First in-flight synchrotron X-ray absorption and photoemission study of carbon soot nanoparticles.

Many studies have been conducted on the environmental impacts of combustion generated aerosols. Due to their complex composition and morphology, their chemical reactivity is not well understood and new developments of analysis methods are needed. We report the first demonstration of in-flight X-ray based characterizations of freshly emitted soot particles, which is of paramount importance for understanding the role of one of the main anthropogenic particulate contributors to global climate change. Soot particles, produced by a burner for several air-to-fuel ratios, were injected through an aerodynamic lens, focusing them to a region where they interacted with synchrotron radiation. X-ray photoelectron spectroscopy and carbon K-edge near-edge X-ray absorption spectroscopy were performed and compared to those obtained for supported samples. A good agreement is found between these samples, although slight oxidation is observed for supported samples. Our experiments demonstrate that NEXAFS characterization of supported samples provides relevant information on soot composition, with limited effects of contamination or ageing under ambient storage conditions. The highly surface sensitive XPS experiments of airborne soot indicate that the oxidation is different at the surface as compared to the bulk probed by NEXAFS. We also report changes in soot's work function obtained at different combustion conditions.

Adjacent Fe-Vacancy Interactions as the Origin of Room Temperature Ferromagnetism in (In(1-x)Fe(x))2O3.

Dilute magnetic semiconductors (DMSs) show great promise for applications in spin-based electronics, but in most cases continue to elude explanations of their magnetic behavior. Here, we combine quantitative x-ray spectroscopy and Anderson impurity model calculations to study ferromagnetic Fe-substituted In2O3 films, and we identify a subset of Fe atoms adjacent to oxygen vacancies in the crystal lattice which are responsible for the observed room temperature ferromagnetism. Using resonant inelastic x-ray scattering, we map out the near gap electronic structure and provide further support for this conclusion. Serving as a concrete verification of recent theoretical results and indirect experimental evidence, these results solidify the role of impurity-vacancy coupling in oxide-based DMSs.

Measuring partial fluorescence yield using filtered detectors.

Typically, X-ray absorption near-edge structure measurements aim to probe the linear attenuation coefficient. These measurements are often carried out using partial fluorescence yield techniques that rely on detectors having photon energy discrimination improving the sensitivity and the signal-to-background ratio of the measured spectra. However, measuring the partial fluorescence yield in the soft X-ray regime with reasonable efficiency requires solid-state detectors, which have limitations due to the inherent dead-time while measuring. Alternatively, many of the available detectors that are not energy dispersive do not suffer from photon count rate limitations. A filter placed in front of one of these detectors will make the energy-dependent efficiency non-linear, thereby changing the responsivity of the detector. It is shown that using an array of filtered X-ray detectors is a viable method for measuring soft X-ray partial fluorescence yield spectra without dead-time. The feasibility of this technique is further demonstrated using α-Fe2O3 as an example and it is shown that this detector technology could vastly improve the photon collection efficiency at synchrotrons and that these detectors will allow experiments to be completed with a much lower photon flux reducing X-ray-induced damage.

Role of oxygen holes in Li(x)CoO(2) revealed by soft X-ray spectroscopy.

The fundamental electronic structure of the widely used battery material Li(x)CoO(2) still remains a mystery. Soft x-ray absorption spectroscopy of Li(x)CoO(2) reveals that holes with strong O 2p character play an essential role in the electronic conductivity of the Co(3+)/Co(4+) mixed valence CoO(2) layer. The oxygen holes are bound to the Co(4+) sites and the Li-ion vacancy, suggesting that the Li-ion flow can be stabilized by oxygen hole back flow. Such an oxygen hole state of Li(x)CoO(2) is unique among the various oxide-based battery materials and is one of the key ingredients to improving their electronic and Li-ion conductivities.

Probing the role of co substitution in the electronic structure of iron pnictides.

The role of Co substitution in the low-energy electronic structure of Ca(Fe(0.944)Co(0.056))(2)As(2) is investigated by resonant photoemission spectroscopy and density-functional theory. The Co 3d state center of mass is observed at 250 meV higher binding energy than that of Fe, indicating that Co possesses one extra valence electron and that Fe and Co are in the same oxidation state. Yet, significant Co character is detected for the Bloch wave functions at the chemical potential, revealing that the Co 3d electrons are part of the Fermi sea determining the Fermi surface. This establishes the complex role of Co substitution in CaFe(2)As(2) and the inadequacy of a rigid-band shift description.

Determination of total x-ray absorption coefficient using non-resonant x-ray emission.

An alternative measure of x-ray absorption spectroscopy (XAS) called inverse partial fluorescence yield (IPFY) has recently been developed that is both bulk sensitive and free of saturation effects. Here we show that the angle dependence of IPFY can provide a measure directly proportional to the total x-ray absorption coefficient, µ(E). In contrast, fluorescence yield (FY) and electron yield (EY) spectra are offset and/or distorted from µ(E) by an unknown and difficult to measure amount. Moreover, our measurement can determine µ(E) in absolute units with no free parameters by scaling to µ(E) at the non-resonant emission energy. We demonstrate this technique with measurements on NiO and NdGaO(3). Determining µ(E) across edge-steps enables the use of XAS as a non-destructive measure of material composition. In NdGaO(3), we also demonstrate the utility of IPFY for insulating samples, where neither EY or FY provide reliable spectra due to sample charging and self-absorption effects, respectively.

Ultrathin W-Al dual interlayer approach to depositing smooth and adherent nanocrystalline diamond films on stainless steel.

The adherence of diamond coated on steel is commonly low and needs to be strengthened with thick intermediate layers. In this paper, a nanoscale W-Al dual metal interlayer has been applied on SS304 substrates to facilitate deposition of continuous, adherent and smooth diamond thin films. During the microwave plasma-enhanced chemical vapor deposition process, the Al inner layer 30 nm thick diffuses into steel surface inhibiting carbon diffusion and graphitization. The W outer layer 20 nm thick is transformed into W carbides, both preventing carbon diffusion and enhancing diamond nucleation. The diamond films synthesized are of high purity and have smooth surfaces and dense structures. Indentation and shear deformation tests indicate high delaminating tolerance of the diamond films.

Comparative theoretical and experimental study of the radiation-induced decomposition of glycine.

The radiation-induced decomposition of glycine is studied using a combination of near-edge X-ray absorption fine structure (NEXAFS) measurements and DFT calculations. The measured spectra show strong dose- or time-dependent effects consistent with a complex, multistep decomposition. Principal component analysis was used to determine the number of distinct molecules that were needed to explain the observed changes in the measured spectra, and the emerging absorption features are assigned to various product molecules through comparison with simulated spectra of several model compounds. It is clear from the experiment that the major effect of soft X-ray irradiation is the fragmentation of the molecule, primarily at the carbonyl sites. Peptide formation is shown to occur under irradiation; a condensation reaction initiated by the removal of a carbonyl oxygen is the proposed mechanism. This study utilizes a novel approach to the study of radiation damage that can occur during measurements and suggests that it may be possible to use simulated model spectra to correct for these effects in measured spectra.

Lateralization of categorical perception of color changes with color term acquisition.

Categorical perception (CP) of color is the faster and more accurate discrimination of two colors from different categories than two colors from the same category, even when same- and different-category chromatic separations are equated. In adults, color CP is lateralized to the left hemisphere (LH), whereas in infants, it is lateralized to the right hemisphere (RH). There is evidence that the LH bias in color CP in adults is due to the influence of color terms in the LH. Here we show that the RH to LH switch in color CP occurs when the words that distinguish the relevant category boundary are learned. A colored target was shown in either the left- or right-visual field on either the same- or different-category background, with equal hue separation for both conditions. The time to initiate an eye movement toward the target from central fixation at target onset was recorded. Color naming and comprehension was assessed. Toddlers were faster at detecting targets on different- than same-category backgrounds and the extent of CP did not vary with level of color term knowledge. However, for toddlers who knew the relevant color terms, the category effect was found only for targets in the RVF (LH), whereas for toddlers learning the color terms, the category effect was found only for targets in the LVF (RH). The findings suggest that lateralization of color CP changes with color term acquisition, and provide evidence for the influence of language on the functional organization of the brain.

The effect of the surface of SnO2 nanoribbons on their luminescence using x-ray absorption and luminescence spectroscopy.

X-ray excited optical luminescence (XEOL) and x-ray absorption near-edge structure in total electron, x-ray fluorescence, and photoluminescence yields at Sn M5,4-, O K-, and Sn K-edges have been used to study the luminescence from SnO2 nanoribbons. The effect of the surface on the luminescence from SnO2 nanoribbons was studied by preferential excitation of the ions in the near-surface region and at the normal lattice positions, respectively. No noticeable change of luminescence from SnO2 nanoribbons was observed if the Sn ions in the near-surface region were excited selectively, while the luminescence intensity changes markedly when Sn or O ions at the normal lattice positions were excited across the corresponding edges. Based on the experimental results, we show that the luminescence from SnO2 nanoribbons is dominated by energy transfer from the excitation of the whole SnO2 lattice to the surface states. Surface site specificity is not observable due to its low concentration and weak absorption coefficient although the surface plays an important role in the emission as a luminescence center. The energy transfer and site specificity of the XEOL or the lack of the site specificity from a single-phase sample is discussed.

Categorical perception of color is lateralized to the right hemisphere in infants, but to the left hemisphere in adults.

Both adults and infants are faster at discriminating between two colors from different categories than two colors from the same category, even when between- and within-category chromatic separation sizes are equated. For adults, this categorical perception (CP) is lateralized; the category effect is stronger for the right visual field (RVF)-left hemisphere (LH) than the left visual field (LVF)-right hemisphere (RH). Converging evidence suggests that the LH bias in color CP in adults is caused by the influence of lexical color codes in the LH. The current study investigates whether prelinguistic color CP is also lateralized to the LH by testing 4- to 6-month-old infants. A colored target was shown on a differently colored background, and time to initiate an eye movement to the target was measured. Target background pairs were either from the same or different categories, but with equal target-background chromatic separations. Infants were faster at initiating an eye movement to targets on different-category than same-category backgrounds, but only for targets in the LVF-RH. In contrast, adults showed a greater category effect when targets were presented to the RVF-LH. These results suggest that whereas color CP is stronger in the LH than RH in adults, prelinguistic CP in infants is lateralized to the RH. The findings suggest that language-driven CP in adults may not build on prelinguistic CP, but that language instead imposes its categories on a LH that is not categorically prepartitioned.

Substituent effects in the iron 2p and carbon 1s edge near-edge X-ray absorption fine structure (NEXAFS) spectroscopy of ferrocene compounds.

The iron 2p and carbon 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of substituted ferrocene compounds (Fe(Cp-(CH3)5)2, Fe(Cp)(Cp-COOH), Fe(Cp-COOH)2, and Fe(Cp-COCH3)2) are reported and are interpreted with the aid of extended Hückel molecular orbital (EHMO) theory and density functional theory (DFT). Significant substituent effects are observed in both the Fe 2p and C 1s NEXAFS spectra. These effects can be related to the electron donating/withdrawing properties of the cyclopentadienyl ligands and their substituents as well as the presence of pi* conjugation between the cyclopentadienyl ligand and unsaturated substituents.

Further evidence that Whorfian effects are stronger in the right visual field than the left.

The Whorf hypothesis holds that differences between languages induce differences in perception and/or cognition in their speakers. Much of the experimental work pursuing this idea has focused on the domain of color and has centered on the issue of whether linguistically coded color categories influence color discrimination. A new perspective has been cast on the debate by recent results that suggest that language influences color discrimination strongly in the right visual field but not in the left visual field (LVF). This asymmetry is likely related to the contralateral projection of visual fields to cerebral hemispheres and the specialization of the left hemisphere for language. The current study presents three independent experiments that replicate and extend these earlier results by using different tasks and testing across different color category boundaries. Our results differ in one respect: although we find that Whorfian effects on color are stronger for stimuli in the right visual field than in the LVF, we find that there are significant category effects in the LVF as well. The origin of the significant category effect in the LVF is considered, and two factors that might account for the pattern of results are proposed.

Combined X-ray absorption spectroscopy and density functional theory examination of ferrocene-labeled peptides.

A combination of soft X-ray absorption spectroscopy (XAS) measurements and StoBe density functional theory (DFT) calculations has been used to study the electronic structures of the ferrocene-labeled peptides Fc-Pro(n)-OBz (n = 1-4). Excellent agreement between the measured and the simulated data is observed in all cases, and the origin of all major spectral features was assigned. The breaking of the degeneracy of the ferrocene 3e(2u)-like unoccupied molecular orbital under the influence of a substituent attached to a Cp ring was observed experimentally. The influence of the bonding environment on the O 1s and N 1s XAS spectra was examined. A corrected assignment of one of the major features in the Fe 2p XAS spectra of ferrocene is proposed and supported by the DFT simulations, as well as the measured spectra.

Grounding spatial language in perception: an empirical and computational investigation.

The present paper grounds the linguistic cdategorization of space in aspects of visual perception; specifically, the structure of projective spatial terms such as above are grounded in the process of attention and in vector-sum coding of overall direction. This is formalized in the attentional vector-sum (AVS) model. This computational model accurately predicts linguistic acceptability judgments for spatial terms, under a variety of spatial configurations. In 7 experiments, the predictions of the AVS model are tested against those of 3 competing models. The results support the AVS model and disconfirm its competitors. The authors conclude that the structure of linguistic spatial categories can be partially explained in terms of independently motivated perceptual processes.

Linguistic and non-linguistic spatial categorization.

Three experiments examine the relation between linguistic and non-linguistic categorization of spatial relations. We compare linguistic and non-linguistic responses to the same spatial stimuli. Contrary to earlier claims in the literature (Hayward, W. G. & Tarr, M. J. (1995). Spatial language and spatial representation. Cognition, 55, 39-84), we find that linguistic and non-linguistic spatial categories do not correspond. Rather, they appear to have an inverse relation such that the prototypes of linguistic categories, such as 'above', are boundaries in non-linguistic spatial categorization. Evidence for this inverse relation comes from linguistic acceptability judgments and the pattern of bias in participants' reproductions of location. Our findings suggest that while linguistic and non-linguistic spatial organization rely on a common underlying structure, that structure may play different roles in the two organizational systems.