Vibration-Driven Self-Doping of Dangling-Bond Wires on Si(553)-Au Surfaces.

Density-functional theory is used to explore the Si(553)-Au surface dynamics. Our study (i) reveals a complex two-stage order-disorder phase transition where with rising temperature first the ×3 order along the Si step edges and, subsequently, the ×2 order of the Au chains is lost, (ii) identifies the transient modification of the electron chemical potential during soft Au chain vibrations as instrumental for disorder at the step edge, and (iii) shows that the transition leads to a self-doping of the Si dangling-bond wire at the step edge. The calculations are corroborated by Raman measurements of surface phonon modes and explain previous electron diffraction, scanning tunneling microscopy, and surface transport data.

Oxygen and potassium vacancies in KTP calculated from first principles.

The atomic geometry and energetics of oxygen and potassium vacancies in potassium titanyl phosphate (KTP) as well as their electronic and optical properties are studied within density-functional theory in dependence of their charge state. Oxygen vacancies formed between Ti and P are characterized by a negative-U behavior. Their neutral charge state is favored for Fermi levels near the conduction band and gives rise to a defect level in the band gap, which leads to an additional optical absorption peak. In contrast, the two-fold positive charge state, stable for low and intermediate values of the Fermi level, modifies the KTP optical response only slightly. Oxygen vacancies formed between two Ti atoms are two-fold positively charged, while potassium vacancies are negatively charged irrespective of the Fermi level position. In both these cases, the KTP optical response is essentially not affected.

Investigation of near-surface defects of nanodiamonds by high-frequency EPR and DFT calculation.

Nanodiamonds (NDs) hosting nitrogen-vacancy (NV) centers are a promising platform for quantum sensing applications. Sensitivity of the applications using NV centers in NDs is often limited due to the presence of paramagnetic impurity contents near the ND surface. Here, we investigate near-surface paramagnetic impurities in NDs. Using high-frequency (HF) electron paramagnetic resonance spectroscopy, the near-surface paramagnetic impurity within the shell of NDs is probed and its g-value is determined to be 2.0028(3). Furthermore, HF electron-electron double resonance-detected nuclear magnetic resonance spectroscopy and a first principles calculation show that a possible structure of the near-surface impurity is the negatively charged vacancy V-. The identification of the near-surface impurity by the present investigation provides a promising pathway to improve the NV properties in NDs and the NV-based sensing techniques.

Identifying On-Surface Site-Selective Chemical Conversions by Theory-Aided NEXAFS Spectroscopy: The Case of Free-Base Corroles on Ag(111).

We demonstrate here that theory-assisted near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy enables the site-sensitive monitoring of on-surface chemical reactions, thus, providing information not accessible by other techniques. As a prototype example, we have used free-base 5,10,15-tris(pentafluorophenyl)corroles (3H-TpFPC) adsorbed on Ag(111) and present a detailed investigation of the angle-dependent NEXAFS of this molecular species as well as of their thermally induced derivatives. For this, we have recorded experimental C and N K-edge NEXAFS spectra and interpret them based on XAS cross-section calculations by using a continuous fraction approach and core-hole including multiprojector PAW pseudopotentials within DFT. We have characterized the as-deposited low temperature (200 K) phase and unraveled the subsequent changes induced by dehydrogenation (at 330 K) and ring-closure reactions (at 430 K). By exemplarily obtaining profound insight into the on-surface chemistry of free-base corrolic species adsorbed on a noble metal this work highlights how angle-dependent XAS combined with accurate theoretical modeling can serve for the investigation of on-surface reactions, whereby even highly similar molecular structures, such as tautomers and isomers, can be distinguished.

Advanced capabilities for materials modelling with Quantum ESPRESSO.

Quantum EXPRESSO is an integrated suite of open-source computer codes for quantum simulations of materials using state-of-the-art electronic-structure techniques, based on density-functional theory, density-functional perturbation theory, and many-body perturbation theory, within the plane-wave pseudopotential and projector-augmented-wave approaches. Quantum EXPRESSO owes its popularity to the wide variety of properties and processes it allows to simulate, to its performance on an increasingly broad array of hardware architectures, and to a community of researchers that rely on its capabilities as a core open-source development platform to implement their ideas. In this paper we describe recent extensions and improvements, covering new methodologies and property calculators, improved parallelization, code modularization, and extended interoperability both within the distribution and with external software.

Optically excited structural transition in atomic wires on surfaces at the quantum limit.

Transient control over the atomic potential-energy landscapes of solids could lead to new states of matter and to quantum control of nuclear motion on the timescale of lattice vibrations. Recently developed ultrafast time-resolved diffraction techniques combine ultrafast temporal manipulation with atomic-scale spatial resolution and femtosecond temporal resolution. These advances have enabled investigations of photo-induced structural changes in bulk solids that often occur on timescales as short as a few hundred femtoseconds. In contrast, experiments at surfaces and on single atomic layers such as graphene report timescales of structural changes that are orders of magnitude longer. This raises the question of whether the structural response of low-dimensional materials to femtosecond laser excitation is, in general, limited. Here we show that a photo-induced transition from the low- to high-symmetry state of a charge density wave in atomic indium (In) wires supported by a silicon (Si) surface takes place within 350 femtoseconds. The optical excitation breaks and creates In-In bonds, leading to the non-thermal excitation of soft phonon modes, and drives the structural transition in the limit of critically damped nuclear motion through coupling of these soft phonon modes to a manifold of surface and interface phonons that arise from the symmetry breaking at the silicon surface. This finding demonstrates that carefully tuned electronic excitations can create non-equilibrium potential energy surfaces that drive structural dynamics at interfaces in the quantum limit (that is, in a regime in which the nuclear motion is directed and deterministic). This technique could potentially be used to tune the dynamic response of a solid to optical excitation, and has widespread potential application, for example in ultrafast detectors.

Density functional theory of the CuA -like Cu2 S2 diamond core in Cu 2II(NGuaS)2 Cl2.

Density functional theory (DFT) calculations with localized as well as plane-wave basis functions are performed for the recently reported dicopper thiolate species Cu2 (NGuaS)2 Cl2 [NGuaS = 2-(1,1,3,3-tetramethylguanidino) benzenethiolate, C11 H16 N3 S] and its bromo derivative [Neuba et al., Angew. Chem. Int. Ed. 2012, 51, 1714.]. For both hybrid and semilocal functionals, the neutral complexes are found to have broken symmetry (BS) character, with electron paramagnetic resonance silent, antiferromagnetically coupled [Cu(2+) …Cu(2+) ] site in which the coupling is driven by super exchange interaction within the Cu2 S2 diamond core. The accurate theoretical description of the geometric structure, however, provides a major challenge for DFT: (i) the multideterminant character of the ground state wave function has to be covered by the BS approach. It requires (ii) metageneralized gradient approximations, that is hybrid functionals with an explicit dependence on the kinetic energy of the individual orbitals: In combination with a dispersion correction, the metafunctional TPSSh results in a CuCu distance close to the experimentally observed value of 2.7 Å. For the negative charge state of the complex, a mixed-valent [Cu(1.5+) …Cu(1.5+) ] electronic structure with a smaller CuCu distance of 2.6 Å is predicted, similar to the value of the CuA site of cytochrome c oxidase.

LESSONS LEARNED FROM THE EURADOS SURVEY ON INDIVIDUAL MONITORING DATA AND INTERNAL DOSE ASSESSMENTS OF FOREIGNERS EXPOSED IN JAPAN FOLLOWING THE FUKUSHIMA DAIICHI NPP ACCIDENT.

European Radiation Dosimetry Group e.V. (EURADOS) survey on individual monitoring data and dose assessment has been carried out for 550 foreigners returning home after being exposed in Japan to intakes of radionuclides (mainly (131)I, (132)I, (132)Te, (134)Cs and (137)Cs) as a consequence of the Fukushima Daiichi NPP accident. In vivo and in vitro measurements were performed in their respective countries at an early stage after that accident. Intakes of radionuclides were detected in 208 persons from Europe and Canada, but the committed effective dose E(50) was below the annual dose limit for the public (<1 mSv) in all the cases. Lessons learned from this EURADOS survey are presented here regarding not only internal dosimetry issues, but also the management of the emergency situation, the perception of the risk of health effects due to radiation and the communication with exposed persons who showed anxiety and lack of trust in monitoring data and dose assessments.

Influence of structural defects and oxidation onto hole conductivity in P3HT.

The effect of structural imperfections as well as oxygen impurities on the quantum conductance of poly(3-hexylthiophene) is calculated from first-principles by solving the scattering problem for molecular structures obtained within density functional theory. It is shown that the conductivity of molecular crystals perpendicular to the polymer chains depends strongly on the stacking geometry and is roughly described within the Wentzel-Kramers-Brillouin approximation. Furthermore, it is found that local relaxation for twisted or bent polymer chains efficiently restores the conductance that drops substantially for sharp kinks with curvature radii smaller than 17 Å and rotations in excess of ∼60°. In contrast, isomer defects in the coupling along the chain direction are of minor importance for the intrachain transmission. Also, oxidation of the side chains as well as molecular sulfur barely changes the coherent transport properties, whereas oxidation of thiophene group carbon atoms drastically reduces the conductance.

Atomic structure of interface states in silicon heterojunction solar cells.

Combining orientation dependent electrically detected magnetic resonance and g tensor calculations based on density functional theory we assign microscopic structures to paramagnetic states involved in spin-dependent recombination at the interface of hydrogenated amorphous silicon crystalline silicon (a-Si:H/c-Si) heterojunction solar cells. We find that (i) the interface exhibits microscopic roughness, (ii) the electronic structure of the interface defects is mainly determined by c-Si, (iii) we identify the microscopic origin of the conduction band tail state in the a-Si:H layer, and (iv) present a detailed recombination mechanism.

Identification of the nitrogen split interstitial (N-N)(N) in GaN.

Combining electron paramagnetic resonance, density functional theory, and positron annihilation spectroscopy (PAS), we identify the nitrogen interstitial defect in GaN. The isolated interstitial is unstable and transforms into a split interstitial configuration (N-N)(N). It is generated by particle irradiation with an introduction rate of a primary defect, pins the Fermi level at E(C)-1.0 eV for high fluences, and anneals out at 400 °C. The associated defect, the nitrogen vacancy, is observed by PAS only in the initial stage of irradiation.

Inventory and geochemical host phases of natural radionuclides in tin mining materials from Nigeria.

On the Nigerian Jos Plateau tin mining is extensively carried out in open pit style. Several types of materials occurring there (raw materials, waste, and soil) were analysed radiometrically. The geochemical host phases of the natural radionuclides were determined by a sequential extraction procedure according to the European BCR standard. It was found that especially easily mobilisable (228)Ra must be taken into consideration as a radioactive contaminant for the mining area.

Uranium and thorium in soils, mineral sands, water and food samples in a tin mining area in Nigeria with elevated activity.

The activity concentrations of uranium and thorium have been determined in soils and mineral sands from the Nigerian tin mining area of Bisichi, located in the Jos Plateau, and from two control areas in Nigeria (Jos City and Akure) using high-purity germanium detectors (HPGe). High resolution sector field inductively coupled plasma mass spectroscopy (HR-SF-ICP-MS) was used to determine uranium and thorium in liquids and foodstuffs consumed locally in the mining area. The activities of uranium and thorium measured in the soils and mineral sands from Bisichi ranged from 8.7 kBq kg(-1) to 51 kBq kg(-1) for (238)U and from 16.8 kBq kg(-1) to 98 kBq kg(-1) for (232)Th, respectively. These values were significantly higher than those in the control areas of Jos City and Akure and than the reference values reported in the literature. They even exceeded the concentrations reported for areas of high natural radioactive background. Radionuclide concentrations in samples of the local foodstuffs and in water samples collected in Bisichi were found to be higher than UNSCEAR reference values. The results reveal the pollution potential of the mining activities on the surrounding areas.

Investigations on the activity concentrations of 238U, 226RA, 228RA, 210PB and 40K in Jordan phosphogypsum and fertilizers.

The activity concentrations of naturally occurring radionuclides ((238)U, (226)Ra, (228)Ra, (210)Pb and (40)K) in Jordanian phosphate ore, fertilizer material and phosphogypsum piles were investigated. The results show the partitioning of radionuclides in fertilizer products and phosphogypsum piles. The outcome of this study will enrich the Jordanian radiological map database, and will be useful for an estimation of the radiological impact of this industrial complex on the immediate environment. The activity concentration of (210)Pb was found to vary from 95 +/- 8 to 129 +/- 8 Bq kg(-1) with a mean value of 111 +/- 14 Bq kg(-1) in fertilizer samples, and from 364 +/- 8 to 428 +/- 10 Bq kg(-1) with a mean value of 391 +/- 30 Bq kg(-1) in phosphogypsum samples; while in phosphate wet rock samples, it was found to vary between 621 +/- 9 and 637 +/- 10 Bq kg(-1), with a mean value of 628 +/- 7 Bq kg(-1). The activity concentration of (226)Ra in fertilizer samples (between 31 +/- 4 and 42 +/- 5 Bq kg(-1) with a mean value of 37 +/- 6 Bq kg(-1)) was found to be much smaller than the activity concentration of (226)Ra in phosphogypsum samples (between 302 +/- 8 and 442 +/- 8 Bq kg(-1) with a mean value of 376 +/- 62 Bq kg(-1)). In contrast, the activity concentration of (238)U in fertilizer samples (between 1011 +/- 13 and 1061 +/- 14 Bq kg(-1) with a mean value of 1033 +/- 22 Bq kg(-1)) was found to be much higher than the activity concentration of (238)U in phosphogypsum samples (between 14 +/- 5 and 37 +/- 7 Bq kg(-1) with a mean value of 22 +/- 11 Bq kg(-1)). This indicates that (210)Pb and (226)Ra show similar behaviour, and are concentrated in phosphogypsum piles. In addition, both isotopes enhanced the activity concentration in phosphogypsum piles, while (238)U enhanced the activity concentration in the fertilizer. Due to the radioactivity released from the phosphate rock processing plants into the environment, the highest collective dose commitment for the lungs was found to be 1.02 person nGy t(-1). Lung tissue also shows the highest effect due the presence of (226)Ra in the radioactive cloud (0.087 person nGy t(-1)).

Measurement techniques for tracer kinetic studies with stable isotopes of zirconium.

Biokinetic models are used in radiation protection to assess internal radiation doses. Experiments with stable isotopes as tracers can be performed to obtain characteristic parameters of these models. Two methods for the measurement of zirconium isotopes in human biological samples are presented--thermal ionisation mass spectrometry (TIMS) and proton nuclear activation analysis (PNA). Descriptions include sample preparation, operating conditions, relative uncertainties and method detection limits as well as important properties of both methods.

Long-term corrosion and leaching of depleted uranium (DU) in soil.

Corrosion and leaching of depleted uranium (DU) was investigated for 3 years using six DU munitions (145-264 g DU) each buried in a column with a soil core of about 3.3 kg dry soil mass. The columns were installed in an air-conditioned laboratory. Each week they were irrigated and (238)U was determined in the effluents by inductively coupled plasma mass spectrometry. In addition, (235)U was measured occasionally to assure that the (238)U was predominantly from the DU munition. On average, 14.5 g corresponding to 7.9% of the initial DU mass was corroded after 3 years, indicating an increased corrosion as compared to the first year of observation. The leaching rates increased much stronger than the corrosion rates by factors of more than 100, resulting in a mean total amount of leached (238)U of 13 mg as compared to 0.03 mg after the first year. Uranium species identified in the seepage water by time-resolved laser-induced fluorescence spectroscopy were mainly hydroxo and carbonate compounds, while those in the corroded material were phosphate compounds. It is concluded that the dramatic increase of the leaching and its large temporal variability do not allow any extrapolation for the future. However, the high (238)U concentrations observed in the seepage water highlight the need for further investigations on the transport of (238)U through soil, in particular with regard to the potential future (238)U contamination of groundwater in areas affected by DU weapons.

Observation of changes in urinary excretion of thorium in humans following ingestion of a therapeutic soil.

The study investigated the changes in urinary thorium excretion by humans following ingestion of a therapeutic soil, which contains about 10 ppm of thorium. This well-known healing earth in Germany has been considered as an alternative medicine for diarrhoea and gastric hyper-acidity. Six adult volunteers ingested this therapeutic soil in varying quantities for 1-15 days at levels approximating those described in the package insert of the medicine (10-60 g of soil per day). The subjects ingested about 0.1-0.6 mg of thorium daily, which is 100-600 times higher than the normal daily intake of about 1 microg thorium in Germany. All 24-h urine samples collected from the subjects during pre-ingestion, ingestion and post-ingestion periods of the soil were analyzed for (232)Th using inductively coupled plasma mass spectrometry (ICP-MS). The measured excretion values varied in a wide range. Apparently, the high thorium amounts administered did not increase the (232)Th excretion in urine as expected, suggesting that this soil ingestion will not result in a considerably higher and harmful uptake of thorium into the human body.

Intra-cultivar variability of the soil-to-grain transfer of fallout 137Cs and 90Sr for winter wheat.

Differences between the root uptake of fallout radionuclides by different cultivars ('inter-cultivar' variability) growing on the same field may be influenced not only by genetic differences of the cultivars, but also by the spatial variability of the soil-to-grain transfer within the cultivation area of each cultivar. This 'intra-cultivar' variability was investigated in 2001 and 2002 for 137Cs and 90Sr using three winter wheat cultivars with four replicates for each cultivar at three different sites in Bavaria, Germany. The intra-cultivar variability proved to be in the same range as the inter-cultivar variability which was determined earlier at the same sites for both radionuclides. An ANOVA of the 137Cs data set revealed that the variability of the 137Cs soil-to-grain transfer was caused by the soil and climate (year) at the field sites and the interaction of cultivar and field. A significant contribution of the factor 'cultivar' alone to the variability could not be detected. This may be due to the complex environmental conditions to which plants are exposed in field experiments. To find wheat cultivars with minimal uptake of fallout radionuclides it may be better to examine the molecular mechanisms of their root uptake in order to identify targets for breeding "safer" plants.

Soil-to-grain transfer of fallout 90Sr for 28 winter wheat cultivars.

In order to identify wheat cultivars with minimum soil-to-grain transfer of fallout 90Sr, 28 winter wheat cultivars were investigated at three different sites with different soil types in Upper Bavaria. Each cultivar was grown on an area of 10 m2 and harvested in August 1999. Mean soil-to-grain concentration ratios (C(r)) were 0.151 +/- 0.029, 0.205 +/- 0.035 and 0.060 +/- 0.012, respectively. The C(r) values obtained varied by factors of up to 2.6 for the different cultivars at a given site, and by factors of up to 5.0 for the different sites and a given cultivar. Site-averaged normalized concentration ratios (SANC(r)) ranged from 0.666 +/- 0.062 to 1.503 +/- 0.161. The cultivars Convent, Ludwig, and Semper, showed the lowest uptake of (90)Sr compared to the mean of all cultivars at each site. A cultivar that shows both minimum uptake of 90Sr and 137Cs could not be identified. The results suggest that 90Sr rather than 137Cs might be the limiting radionuclide concerning the use of contaminated land for wheat production. Thus, more efforts might be necessary identifying wheat cultivars with minimum 90Sr uptake.