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Iodine species are important in the marine atmosphere for oxidation and new-particle formation. Understanding iodine chemistry and iodine new-particle formation requires high time resolution, high sensitivity, and simultaneous measurements of many iodine species. Here, we describe the application of a bromide chemical ionization mass spectrometer (Br-CIMS) to this task. During the iodine oxidation experiments in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber, we have measured gas-phase iodine species and sulfuric acid using two Br-CIMS, one coupled to a Multi-scheme chemical IONization inlet (Br-MION-CIMS) and the other to a Filter Inlet for Gasses and AEROsols inlet (Br-FIGAERO-CIMS). From offline calibrations and intercomparisons with other instruments, we have quantified the sensitivities of the Br-MION-CIMS to HOI, I2, and H2SO4 and obtained detection limits of 5.8 × 106, 3.8 × 105, and 2.0 × 105 molec. cm−3, respectively, for a 2 min integration time. From binding energy calculations, we estimate the detection limit for HIO3 to be 1.2 × 105 molec. cm−3, based on an assumption of maximum sensitivity. Detection limits in the Br-FIGAERO-CIMS are around 1 order of magnitude higher than those in the Br-MION-CIMS; for example, the detection limits for HOI and HIO3 are 3.3 × 107 and 5.1 × 106 molec. cm−3, respectively. Our comparisons of the performance of the MION inlet and the FIGAERO inlet show that bromide chemical ionization mass spectrometers using either atmospheric pressure or reduced pressure interfaces are well-matched to measuring iodine species and sulfuric acid in marine environments.

The four hole oxidation of water has long been considered the kinetic bottleneck for overall solar-driven water splitting, and thus requires the formation of long-lived photogenerated holes to overcome this kinetic barrier. However, photogenerated charges are prone to recombination unless they can be spatially separated. This can be achieved by coupling materials with staggered conduction and valence band positions, providing a thermodynamic driving force for charge separation. This has most aptly been demonstrated in the WO3/BiVO4 junction, in which quantum efficiencies for the water oxidation reaction can approach near unity. However, the charge carrier dynamics in this system remain elusive over timescales relevant to water oxidation (μs–s). In this work, the effect of charge separation on carrier lifetime, and the voltage dependence of this process, is probed using transient absorption spectroscopy and transient photocurrent measurements, revealing sub-μs electron transfer from BiVO4 to WO3. The interface formed between BiVO4 and WO3 is shown to overcome the “dead-layer effect” encountered in BiVO4 alone. Moreover, our study sheds light on the role of the WO3/BiVO4 junction in enhancing the efficiency of the water oxidation reaction, where charge separation across the WO3/BiVO4 junction improves both the yield and lifetime of holes present in the BiVO4 layer over timescales relevant to water oxidation.

Human exhaled breath consists of more than 3000 volatile organic compounds, many of which are relevant biomarkers for various diseases. Although gas chromatography has been the gold standard for volatile organic compound (VOC) detection in exhaled breath, recent developments in mid-infrared (MIR) laser spectroscopy have led to the promise of compact point-of-care (POC) optical instruments enabling even single breath diagnostics. In this review, we discuss the evolution of MIR sensing technologies with a special focus on photoacoustic spectroscopy, and its application in exhaled breath biomarker detection. While mid-infrared point-of-care instrumentation promises high sensitivity and inherent molecular selectivity, the lack of standardization of the various techniques has to be overcome for translating these techniques into more widespread real-time clinical use.

The Didim meteorite contains multiple lithologies and clasts of different petrologic types in a single stone. A mixture of H5 clasts in an unequilibrated H3 host was previously observed in Didim, according to the initial characterization reported in the Meteoritical Bulletin Database, providing an opportunity to investigate molecular composition that contains varying degree of equilibrium with varying mineralogy. We have taken a from large scale to small scale approach to spectroscopically investigate the chemical content of Didim. Centimeter-scale biconical reflectance spectra show that Didim contains abundant olivine, pyroxene, and other optically active minerals, evident from a strong Band I near 0.93 mu m and a weak Band II near 1.75 mu m. Micrometer-scale Raman spectroscopic investigations reveal the presence of carbonaceous material in addition to forsteritic olivine, pyroxene (augite and enstatite), feldspars, and opaque phases such as chromite and hematite. 3-D Raman tomographic imaging shows that the carbonaceous material near chondrules extends underneath a large olivine grain, going further down toward the interior, indicating that the observed carbonaceous matter is likely indigenous. Nano-scale infrared measurements reveal that the observed chemical materials in Didim contain spectral, and therefore, molecular, variations at the similar to 20 nm spatial scale. These chemical variations are normally not accessible via conventional infrared techniques, and indicate the presence of different cations in the molecular composition of observed minerals. By taking the large scale to small scale approach, we show that these compositional variations can be captured and investigated nondestructively in meteorites to understand formation/evolution of chemical components in the parent body. TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK); EuroPlanet2020RI - European Union [654208]; RISE2 node of NASA's Solar System Exploration Research Virtual Institute (SSERVI); TARLA project - Ministry of Development of Turkey [DPT2006K12-827]; Centre National d'Etudes Spatiales (CNES-France)Centre National D'etudes Spatiales We thank Istanbul Technical University staff members for preparing the thick meteorite sample for measurements. Members of the Planetary Spectroscopy Laboratory (DLR) are thanked for their assistance with reflectance experiments. We thank the Associate Editor and the anonymous reviewers for their constructive reviews and comments, which significantly improved this manuscript. Melissa D. Lane is also thanked for insightful discussions. We gratefully acknowledge support from TUBITAK (PI: M. Yesiltas), and EuroPlanet2020RI (PI: M. Yesiltas), which received funding from the European Union's Horizon 2020 research and innovation programme under grant agreement no 654208. This work was also supported by the RISE2 node of NASA's Solar System Exploration Research Virtual Institute (SSERVI; PI: T.D. Glotch). M.K. acknowledges the TARLA project, founded by the Ministry of Development of Turkey (project code: DPT2006K12-827). R.B. acknowledges support by the Centre National d'Etudes Spatiales (CNES-France, Hayabusa2 mission). The data presented here will be made publicly available at Turkish Spectral Database upon publication (http://tsd.klu.edu.tr).

Portable and cost-effective gas sensors are gaining demand for a number of environmental, biomedical, and industrial applications, yet current devices are confined into specialized labs and cannot be extended to general use. Here, we demonstrate a part-per-billion-sensitive refractive index gas sensor on a photonic chip based on silicon nitride waveguides functionalized with a mesoporous silica top-cladding layer. Low-concentration chemical vapors are detected by monitoring the output spectral pattern of an integrated unbalanced Mach-Zehnder interferometer having one coated arm exposed to the gas vapors. We retrieved a limit of detection of 65 ppb, 247 ppb, and 1.6 ppb for acetone, isopropyl alcohol, and ethanol, respectively. Our on-chip refractive index sensor provides, to the best of our knowledge, an unprecedented limit of detection for low gas concentrations based on photonic integrated circuits. As such, our results herald the implementation of compact, portable, and inexpensive devices for on-site and real-time environmental monitoring and medical diagnostics.

Multi-electron heterogeneous catalysis is a pivotal element in the ( photo) electrochemical generation of solar fuels. However, mechanistic studies of these systems are difficult to elucidate by means of electrochemical methods alone. Here we report a spectro-electrochemical analysis of hydrogen evolution on ruthenium oxide employed as an electrocatalyst and as part of a cuprous oxide-based photocathode. We use optical absorbance spectroscopy to quantify the densities of reduced ruthenium oxide species, and correlate these with current densities resulting from proton reduction. This enables us to compare directly the catalytic function of dark and light electrodes. We find that hydrogen evolution is second order in the density of active, doubly reduced species independent of whether these are generated by applied potential or light irradiation. Our observation of a second order rate law allows us to distinguish between the most common reaction paths and propose a mechanism involving the homolytic reductive elimination of hydrogen.

International audience; Recent chlorophyll-a fluorescence yield measurements, using single-turnover saturating flashes (STSFs), have revealed the involvement of a rate-limiting step in the reactions following the charge separation induced by the first flash (Magyar et al. 2018). As also shown here, in diuron-inhibited PSII core complexes isolated from Thermosynechococcus vulcanus the fluorescence maximum could only be reached by a train of STSFs. In order to elucidate the origin of the fluorescence yield increments in STSF series, we performed transient absorption measurements at 819 nm, reflecting the photooxidation and re-reduction kinetics of the primary electron donor P680. Upon single flash excitation of the dark-adapted sample, the decay kinetics could be described with lifetimes of 17 ns (~50%) and 167 ns (~30%), and a longer-lived component (~20%). This kinetics are attributed to re-reduction of P680•+ by the donor side of PSII. In contrast, upon second-flash (with Δt between 5 μs and 100 ms) or repetitive excitation, the 819 nm absorption changes decayed with lifetimes of about 2 ns (~60%) and 10 ns (~30%), attributed to recombination of the primary radical pair P680•+ Pheo•- , and a small longer-lived component (~10%). These data confirm that only the first STSF is capable of generating stable charge separation - leading to the reduction of QA ; and thus, the fluorescence yield increments elicited by the consecutive flashes must have a different physical origin. Our double-flash experiments indicate that the rate-limiting steps, detected by chlorophyll-a fluorescence, are not correlated with the turnover of P680. This article is protected by copyright. All rights reserved.

The low-frequency collective vibrational modes in proteins as well as the protein-water interface have been suggested as dominant factors controlling the efficiency of biochemical reactions and biological energy transport. It is thus crucial to uncover the mystery of the hydration structure and dynamics as well as their coupling to collective motions of proteins in aqueous solutions. Here, we report dielectric properties of aqueous bovine serum albumin protein solutions as a model system using an extremely sensitive dielectric spectrometer with frequencies spanning from megahertz to terahertz. The dielectric relaxation spectra reveal several polarization mechanisms at the molecular level with different time constants and dielectric strengths, reflecting the complexity of protein-water interactions. Combining the effective-medium approximation and molecular dynamics simulations, we have determined collective vibrational modes at terahertz frequencies and the number of water molecules in the tightly bound and loosely bound hydration layers. High-precision measurements of the number of hydration water molecules indicate that the dynamical influence of proteins extends beyond the first solvation layer, to around 7 Å distance from the protein surface, with the largest slowdown arising from water molecules directly hydrogen-bonded to the protein. Our results reveal critical information of protein dynamics and protein-water interfaces, which determine biochemical functions and reactivity of proteins. Published version

Heterogeneously integrating III-V materials on silicon photonic integrated circuits has emerged as a promising approach to make advanced laser sources for optical communication and sensing applications. Tunable semiconductor lasers operating in the 2-2.5 mu m range are of great interest for industrial and medical applications since many gases (e.g., CO2, CO, CH4) and biomolecules (such as blood glucose) have strong absorption features in this wavelength region. The development of integrated tunable laser sources in this wavelength range enables low-cost and miniature spectroscopic sensors. Here we report heterogeneously integrated widely tunable III-V-on-silicon Vernier lasers using two silicon microring resonators as the wavelength tuning components. The laser has a wavelength tuning range of more than 40 nm near 2.35 mu m. By combining two lasers with different distributed Bragg reflectors, a tuning range of more than 70 nm is achieved. Over the whole tuning range, the side-mode suppression ratio is higher than 35 dB. As a proof-of-principle, this III-V-on-silicon Vernier laser is used to measure the absorption lines of CO. The measurement results match very well with the high-resolution transmission molecular absorption (HITRAN) database and indicate that this laser is suitable for broadband spectroscopy. (C) 2018 Chinese Laser Press

WOS: 000432672300034, Previously, it has been demonstrated the electrical and magnetic properties of YMnO3 (YMO) can be tuned with substitution of different elements into Y and/or Mn sites. In this study, the electrical properties of YMO were explored via substituting osmium (Os) into Mn site with various mol %. The crystalline morphology of synthesized YMnO3 and YMn1-xOsxO3 (YMOO) (x = 0.01, 0.05, 0.10) powders were characterized with X-ray diffractometer (XRD) and infrared spectroscopy (IR) measurements. The crystalline morphology of synthesized powders was studied via scanning electron microscope (SEM). Oxidation states of constituent elements have been examined by X-ray photoelectron spectroscopy (XPS). Electrical properties of YMO and YMOO powders were investigated by dielectric/impedance spectrometer at various temperatures and frequencies. Electric modulus measurements unveiled that for each of x = 0, 0.01 and 0.05 samples there are three relaxation peaks while x = 0.10 sample shows four relaxation peaks. It has been shown that dielectric constant and conductivity properties of parent YMO can be enhanced via Os substitution, particularly, 10 mol % Os doped sample has the highest dielectric constant and conductivity at various temperatures and frequency regions. Moreover, the conduction mechanisms were also examined. It turned out that in order to explain conduction mechanism, multiple models need to be considered in the studied materials, Scientific and Technological Research Council of Turkey (TUBITAK) [116F025], This work was supported by The Scientific and Technological Research Council of Turkey (TUBITAK) through Grant No: 116F025.

A combination of X-ray photoelectron spectroscopy (XPS) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy have been used to provide an experimental measure of nitrogen atomic charge in nine ionic liquids (ILs). These experimental results are used to validate charges calculated with three computational methods: charges from electrostatic potentials using a grid-based method (ChelpG), natural bond orbital (NBO) population analysis and the atoms in molecules (AIM) approach. By combining these results with those from a previous study on sulfur, we find that ChelpG charges provide the best description of charge distribution in ILs. However, we find that ChelpG charges can lead to significant conformational dependence and therefore advise that small differences in ChelpG charges (

We present the Is X-ray photoemission spectrum of alpha-Fe2O3 in comparison with its 2p photoemission spectrum. We show that in case of transition metal oxides, because the 1s core hole is not affected by core hole spin-orbit coupling and almost not affected by core-valence multiplet effects, the Fe 1s spectrum and the complementary charge transfer multiplet calculations allow for an accurate determination of the charge transfer parameters. The consistency of the obtained parameters for the 1s photoemission was confirmed with 2p photoemission calculations and compared to 2p experimental photoemission spectra. (C) 2015 Elsevier B.V. All rights reserved.

High-resolution vacuum ultraviolet photoabsorption measurements in the wavelength range of 115-320 nm (10.8-3.9 eV) have been performed together with comprehensive relativistic time-dependent density functional calculations (TDDFT) on the low-lying excited sates of tungsten hexacarbonyl, W(CO). The higher resolution obtained reveals previously unresolved spectral features of W(CO). The spectrum shows two higher-energy bands (in the energy ranges of 7.22-8.12 eV and 8.15-9.05 eV), one of them with clear vibrational structure, and a few lower-energy shoulders in addition to a couple of lower-energy metal-to-ligand charge-transfer (MLCT) bands reported in the literature before. Absolute photoabsorption cross sections are reported and, where possible, compared to previously published results. On the basis of this combined experimental/theoretical study the absorption spectrum of the complex has been totally re-assigned between 3.9 and 10.8 eV under the light of spin-orbit coupling (SOC) effects. The present comprehensive knowledge of the nature of the electronically excited states may be of relevance to estimate neutral dissociation cross sections of W(CO), a precursor molecule in focused electron beam induced deposition (FEBID) processes, from electron scattering measurements., MM and FFS acknowledge the Portuguese National Funding Agency FCT-MCTES through grants PD/BD/106038/2015 and researcher position IF-FCT IF/00380/2014, respectively, and together with PLV the research grant UID/FIS/00068/2013. KR acknowledges the Swiss National Science Foundation for an Early Postdoc Mobility fellowship. This work was also supported by Radiation Biology and Biophysics Doctoral Training Programme (RaBBiT, PD/00193/2012); UID/Multi/ 04378/ 2013 (UCIBIO). GG acknowledges partial financial support from the Spanish Ministerio de Economia, Industria y Competitividad (Project No. FIS2016-80440). CD thanks The Labex “Chimie des Systèmes Complexes” (ANR-10-LABX- 0026_CSC). The quantum chemical calculations have been performed on the computer nodes of the LCQS, Strasbourg and thanks to the computer facilities of the High Performance Computing (HPC) regional center of University of Strasbourg. The authors wish to acknowledge the beam time at the ASTRID2 synchrotron at ISA, Aarhus University, Denmark. We also acknowledge the financial support provided by the European Community's Seventh Framework Programme (FP7/ 2007-2013) CALIPSO under grant agreement number 312284. Some of this work forms part of the EU/ESF COST Action CELINA CM1301, 11 pags., 4 figs., 2 tabs. -- This article is part of the Thematic Series "Chemistry for electron-induced nanofabrication".

Ultrafast X-ray crystallography of the photoactive yellow protein with femtosecond delays using an X-ray free electron laser has successfully probed the dynamics of an early Franck-Condon species. The femtosecond pump-probe application of protein crystallography represents a new experimental regime that provides an X-ray structural probe for coherent processes that were previously accessible primarily using ultrafast spectroscopy. We address how the optical regime of the visible pump, that is necessary to successfully resolve ultrafast structural differences, affects the motions that are measured using the technique. The sub-picosecond photochemical dynamics in PYP involves evolution of a mixture of electronic ground and excited state populations. Additional to photoisomerisation that is considered to proceed through activated barrier crossing, within the dephasing time structural motion include vibrational coherence arising from excited states, the ground state and a ground state intermediate under experimental conditions used for ultrafast crystallography. Intense optical pulses are required to convert population levels in PYP crystals that allow detection by X-ray crystallography, but the compromise currently needed for the optical bandwidth and power has consequences with regard to the contributions to the motions that are experimentally measured with femtosecond delays. We briefly review the ultrafast spectroscopy literature of the primary photoreactions of PYP and discuss relevant physical models taken from coherent control and femtosecond coherence spectroscopy literature that address both the population transfer as well as the vibrational coherences. We apply linear response theory, with the additional use of a high power approximation, of on-resonance impulsive vibrational coherence in the ground state and the non-impulsive coherence in the excited state and discuss experimental approaches to manipulate the coherence contributions. The results are generalised and extended to discuss the future capabilities of high repetition rate X-ray free electron laser instruments providing enhanced sensitivity to perform the crystallographic equivalent of an impulsive Raman measurement of vibrational coherence.

For the first time, ultrafast deactivations of photoexcited water-solvated pyrimidine nucleosides are mapped employing hybrid QM(CASPT2)/MM(AMBER) optimizations that account for explicit solvation, sugar effects, and dynamically correlated potential energy surfaces. Low-energy S1/S0 ring-puckering and ring-opening conical intersections (CIs) are suggested to drive the ballistic coherent subpicosecond (

Small molecules exhibit characteristic ro-vibrational transitions in the near- and mid-infrared spectral regions, which are strongly influenced by isotopic substitution. This gift of nature has made it possible to use laser spectroscopy for the accurate analysis of the isotopic composition of gaseous samples. Nowadays, laser spectroscopy is clearly recognized as a valid alternative to isotope ratio mass spectrometry. Laser-based instruments are leaving the research laboratory stage and are being used by a growing number of isotope researchers for significant advances in their own field of research. In this review article, we discuss the current status and new frontiers of research on high-sensitivity and high-precision laser spectroscopy for isotope ratio analyses. Although many of our comments will be generally applicable to laser isotope ratio analyses in molecules of environmental importance, this paper concerns itself primarily with water and carbon dioxide, two molecules that were studied extensively in our respective laboratories. A complete coverage of the field is practically not feasible in the space constraints of this issue, and in any case doomed to fail, considering the large body of work that has appeared ever since the review by Kerstel in 2004 (Handbook of Stable Isotope Analytical Techniques, Chapt. 34, pp. 759–787).

The effect of deuteriation on the photophysical properties of two series of regioselectively deuteriated Ru(II) complexes ([Ru(bipy)(x)(ph(2)phen)(3-x)](2+), where x = 0-3 and ph(2)phen is 4,7-diphenyt-1,10-phenanthroline and [Ru(biPY)(2)(dcbipy(2-))], where H(2)dcbipy is 4,4'-dicarboxy-2,2'-bipyridyl) is reported. Although overall, deuteriation results in an increase in emission lifetime for all complexes, the effect of substitution of hydrogen for deuterium shows strong regioselectivity both in terms of the ligand and the position on individual ligands that are exchanged. (c) 2006 Elsevier B.V. All rights reserved.

A new ab initio approach to the calculation of X-ray spectra is demonstrated. It combines a high-level quantum chemical description of the chemical interactions and local atomic multiplet effects. We show here calculated L-edge X-ray absorption (XA) and resonant inelastic X-ray scattering spectra for aqueous Ni(2+) and XA spectra for a polypyridyl iron complex. Our quantum chemical calculations on a high level of accuracy in a post-Hartree-Fock framework give excellent agreement with experiment. This opens the door to reliable and detailed information on chemical interactions and the valence electronic structure in 3d transition-metal complexes also in transient excited electronic states. As we combine a molecular-orbital description with a proper treatment of local atomic electron correlation effects, our calculations uniquely allow, in particular, identifying the influence of interatomic chemical interactions versus intra-atomic correlations in the L-edge X-ray spectra.

Studies on the exohedral and endohedral functionalization of carbon nanotubes (CNTs) with organic or inorganic chromophores and luminophores have increased substantially in recent years, making use of covalent, supramolecular, electrostatic, and host-guest preparative strategies. Research in this field has fundamental interest because the mixing of two radically different components (molecule/metal complex versus CNT) typically affords materials with exceptional electronic and structural properties while also offering the possibility of studying in detail the interactions between molecules/complexes and nanomaterials. Application perspectives can be also envisaged, particularly in the areas of light-to-electricity (e.g., photovoltaics) and electricity-to-light (e.g., electroluminescence) conversion. Here, we focus in particular on some recent results obtained in the preparation of luminescent hybrids in which suitably designed emitting moieties, placed inside or outside of carbon nanotubes through noncovalent interactions, can afford brightly glowing black photoluminescent nanostructures.

The coenzyme B-12-dependent photoreceptor protein, CarH, is a bacterial transcriptional regulator that controls the biosynthesis of carotenoids in response to light. On binding of coenzyme B-12 the monomeric apoprotein forms tetramers in the dark, which bind operator DNA thus blocking transcription. Under illumination the CarH tetramer dissociates, weakening its affinity for DNA and allowing transcription. The mechanism by which this occurs is unknown. Here we describe the photochemistry in CarH that ultimately triggers tetramer dissociation; it proceeds via a cob(III)alamin intermediate, which then forms a stable adduct with the protein. This pathway is without precedent and our data suggest it is independent of the radical chemistry common to both coenzyme B-12 enzymology and its known photochemistry. It provides a mechanistic foundation for the emerging field of B-12 photobiology and will serve to inform the development of a new class of optogenetic tool for the control of gene expression.

1s2p resonant inelastic X-ray scattering (RIXS) spectroscopy has been measured for a series of iron oxides, including octahedral and tetrahedral Fe(II) and Fe(III) systems. Their spectral shapes have been analyzed and explained using crystal-field multiplet simulations. The RIXS planes and the K-edge and L-edge X-ray absorption spectra related to these RIXS planes will be discussed with respect to their analytical opportunities. It is concluded that the full power and possibilities of 1s2p RIXS needs an overall resolution of 0.3 eV. This will yield a technique with more detailed information than K-edge and L-edge X-ray absorption combined, obtained in a single experiment. Another major advantage is that 1s2p RIXS involves only hard X-rays, and experiments under essentially any condition and on any system are feasible.

In benzophenone, intersystem crossing occurs efficiently between the S-1(n pi(star)) state and the T-1 state of dominant n pi(star) character, leading to excited triplet states after photoexcitation. The transition mechanism between S-1(n pi(star)) and T-1 is still a matter of debate, despite several experimental studies. Quantum mechanical calculations have been performed in order to assess the relative efficiencies of previously proposed mechanisms, in particular, the direct S-1 -> T-1 and indirect S-1 -> T-2(pi pi(star)) -> T-1 ones. Multiconfigurational wave function based methods are used to discuss the nature of the relevant states and also to determine minimum energy paths and conical intersections. It is found that the T-1 state has a mixed n pi(star)/pi pi(star) character and that the T-2(pi pi(star)) state acts as an intermediate state between the S-1 and T-1 states. This result is in line with recent experiments, which suggested a two-step kinetic model to populate the phosphorescent state after photoexcitation [Aloise et al., J. Phys. Chem. A, 2008, 112, 224-231].

The oxidation of methanol over highly dispersed vanadia supported on TiO2 (anatase) has been investigated using in situ Fourier transform infrared spectroscopy (FTIR), near ambient pressure X-ray photoelectron spectroscopy (NAP XPS), X-ray absorption near-edge structure (XANES), and a temperature-programmed reaction technique. The data were complemented by kinetic measurements collected in a flow reactor. It was found that dimethoxymethane competes with methyl formate at low temperatures, while the production of formaldehyde is greatly inhibited. Under the reaction conditions, the FTIR spectra show the presence of non-dissociatively adsorbed molecules of methanol, in addition to adsorbed methoxy, dioxymethylene, and formate species. According to the NAP XPS and XANES data, the reaction involves a reversible reduction of V5+ cations, indicating that the vanadia lattice oxygen participates in the oxidation of methanol via the classical Mars-van Krevelen mechanism. A detailed mechanism for the oxidation of methanol on vanadia catalysts is discussed. (C) 2013 Elsevier Inc. All rights reserved.

We show that linear polarized x-ray-absorption spectroscopy can be used to measure the temperature and thickness dependence of magnetic moments in NiO thin films. We demonstrate that both the long-range order and the nearest-neighbor spin-spin correlations can be revealed. NiO (100) films with thicknesses of 5, 10, and 20 monolayers epitaxially grown on MgO (100) are studied. The N\'eel temperature is found to be strongly reduced from the bulk value even for the 20 monolayer film.

The visible absorption spectrum of NO2 is very dense and irregular, and shows signs of a chaotic frequency and intensity distribution in the higher energy region. The complexity of the spectrum is related to a conical intersection of the potential energy surfaces of the two lowest electronic states. Above the conical intersection strong vibronic interactions lead to hybrid eigenstates, which can be viewed as mixtures of low vibrational levels of the electronically excited state and high vibrational levels of the electronic ground state. As a contribution to the elucidation of the nature of the vibronic bands of NO2 we have measured high-resolution spectra of a number of vibronic bands in the region between 10 000 and 14 000 cm−1 by exciting a supersonically cooled beam of NO2 molecules with a narrow-band Ti:Sapphire ring laser. The energy absorbed by the molecules was detected by a bolometer, and in some cases, laser-induced fluorescence was detected. The hyperfine structure is dominated by the Fermi-contact interaction and the magnitude of this interaction is a direct measure of the (electronic) composition of the hybrid eigenstates. In the present paper we have restricted our analysis to transitions of K⎯=0 stacks. The fine- and hyperfine structure of each rotational transition can be analyzed by using an effective Hamiltonian approach. The very good agreement that is found between the calculated transition strengths and the measured line intensities is evidence that in the spectral region studied, rovibronic interactions play a minor role. The composition of the hybrid eigenstates is compared with ab initio calculations reported in the literature, leading to the conclusion that measurements of the hyperfine structure are a helpful tool in characterizing vibronic bands.

This paper demonstrates that spin-polarized x-ray-excitation spectra can be obtained using K alpha emission as well as K beta lines. A spin-polarized analysis of K alpha x-ray emission and the excitation spectra by K alpha detection on a Ni compound is reported. A systematic analysis of the first-row transition-metal ions using the ligand-field multiplet calculation is presented for K alpha and K beta emission spectra.

A wavelength-resolved (λpump = 295, 285, 270, and 267 nm) photodissociation study of para-methylthiophenol (p-MePhSH) in ethanol solution has been performed using femtosecond transient absorption (TA) spectroscopy, and the results compared with those from studies of the corresponding photodissociation in cyclohexane solution at 270 nm. Anisotropy spectra are used to identify the electronic character of the initially populated excited state(s). S-H bond fission is found to occur via the dissociative S2(1(1)πσ*) state, which can be populated directly, or by ultrafast nonradiative transitions from the S3(2(1)ππ*) state, or by very efficient tunneling from the S1(1(1)ππ*) state, depending on the excitation wavelength, in line with conclusions from previous gas-phase studies of this same molecular photodissociation (Oliver, T. A. A.; King, G. A.; Tew, D. P.; Dixon R. N.; Ashfold, M. N. R. J. Phys. Chem. A 2012, 116, 12444). p-MePhS radicals are observed on a time scale faster than the instrument response at all wavelengths, but the available time resolution affords a rare opportunity to explore the branching between different electronic states of a product (the à and X̃ states of the p-MePhS radical in this case). The present study provides estimates of this branching in the products formed immediately after the first pass through the conical intersection (CI) between the S2 and S0 states. At 270 nm, for example, we identify a marked population inversion in the radical products, in contrast to the reported gas phase behavior. The finding that the contrast in branching ratio is largest between cyclohexane solution and the gas phase, with ethanol being intermediate, can be rationalized by recognizing the differing distributions of the S-H torsion angle (relative to the ring plane) in a room temperature solution compared with those in a jet-cooled molecular beam. The available time resolution also allows exploration of the electronic quenching of nascent à state radicals as solvent motion encourages recrossing of the S2/S0 CI. The average separation distance, , between the H + p-MePhS products arising in successful dissociation events is seen to increase with decreasing photolysis wavelength. This finding accords with the previous gas phase results, which determined that most of the excess energy following population of the dissociative S2 state (directly, or by ultrafast coupling from the S3 state) is released as product translation, and the expectation that should scale with the total kinetic energy release. The present work also confirms that geminate recombination of the H + p-MePhS products leads not just to reformation of parent p-MePhSH molecules but also to alternative adducts wherein the H atom bonds to the benzene ring. Analysis of the present data and results of high level ab initio calculations together with recent UV-IR pump-probe measurements (Murdock, D.; Harris, S. J.; Karsili, T. N. V.; Greetham, G. M.; Clark, I. P.; Towrie, M.; Orr-Ewing, A. J.; Ashfold, M. N. R. J. Phys. Chem. Lett. 2012, 3, 3715) allows identification of the likely adduct structures.

The temperature-dependent 1s2p resonant inelastic X-ray scattering (RIXS) spectra of CoO have been measured with 0.3 eV overall resolution, and the RIXS planes have been analyzed with multiplet calculations. The analysis of the high-resolution 1s2p RIXS plane allows a more detailed determination of the ground-state electronic structure, as compared to Is X-ray absorption spectroscopy (XAS). The apparent absence of interference effects suggests that the lifetime broadening of the pre-edge states is (significantly) reduced from the edge lifetime broadening. The temperature-dependent RIXS planes are explained as a combination of the ground state and first excited state due to thermal population of the excited state, which are a result of the symmetry distortion, 3d spin orbit coupling, and magnetic exchange interactions. No features due to charge transfer and nonlocal transitions are observed due to the relatively small cobalt oxygen overlap as compared to higher valent systems. The successful determination of the spin state and crystal field parameters using hard X-ray experiments promises to make 1s2p RIXS a useful technique for in situ transition metal oxide studies.

Bonding of the Ni$^{2+}$(aq) complex is investigated with an unprecedented combination of resonant inelastic X-ray scattering (RIXS) measurements and ab initio calculations at the Ni L absorption edge. The spectra directly reflect the relative energies of the ligand-field and charge-transfer valence-excited states. They give element-specific access with atomic resolution to the ground-state electronic structure of the complex and allow quantification of ligand-field strength and 3d–3d electron correlation interactions in the Ni$^{2+}$(aq) complex. The experimentally determined ligand-field strength is 10Dq = 1.1 eV. This and the Racah parameters characterizing 3d–3d Coulomb interactions B = 0.13 eV and C = 0.42 eV as readily derived from the measured energies match very well with the results from UV–vis spectroscopy. Our results demonstrate how L-edge RIXS can be used to complement existing spectroscopic tools for the investigation of bonding in 3d transition-metal coordination compounds in solution. The ab initio RASPT2 calculation is successfully used to simulate the L-edge RIXS spectra.

Soil carbon dioxide (CO2) efflux is an important component of the carbon (C) cycle but the biological and physical processes involved in soil CO2 production and transport are not fully understood. To improve our knowledge, we present a new approach to measure simultaneously soil CO2 concentrations and efflux, and their respective isotopic signatures (C-13-CO2). To quantify soil air (CO2)-C-13 and (CO2)-C-12 concentrations, we adapted a method based on CO2 diffusion from soil pores into tubes with a highly gas-permeable membrane wall. These tubes were placed horizontally at different depths in the soil. Air was sampled automatically from the tubes and injected through a diluting system into a tuneable diode laser absorption spectrometer. The CO2 and C-13-CO2 vertical profiles were thus obtained at hourly intervals. Our tests demonstrated the absence of fractionation in the membrane tubes for C-13-CO2. Subsequently, we set up field experiments for two forest soils, which showed that natural soil CO2 concentrations and C-13-CO2 were not affected significantly by the measurement system. While C-13-CO2 in air-filled pores below 5cm was constant over 3days, we observed large diurnal variations in C-13-CO2 efflux. However, the average difference between the two measurements was close to -4.4 parts per thousand, which supports steady-state diffusion over this 3-day period. This new method seems to be a very effective way to measure the C-13-CO2 profile of the soil atmosphere, and demonstrates that the fractionation that occurs during diffusion is the main transport process that affects the C-13-CO2 of the soil CO2 efflux on a daily timescale while advection may account for within-day variations.

It is demonstrated that enhanced mode suppression in stimulated photon echo experiments can be obtained by diagonal time gating of the echo. This technique is especially important when the optical dynamics of the system is non-Markovian. A two-mode Brownian oscillator model is used to analyze the effect of time gating on the stimulated photon echo. The method is demonstrated on a dye solution of DTTCI in ethylene glycol at room temperature. Experimentally, time gating of the echo is accomplished by means of femtosecond phase-locked heterodyne detected stimulated photon echo. The vibrational dynamics in this system are explored by conventional stimulated photon echo experiments, Especially stimulated photon echo-maximum shift measurements are found to be particularly useful. (C) 1996 American Institute of Physics.

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in LixFePO4 nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of LixFePO4 nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO4 single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the LixFePO4 system.

In view of the limited oil reserves the methanol-to-olefin (MTO) process is an interesting catalytic route to provide raw materials for chemical industries. In the last decades, a vast number of studies have been devoted to increase our understanding of this important catalytic reaction leading to a consensus concerning the mechanism.[1–4] Accordingly, MTO is thought to proceed through the so-called “hydrocarbon pool” (HCP) mechanism,[5, 6] in which methanol is added to an organic scaffold present within the zeolite framework. This is followed by elimination of olefinic species in a closed catalytic cycle. Microporous silicoaluminophosphates and aluminosilicates, such as SAPO-34 and ZSM-5, are often used as MTO catalysts because of their unique acidic and structural properties. In the case of ZSM-5 the formation of ethene and propene is governed by two different catalytic routes,[7,8] allowing in principle to control the ethene/propene ratio. Unfortunately, throughout the MTO reaction undesired carbon deposits are formed in the narrow micropore system of ZSM-5, leading to severely restricted diffusion and therefore limited catalytic activity.[9] To overcome these limitations efforts have been made to improve the pore accessibility during synthesis,[10–12] and/or in post-synthetic steps,[13, 14] resulting in significant improvements in the diffusion properties of ZSM-5. In this work, two commercial ZSM-5 zeolites with dimensions of approximately 200–800 nm have been studied by scanning transmission X-ray microscopy (STXM). The first sample, denoted as ZSM-5-C, was calcined for 6 h at 5508C, whereas the second sample, further labeled as ZSM-5-S, was steamed for 3 h at 7008C. Details on the preparation and characteristics of ZSM-5-C and ZSM-5-S can be found in the Supporting Information (Figures S1–S13, Tables S1–S6). We will show how STXM, in combination with bulk characterization techniques, allows investigating the physicochemical properties of ZSM-5 zeolites in a novel way at the nanoscale.[ 15, 16] More specifically, detailed chemical maps, with a spatial resolution of 70 nm, have been obtained of aluminum, oxygen, and carbon, even under realistic reaction conditions.[17–19] In this manner, the influence of steaming on the state of aluminum, that is, the coordination and spatial distribution, as well as on the MTO performance, has been unraveled.

A series of three 5'-aryl-2,5-dithienylthiazolo[5,4-d]thiazole (DTTzTz) semiconducting molecules with different aryl substituents has been investigated as alternative acceptor materials in combination with the donor polymer poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene vinylene] (MDMO-PPV) in order to evaluate the photoinduced charge transfer (CT) efficiency in the resulting blends, designed towards possible application in organic photovoltaics. Photoluminescence quenching together with polaron detection by electron paramagnetic resonance and photoinduced absorption (PIA) demonstrate an increasing charge transfer efficiency when the DTTzTz substituents are varied from thien-2-yl to 4-trifluoromethylphenyl and 4-cyanophenyl groups, correlating well with the increasing acceptor strength in this series of molecules. In line with this observation, there is a decrease in the effective optical bandgap relative to pure MDMO-PPV that becomes more pronounced along this series of acceptor compounds, reaching 0.12 eV in the blend with 4-CN-Ph-DTTzTz. Intermolecular interactions between the blend components lead to lower energy transitions which are found to contribute significantly to the device external quantum efficiency. The high V-OC reached in devices based on MDMO-PPV: 4-CN-Ph-DTTzTz blends meets the expectations for such a donor: acceptor combination. However, thermal activation of charge carrier recombination occurs because of the weak driving force for charge transfer, as shown by time-dependent PIA measurements, and this is suggested as a cause for the observed low photovoltaic performance.

In this paper, we analyze the sensitivity enhancement attainable by combining a wavelength modulation (WM) technique to integrated cavity output spectroscopy (ICOS), pointing out how the spectrometer’s parameters and the acquisition strategy affect the detection noise in both techniques. We point out that WM-ICOS is mainly limited by the slow scan rate that it requires, compared to regular ICOS. Nevertheless, according to our analysis, WM can still appreciably improve the SNR of an ultrasensitive ICOS system, if the cavity transmission is so low that the detector noise is not negligible. In light of these considerations, we directly compare the performance of ICOS and WM-ICOS in a high sensitivity ambient-air methane detection experiment, finding a good agreement with the theoretical influence of the various spectrometer parameters.

In this paper we will present measurements, using various kinds of spectroscopy, on the hole-doped compound Bi2Sr2Ca1-xY(x)Cu(2)O(8+delta), with x ranging from 0.0 to 1.0. Cu 2p x-ray photoelectron spectra are compared with cluster calculations using nonlocal screening effects. The consequences of hole doping and multiplet interaction are also studied. The photoemission and inverse-photoemission data indicate that the appearance of intensity at the Fermi level is a result of the shift of the chemical potential to the top of the valence band combined with a shift of spectral weight from high- to low-energy states.

Radiocarbon ($^{14}\mathrm{C}$) concentrations at a 43 parts-per-quadrillion level are measured by using saturated-absorption cavity ringdown spectroscopy by exciting radiocarbon-dioxide ($^{14}\mathrm{C}^{16}\mathrm{O}_{2}$) molecules at the $4.5\text{ }\text{ }\ensuremath{\mu}\mathrm{m}$ wavelength. The ultimate sensitivity limits of molecular trace gas sensing are pushed down to attobar pressures using a comb-assisted absorption spectroscopy setup. Such a result represents the lowest pressure ever detected for a gas of simple molecules. The unique sensitivity, the wide dynamic range, the compactness, and the relatively low cost of this table-top setup open new perspectives for $^{14}\mathrm{C}$-tracing applications, such as radiocarbon dating, biomedicine, or environmental and earth sciences. The detection of other very rare molecules can be pursued as well thanks to the wide and continuous mid-IR spectral coverage of the described setup.

Solution-phase photoinduced low-spin to high-spin conversion in the Fe(II) polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)(3) is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) --> (1)MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L(2)- and L(3)-edges were observed concomitant with formation of the transient high-spin (5)T(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of approximately 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 A increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

The present status of in-situ scanning transmission X-ray microscopy (STXM) is reviewed, with an emphasis on the abilities of the STXM technique in comparison with electron microscopy. The experimental aspects and interpretation of X-ray absorption spectroscopy (XAS) are briefly introduced and the experimental boundary conditions that determine the potential applications for in-situ XAS and in-situ STXM studies are discussed. Nanoscale chemical imaging of catalysts under working conditions is outlined using cobalt and iron Fischer-Tropsch catalysts as showcases. In the discussion, we critically compare STXM-XAS and STEM-EELS (scanning transmission electron microscopy-electron energy loss spectroscopy) measurements and indicate some future directions of in-situ nanoscale imaging of catalytic solids and related nanomaterials.

(2+1) Resonance-enhanced multiphoton ionization (REMPI) spectra were recorded for hexafluorobenzene (HFBz) and 1,3,5-trifluorobenzene (TRFBz) using UV laser light. Vibronic structure of the Rydberg series converging to the first ionization threshold are resolved. While only one Rydberg series is observed for HFBz (region 67 500-70 820 cm(-1)), two of them are detected for TRFBz (region 66 000-69 100 cm(-1)). The resolved vibronic structures are assigned with the aid of theoretical predictions. (C) 2010 Elsevier B.V. All rights reserved. Chemical Physics Letters

The light-induced spin and structure changes upon excitation of the singlet metal-to-ligand charge transfer (1MLCT) state of Fe(II)-polypyridine complexes are investigated in detail in the case of aqueous iron(II)-tris-bipyridine ([FeII(bpy)3]2+) by a combination of ultrafast optical and X-ray spectroscopies. Polychromatic femtosecond fluorescence up-conversion, transient absorption studies in the 290-600nm region and femtosecond X-ray absorption spectroscopy allow us to retrieve the entire photocycle upon excitation of the 1MLCT state from the singlet low-spin ground state (1GS) as the following sequence: 1,3MLCT→5T→1GS, which does not involve intermediate singlet and triplet ligand-field states. The population time of the HS state is found to be ∼150fs, leaving it in a vibrationally hot state that relaxes in 2-3ps, before decaying to the ground state in 650ps. We also determine the structure of the high-spin quintet excited state by picosecond X-ray absorption spectroscopy at the K-edge of Fe. We argue that given the many common electronic (ordering of electronic states) and structural (Fe-N bond elongation in the high-spin state, Fe-N mode frequencies, etc.) similarities between all Fe(II)-polypyridine complexes, the results on the electronic relaxation processes reported in the case of [FeII(bpy)3]2+ are of general validity to the entire family of Fe(II)-polypyridine complexes. © 2009 Elsevier B.V.

The structural and electronic properties of anatase TiO2 nanocrystals (NCs) are investigated through first-principles calculations. The dependence of the structural properties (e.g., NC volume variations) on the surface chemistry is discussed by considering two different surface coverages (dissociated water and hydrogens). Both prevent a pronounced reconstruction of the surface, thus ensuring a better crystalline organization of the atoms with respect to the bare NC. In particular, the results for the hydrated NC do show the largest overlap with the experimental findings. The band-gap blueshift with respect to the bulk shows up for both the bare and the hydrated NC, whereas hydrogen coverage or oxygen desorption from the bare NCs induce occupied electronic states below the conduction levels thus hindering the gap opening due to quantum confinement. These states are spatially localized in a restricted region and can be progressively annihilated by oxygen adsorption on undercoordinated surface titanium atoms. Formation energy calculations reveal that surface hydration leads to the most stable NC, in agreement with the experimental finding that the truncated bipyramidal morphology is typical of the moderate acidic environment. Oxygen desorption from the bare NC is unfavorable, thus highlighting the stabilizing role of surface oxygen stoichiometry for TiO2. Available experimental data on the electronic and structural properties of TiO2 NCs are summarized and compared with our results.

The active site of the oxygen-avid truncated hemoglobin from Bacillus subtilis has been characterized by infrared absorption and resonance Raman spectroscopies, and the dynamics of CO rebinding after photolysis has been investigated by picosecond transient absorption spectroscopy. Resonance Raman experiments on the CO bound adduct revealed the presence of two Fe-CO stretching bands at 545 and 520 cm(-1), respectively. Accordingly, two C-O stretching bands at 1924 and 1888 cm(-1) were observed in infrared absorption and resonance Raman measurements. The very low C-O stretching frequency at 1888 cm(-1) (corresponding to the extremely high RR stretching frequency at 545 cm(-1)) indicates unusually strong hydrogen bonding between CO and distal residues. On the basis of a comparison with. other truncated hemoglobin it is envisaged that the two CO conformers are determined by specific interactions with the TrpG8 and TyrB10 residues. Mutation of TrpG8 to Leu deeply alters the hydrogen-bonding network giving rise mainly to a CO conformer characterized by a Fe-CO stretching band at 489 cm(-1) and a CO stretching band at 1958 cm(-1). Picosecond laser photolysis experiments carried out on the CO bound adduct revealed dynamical processes that take place within a few nanoseconds after photolysis. Picosecond dynamics is largely dominated by CO geminate rebinding and is consistent with strong H-bonding contributions of TyrB10 and TrpG8 to ligand stabilization.