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Journal ArticleDOI: 10.1039/D0CP05323F

Sulfur Kβ X-ray emission spectroscopy: comparison with sulfur K-edge X-ray absorption spectroscopy for speciation of organosulfur compounds

04 Mar 2021-Physical Chemistry Chemical Physics (The Royal Society of Chemistry)-Vol. 23, Iss: 8, pp 4500-4508
Abstract: Until recently, sulfur was known as a "spectroscopically silent" element because of a paucity of convenient spectroscopic probes suitable for in situ chemical speciation. In recent years the technique of sulfur K-edge X-ray absorption spectroscopy (XAS) has been used extensively in sulfur speciation in a variety of different fields. With an initial focus on reduced forms of organic sulfur, we have explored a complementary X-ray based spectroscopy - sulfur Kβ X-ray emission spectroscopy (XES) - as a potential analytical tool for sulfur speciation in complex samples. We compare and contrast the sensitivity of sulfur Kβ XES with that of sulfur K-edge XAS, and find differing sensitivities for the two techniques. In some cases an approach involving both sulfur K-edge XAS and sulfur Kβ XES may be a powerful combination for deducing sulfur speciation in samples containing complex mixtures.

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Topics: Sulfur (59%), X-ray absorption spectroscopy (51%), Spectroscopy (51%)
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6 results found


Open accessJournal ArticleDOI: 10.1039/D1SC01266E
09 Jun 2021-Chemical Science
Abstract: Phosphorus is ubiquitous in biochemistry, being found in the phosphate groups of nucleic acids and the energy-transferring system of adenine nucleotides (e.g. ATP). Kβ X-ray emission spectroscopy (XES) of phosphorus has been largely unexplored, with no previous applications to biomolecules. Here, the potential of P Kβ XES to study phosphate-containing biomolecules, including ATP and NADPH, is evaluated, as is the application of the technique to aqueous solution samples. P Kβ spectra offer a detailed picture of phosphate valence electronic structure, reporting on subtle non-covalent effects, such as hydrogen bonding and ionic interactions, that are key to enzymatic catalysis. Spectral features are interpreted using density functional theory (DFT) calculations, and potential applications to the study of biological energy conversion are highlighted.

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3 Citations


Journal ArticleDOI: 10.1039/D1CC03023J
Marko Petric1, Marko Petric2, Ava Rajh3, Ava Rajh2  +5 moreInstitutions (3)
Abstract: In this work, valence-to-core (VtC) Kβ sulfur X-ray emission spectroscopy (XES) was used to perform quantitative analysis of different sulfur compounds produced in a lithium sulfur (Li–S) battery during discharge. The analysis is based on the theoretical sulfur Kβ XES spectra obtained from ab initio quantum chemical calculations based on density functional theory. The emphasis is given to the Kβ sulfur XES spectra of the polysulfide molecules (Li2Sx, x = 2,⋯,8) produced electrochemically within the Li–S battery. Ab initio molecular dynamics calculations are used further to calculate also the Kβ spectra of Li2Sx dissolved in a model solvent. Calculated spectra were directly compared with the experimental ones collected with a Johansson type tender XES spectrometer on laboratory synthesized Li2Sx reference standards and pre-cycled battery cathodes. These results demonstrate that sulfur VtC XES can be used effectively to quantitatively analyze electrochemical sulfur conversion, also in a smaller laboratory without the need for large scale synchrotron facilities.

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Topics: Sulfur (53%), Ab initio (51%)

1 Citations


Open accessJournal ArticleDOI: 10.1039/D1CP04550D
Abstract: Polymer-based batteries that utilize organic electrode materials are considered viable candidates to overcome the common drawbacks of lithium-sulfur (Li-S) batteries. A promising cathode can be developed using a conductive, flexible, and free-standing polymer, poly(4-thiophen-3-yl)benzenethiol) (PTBT), as the sulfur host material. By a vulcanization process, sulfur is embedded into this polymer. Here, we present a combination of electronic structure theory and statistical mechanics to characterize the structure of the initial state of the charged cathode on an atomic level. We perform a stability analysis of differently sulfurized TBT dimers as the basic polymer unit calculated within density-functional theory (DFT) and combine this with a statistical binding model for the binding probability distributions of the vulcanization process. From this, we deduce sulfur chain length ("rank") distributions and calculate the average sulfur rank depending on the sulfur concentration and temperature. This multi-scale approach allows us to bridge the gap between the local description of the covalent bonding process and the derivation of the macroscopic properties of the cathode. Our calculations show that the main reaction of the vulcanization process leads to high-probability states of sulfur chains cross-linking TBT units belonging to different polymer backbones, with a dominant rank around n = 5. In contrast, the connection of adjacent TBT units of the same polymer backbone by a sulfur chain is the side reaction. These results are experimentally supported by Raman spectroscopy.

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Topics: Sulfur (54%), Vulcanization (51%)

Journal ArticleDOI: 10.1021/ACS.ANALCHEM.1C01503
Abstract: Selenium is in many ways an enigmatic element. It is essential for health but toxic in excess, with the difference between the two doses being narrower than for any other element. Environmentally, selenium is of concern due to its toxicity. As the rarest of the essential elements, its low levels often provide challenges to the analytical chemist. X-ray absorption spectroscopy (XAS) provides a powerful tool for in situ chemical speciation but is severely limited by poor spectroscopic resolution arising from core-hole lifetime broadening. Here we explore selenium Kα1 high energy resolution fluorescence detected XAS (HERFD-XAS) as a novel approach for chemical speciation of selenium, in comparison with conventional Se K-edge XAS. We present spectra of a range of selenium species relevant to environmental and life science studies, including spectra of seleno-amino acids, which show strong similarities with S K-edge XAS of their sulfur congeners. We discuss strengths and limitations of HERFD-XAS, showing improvements in both speciation performance and low concentration detection. We also develop a simple method to correct fluorescence self-absorption artifacts, which is generally applicable to any HERFD-XAS experiment.

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Topics: Selenium (52%)

Journal ArticleDOI: 10.1021/ACS.ANALCHEM.1C01187
Abstract: The chemical and electronic structures of 15 different sulfates are studied using S L2,3 soft X-ray emission spectroscopy (XES). Sulfur L2,3 XES spectra of sulfates are distinctively different from those of other sulfur compounds, which makes XES a powerful technique for sulfate detection. Furthermore, subtle but distinct differences between the spectra of sulfates with different cations are observed, which allow a further differentiation of the specific compound. Most prominently, the position and width of the emission from "S 3s" derived bands systematically vary for different compounds, which can be understood with electronic structure and spectral calculations based on density functional theory.

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56 results found


Journal ArticleDOI: 10.1002/WCMS.81
Frank Neese1Institutions (1)
Abstract: ORCA is a general-purpose quantum chemistry program package that features virtually all modern electronic structure methods (density functional theory, many-body perturbation and coupled cluster theories, and multireference and semiempirical methods). It is designed with the aim of generality, extendibility, efficiency, and user friendliness. Its main field of application is larger molecules, transition metal complexes, and their spectroscopic properties. ORCA uses standard Gaussian basis functions and is fully parallelized. The article provides an overview of its current possibilities and documents its efficiency. © 2011 John Wiley & Sons, Ltd.

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6,918 Citations


Journal ArticleDOI: 10.1038/326655A0
22 Apr 1987-Nature
Abstract: The major source of cloud-condensation nuclei (CCN) over the oceans appears to be dimethylsulphide, which is produced by planktonic algae in sea water and oxidizes in the atmosphere to form a sulphate aerosol Because the reflectance (albedo) of clouds (and thus the Earth's radiation budget) is sensitive to CCN density, biological regulation of the climate is possible through the effects of temperature and sunlight on phytoplankton population and dimethylsulphide production. To counteract the warming due to doubling of atmospheric CO2, an approximate doubling of CCN would be needed.

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Topics: Cloud albedo (58%), Albedo (54%), Cloud condensation nuclei (54%) ... read more

3,572 Citations


Journal ArticleDOI: 10.1021/CT800047T
Abstract: A family of segmented all-electron relativistically contracted (SARC) basis sets for the elements Hf−Hg is constructed for use in conjunction with the Douglas−Kroll−Hess (DKH) and zeroth-order regular approximation (ZORA) scalar relativistic Hamiltonians. The SARC basis sets are loosely contracted and thus offer computational advantages compared to generally contracted relativistic basis sets, while their sufficiently small size allows them to be used in place of effective core potentials (ECPs) for routine studies of molecules. Practical assessments of the SARC basis sets in DFT calculations of atomic (ionization energies) as well as molecular properties (geometries and bond dissociation energies for MHn complexes) confirm that the basis sets yield accurate and reliable results, providing a balanced description of core and valence electron densities. CCSD(T) calculations on a series of gold diatomic compounds also demonstrate the applicability of the basis sets to correlated methods. The SARC basis sets ...

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835 Citations


Open accessJournal ArticleDOI: 10.1126/SCIENCE.AAS9185
08 Jun 2018-Science
Abstract: Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500° to 820°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatography–mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

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243 Citations


Journal ArticleDOI: 10.1021/JA00191A012
Abstract: The utility of sulfur K-edge X-ray absorption spectroscopy for the determination and quantification of sulfur forms in petroleum asphaltenes has been investigated. Both X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra were obtained for a selected group of model compounds and for several petroleum asphaltene samples. For the model compounds the sulfur XANES was found to vary widely from compound to compound and to provide a fingerprint for the form of sulfur involved. The use of third derivatives of the spectra enabled discrimination of mixtures of sulfidic and thiophenic model compounds and allowed approximate quantification of the amount of each component in the mixtures and in the asphaltene samples. These results represent the first demonstration that nonvolatile sulfur forms can be distinguished and approximately quantified by direct measurement.

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Topics: Extended X-ray absorption fine structure (57%), Asphaltene (56%), Sulfur (55%) ... read more

236 Citations