive attributes of these catalysts are examined using the hydrogenation of crotonaldehyde as a test reaction, using a modified infrared gas cell as a batch reactor. Periodic scanning of the infrared spectrum of the gaseous phase present over the Pd/Al(2)O(3) catalysts was used to construct reaction profiles. Four of the catalysts were able to facilitate a 2-stage hydrogenation process (crotonaldehyde → butanal → butanol), whilst one catalyst was totally selective for the first stage hydrogenation process (crotonaldehyde → butanal). Rate coefficients for the first and second stage hydrogenation processes are normalised to the number of surface palladium atoms for the particular catalyst. Correlation of these kinetic parameters as a function of mean particle size indicates the first stage process to be structure insensitive, whilst the second stage hydrogenation is structure sensitive. Chlorine residues associated with the preparative process of one of the catalysts is seen to selectively poison the second stage hydrogenation process for that catalyst. Structure/activity relationships are considered to explain the observed trends.

Growth and structure of crystalline silica sheet on Ru(0001).

Thin SiO2 films were grown on a Ru(0001) single crystal and studied by photoelectron spectroscopy, infrared spectroscopy and scanning probe microscopy. The experimental results in combination with density functional theory calculations provide compelling evidence for the formation of crystalline, double-layer sheet silica weakly bound to a metal substrate.

Model studies in heterogeneous catalysis.

I review a concept that models heterogeneous catalysis based on a surface-science approach. It is shown that models catching part of the complexity of the real system, which is connected with the finite size of active components and the flexibility of the arrangement of atoms in the active component, play an important part in determining the activity and selectivity of the system. I have chosen several examples from our own laboratory to elaborate the details and will put those into perspective with respect to the literature. I will show that Pd nanoparticles in hydrogenation incorporate hydrogen, which turns out to be crucial for the actual hydrogenation step. Another example correlates the structure of vanadia monolayer catalysts with its reactivity in methanol oxidation. With a third example we address the question of charge on Au nanoparticles when anchored to an oxide surface, a problem heavily discussed in the literature. Further examples refer to ultrathin oxide film catalysts in which the oxide metal interface controls either the charge state of Au particles grown on the film, and, in a last example, the oxide film itself exhibits remarkable CO-oxidation activity, which can be traced to a reactive intermediate structure of the ultrathin film.

Measuring the charge state of point defects on MgO/Ag(001).

A detailed understanding of surface defects is highly desirable, e.g. to clarify their role as active sites in catalysis. Here localized defects on the surface of MgO films deposited on Ag(001) are investigated. Since the electronic structure of color centers depends on their local position, spectroscopic signals are highly convoluted and often difficult to disentangle. In this study we aimed to obtain morphological and spectroscopic information on single color centers at a microscopic level with frequency modulated dynamic force microscopy (FM-DFM) and scanning tunneling microscopy (STM) in an ultrahigh vacuum and at low temperature. Four of the major and in literature mostly discussed defect types on MgO have been characterized by their charge state and finally identified by the complementary application of FM-DFM and STM in combination with density functional theory results.

A study of pyrimidine base damage in relation to oxidative stress and cancer.

BACKGROUND: A long-standing hypothesis is that oxidative stress is a risk factor for cancer. Support for this hypothesis comes from observations of higher levels of oxidative damage in the DNA of WBC of cancer patients compared with healthy controls. METHODS: Two generally overlooked types of DNA damage, the formamide modification and the thymine glycol modification, both derived from pyrimidine bases, were assayed as markers of oxidative stress. Damage levels were measured in the DNA of WBC of ovarian cancer patients and of healthy controls. RESULTS: The levels of both modifications were higher in ovarian cancer patients than in healthy controls although in the case of the formamide modification age could not be ruled out as a factor. CONCLUSION: Our results in combination with other published measurements of oxidative DNA damage support the hypothesis that oxidative damage, on average, is higher in WBC of cancer patients than in healthy controls.

Efficiency and spectrum enhancement in a tapered free-electron laser amplifier.

We report the first experimental characterization of efficiency and spectrum enhancement in a laser-seeded free-electron laser using a tapered undulator. Output and spectra in the fundamental and third harmonic were measured versus distance for uniform and tapered undulators. With a 4% field taper over 3 m, a 300% (50%) increase in the fundamental (third harmonic) output was observed. A significant improvement in the spectra with the elimination of sidebands was observed using a tapered undulator. The experiment is in good agreement with predictions using the MEDUSA simulation code.

Free-electron lasers. Status and applications.

A free-electron laser consists of an electron beam propagating through a periodic magnetic field. Today such lasers are used for research in materials science, chemical technology, biophysical science, medical applications, surface studies, and solid-state physics. Free-electron lasers with higher average power and shorter wavelengths are under development. Future applications range from industrial processing of materials to light sources for soft and hard x-rays.

Morphology and CO adsorption on platinum supported on thin Fe(3)O(4)(111) films.

Nucleation, growth and thermal stability of Pt particles supported on well ordered Fe(3)O(4)(111) thin films grown on Pt(111) were studied by scanning tunnelling microscopy (STM) and temperature programmed desorption (TPD) of CO. STM studies showed that Pt grows through the formation of single-layer islands that coalesce at high coverage. Vacuum annealing at 600 K caused Pt sintering and the formation of extended two-dimensional (2D) islands one and two layers in thickness at sub-monolayer coverage. Well faceted, three-dimensional (3D) Pt nanoparticles formed by annealing to temperatures above 800 K were encapsulated by an FeO(111) monolayer. These results were rationalized in terms of the high adhesion energy for Pt on iron oxide surfaces. CO TPD studies showed that 2D structures, formed at 600 K, exhibit much lower CO adsorption capacity as compared to the Pt(111) single crystal surface. This effect has been tentatively assigned to lattice expansion in the Pt 2D islands leading to weakening of the Pt-CO bond due to reduction of the [Formula: see text] back-donation.

Au dimers on thin MgO(001) films: flat and charged or upright and neutral?

A combination of low temperature scanning tunneling microscopy (STM) and theoretical calculations is used to investigate Au dimers, supported on thin MgO(001) films, whose thickness was chosen such that charge transfer from the Ag substrate to the deposited Au is possible. Au dimers exist not only in an upright geometry--as theoretically predicted to be the most stable configuration--but also as flat lying dimers which populate a manifold of different azimuthal orientations. Apart from the difference in adsorption configurations, these two isomers exhibit rather different electronic structures: while upright dimers are neutral, flat ones are charged.

Influence of Pd codeposition on the magnetic properties of Co particles on alumina/NiAl110.

Changes of the magnetic properties of ferromagnetic Co particles deposited at room temperature on a thin alumina film grown on a NiAl(110) substrate were investigated as a function of Pd coverage by subsequent deposition of Pd onto deposited Co particles. From previous x-ray photoelectron spectroscopy, IR, and temperature programmed desorption experiments it was concluded that Pd forms a shell on top of Co particles. However, the current experiments indicate that Pd does induce structural rearrangements within the Co particles which may also involve the intermixing of small amounts of Pd into the Co particles. The latter is inferred from a change in the g-value for small particles. The impact of a larger intermixture of Co and Pd on the magnetic properties will be emphasized by a reversed deposition order where Pd particles were deposited first and subsequently covered by Co. The reversal of the deposition order increases the magnetic anisotropy of the particles considerably.