Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy

Holden, William M.; Jahrman, Evan P.; Govind, Niranjan; Seidler, Gerald T

doi:10.1021/acs.jpca.0c04195

Title: Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy

Journal Article · Tue Jun 02 00:00:00 EDT 2020 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.0c04195· OSTI ID:1646827

Holden, William M. ^[1]; Jahrman, Evan P. ^[1];

^[2];

^[1]

Univ. of Washington, Seattle, WA (United States). Dept. of Physics
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

An extensive experimental and theoretical study of the Kα and Kβ high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented here. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the core-to-core Kα as well as the full range of spectral features in the valence-to-core Kβ spectrum. The ability to accurately calculate the sulfur Kα energy shift supports the use of sulfur Kα XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur Kβ spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successful prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States). Environmental Molecular Sciences Laboratory (EMSL)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC05-76RL01830; KC030105172685; DMR-1719797

OSTI ID:: 1646827

Report Number(s):: PNNL-SA-148445

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 124, Issue 26; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 29 works

Citation information provided by
Web of Science

References (146)

Lithium-Sulfur Batteries: Progress and Prospects Manthiram, Arumugam; Chung, Sheng-Heng; Zu, Chenxi Advanced Materials, Vol. 27, Issue 12 https://doi.org/10.1002/adma.201405115	journal	February 2015
Rechargeable Lithium–Sulfur Batteries Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500062v	journal	July 2014
Li–O₂ and Li–S batteries with high energy storage Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J. Nature Materials, Vol. 11, Issue 1, p. 19-29 https://doi.org/10.1038/nmat3191	journal	January 2012
Iron-Sulfur Clusters: Nature's Modular, Multipurpose Structures Beinert, H. Science, Vol. 277, Issue 5326 https://doi.org/10.1126/science.277.5326.653	journal	August 1997
Interaction of Sulfur with Well-Defined Metal and Oxide Surfaces: Unraveling the Mysteries behind Catalyst Poisoning and Desulfurization Rodriguez, José A.; Hrbek, Jan Accounts of Chemical Research, Vol. 32, Issue 9 https://doi.org/10.1021/ar9801191	journal	September 1999
Sulfur as a catalyst promoter or selectivity modifier in heterogeneous catalysis McCue, Alan J.; Anderson, James A. Catal. Sci. Technol., Vol. 4, Issue 2 https://doi.org/10.1039/C3CY00754E	journal	January 2014
Sulfur in soils Wilhelm Scherer, Heinrich Journal of Plant Nutrition and Soil Science, Vol. 172, Issue 3 https://doi.org/10.1002/jpln.200900037	journal	May 2009
Global and regional trends of atmospheric sulfur Aas, Wenche; Mortier, Augustin; Bowersox, Van Scientific Reports, Vol. 9, Issue 1 https://doi.org/10.1038/s41598-018-37304-0	journal	January 2019
X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor Lancaster, K. M.; Roemelt, M.; Ettenhuber, P. Science, Vol. 334, Issue 6058 https://doi.org/10.1126/science.1206445	journal	November 2011
Valence-to-Core X-ray Emission Spectroscopy: A Sensitive Probe of the Nature of a Bound Ligand Pollock, Christopher J.; DeBeer, Serena Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja200560z	journal	April 2011
Probing Valence Orbital Composition with Iron Kβ X-ray Emission Spectroscopy Lee, Nicole; Petrenko, Taras; Bergmann, Uwe Journal of the American Chemical Society, Vol. 132, Issue 28 https://doi.org/10.1021/ja101281e	journal	July 2010
Insights into the Geometric and Electronic Structure of Transition Metal Centers from Valence-to-Core X-ray Emission Spectroscopy Pollock, Christopher J.; DeBeer, Serena Accounts of Chemical Research, Vol. 48, Issue 11 https://doi.org/10.1021/acs.accounts.5b00309	journal	September 2015
Valence to Core X-ray Emission Spectroscopy Gallo, Erik; Glatzel, Pieter Advanced Materials, Vol. 26, Issue 46 https://doi.org/10.1002/adma.201304994	journal	May 2014
Sulfur-Metal Orbital Hybridization in Sulfur-Bearing Compounds Studied by X-ray Emission Spectroscopy Mori, R. Alonso; Paris, E.; Giuli, G. Inorganic Chemistry, Vol. 49, Issue 14 https://doi.org/10.1021/ic100304z	journal	July 2010
Electronic Structure of Third-Row Elements in Different Local Symmetries Studied by Valence-to-Core X-ray Emission Spectroscopy Petric, Marko; Bohinc, Rok; Bučar, Klemen Inorganic Chemistry, Vol. 55, Issue 11 https://doi.org/10.1021/acs.inorgchem.6b00237	journal	May 2016
Chemical effects in X-ray Kα and Kβ emission spectra of sulfur in organic compounds Yasuda, Seiji; Kakiyama, Hitoo Spectrochimica Acta Part A: Molecular Spectroscopy, Vol. 35, Issue 5 https://doi.org/10.1016/0584-8539(79)80164-6	journal	January 1979
A Modern Laboratory XAFS Cookbook Seidler, Gt; Mortensen, Dr; Ditter, As Journal of Physics: Conference Series, Vol. 712 https://doi.org/10.1088/1742-6596/712/1/012015	journal	May 2016
A laboratory-based hard x-ray monochromator for high-resolution x-ray emission spectroscopy and x-ray absorption near edge structure measurements Seidler, G. T.; Mortensen, D. R.; Remesnik, A. J. Review of Scientific Instruments, Vol. 85, Issue 11 https://doi.org/10.1063/1.4901599	journal	November 2014
Benchtop Nonresonant X-ray Emission Spectroscopy: Coming Soon to Laboratories and XAS Beamlines Near You? Mortensen, Devon R.; Seidler, Gerald T.; Ditter, Alexander S. Journal of Physics: Conference Series, Vol. 712 https://doi.org/10.1088/1742-6596/712/1/012036	journal	May 2016
A compact dispersive refocusing Rowland circle X-ray emission spectrometer for laboratory, synchrotron, and XFEL applications Holden, William M.; Hoidn, Oliver R.; Ditter, Alexander S. Review of Scientific Instruments, Vol. 88, Issue 7 https://doi.org/10.1063/1.4994739	journal	July 2017
An improved laboratory-based x-ray absorption fine structure and x-ray emission spectrometer for analytical applications in materials chemistry research Jahrman, Evan P.; Holden, William M.; Ditter, Alexander S. Review of Scientific Instruments, Vol. 90, Issue 2 https://doi.org/10.1063/1.5049383	journal	February 2019
A novel von Hamos spectrometer for efficient X-ray emission spectroscopy in the laboratory Anklamm, Lars; Schlesiger, Christopher; Malzer, Wolfgang Review of Scientific Instruments, Vol. 85, Issue 5 https://doi.org/10.1063/1.4875986	journal	May 2014
Laboratory-scale X-ray absorption spectroscopy approach for actinide research: Experiment at the uranium L3-edge Bès, R.; Ahopelto, T.; Honkanen, A. -P. Journal of Nuclear Materials, Vol. 507 https://doi.org/10.1016/j.jnucmat.2018.04.034	journal	August 2018
Laboratory-based micro-X-ray fluorescence setup using a von Hamos crystal spectrometer and a focused beam X-ray tube Kayser, Y.; Błachucki, W.; Dousse, J. -Cl. Review of Scientific Instruments, Vol. 85, Issue 4 https://doi.org/10.1063/1.4869340	journal	April 2014
Laboratory von Hámos X-ray spectroscopy for routine sample characterization Németh, Zoltán; Szlachetko, Jakub; Bajnóczi, Éva G. Review of Scientific Instruments, Vol. 87, Issue 10 https://doi.org/10.1063/1.4964098	journal	October 2016
High-resolution Laue-type DuMond curved crystal spectrometer Szlachetko, M.; Berset, M.; Dousse, J. -Cl. Review of Scientific Instruments, Vol. 84, Issue 9 https://doi.org/10.1063/1.4821621	journal	September 2013
Johann-type laboratory-scale x-ray absorption spectrometer with versatile detection modes Honkanen, Ari-Pekka; Ollikkala, Sami; Ahopelto, Taru Review of Scientific Instruments, Vol. 90, Issue 3 https://doi.org/10.1063/1.5084049	journal	March 2019
In-house setup for laboratory-based x-ray absorption fine structure spectroscopy measurements Zeeshan, F.; Hoszowska, J.; Loperetti-Tornay, L. Review of Scientific Instruments, Vol. 90, Issue 7 https://doi.org/10.1063/1.5094873	journal	July 2019
A laboratory-based double X-ray spectrometer for simultaneous X-ray emission and X-ray absorption studies Błachucki, Wojciech; Czapla-Masztafiak, Joanna; Sá, Jacinto Journal of Analytical Atomic Spectrometry, Vol. 34, Issue 7 https://doi.org/10.1039/C9JA00159J	journal	January 2019
A laboratory spectrometer for high throughput X-ray emission spectroscopy in catalysis research Malzer, Wolfgang; Grötzsch, Daniel; Gnewkow, Richard Review of Scientific Instruments, Vol. 89, Issue 11 https://doi.org/10.1063/1.5035171	journal	November 2018
Variable Rowland radius laboratory vacuum surface-sensitive x-ray absorption fine structure spectrometer Yuryev, Yu. N.; Lee, Hwack-Joo; Park, Hyun-Min Review of Scientific Instruments, Vol. 78, Issue 2 https://doi.org/10.1063/1.2669591	journal	February 2007
Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy Holden, William M.; Seidler, Gerald T.; Cheah, Singfoong The Journal of Physical Chemistry A, Vol. 122, Issue 23 https://doi.org/10.1021/acs.jpca.8b02816	journal	May 2018
Determination of Hexavalent Chromium Fractions in Plastics Using Laboratory-Based, High-Resolution X-ray Emission Spectroscopy Jahrman, Evan P.; Seidler, Gerald T.; Sieber, John R. Analytical Chemistry, Vol. 90, Issue 11 https://doi.org/10.1021/acs.analchem.8b00302	journal	April 2018
Probing Surface Defects of InP Quantum Dots Using Phosphorus Kα and Kβ X-ray Emission Spectroscopy Stein, Jennifer L.; Holden, William M.; Venkatesh, Amrit Chemistry of Materials, Vol. 30, Issue 18 https://doi.org/10.1021/acs.chemmater.8b02590	journal	August 2018
4-1: Invited Paper: Role of Phosphorus Oxidation in Controlling the Luminescent Properties of Indium Phosphide Quantum Dots Cossairt, Brandi M.; Stein, Jennifer L.; Holden, William M. SID Symposium Digest of Technical Papers, Vol. 49, Issue 1 https://doi.org/10.1002/sdtp.12481	journal	May 2018
Classification of local chemical environments from x-ray absorption spectra using supervised machine learning Carbone, Matthew R.; Yoo, Shinjae; Topsakal, Mehmet Physical Review Materials, Vol. 3, Issue 3 https://doi.org/10.1103/PhysRevMaterials.3.033604	journal	March 2019
Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles Timoshenko, Janis; Lu, Deyu; Lin, Yuewei The Journal of Physical Chemistry Letters, Vol. 8, Issue 20 https://doi.org/10.1021/acs.jpclett.7b02364	journal	October 2017
Effects of Chemical Binding on the X-Ray $K α_{1, 2}$ Doublet Lines of Sulphur Studied with a Two-Crystal Spectrometer Parratt, Lyman G. Physical Review, Vol. 49, Issue 1 https://doi.org/10.1103/PhysRev.49.14	journal	January 1936
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. I. The Peak Shift of K α and the Number of Valence Electrons of the Sulfur Atom in Compounds Sato, Toshio; Takahashi, Yoshihito; Yabe, Katsumasa Bulletin of the Chemical Society of Japan, Vol. 40, Issue 2 https://doi.org/10.1246/bcsj.40.298	journal	February 1967
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. II. The Number of Valence Electrons of the Sulfur Atom in Organic Compounds Takahashi, Yoshihito; Yabe, Katsumasa; Sato, Toshio Bulletin of the Chemical Society of Japan, Vol. 42, Issue 9 https://doi.org/10.1246/bcsj.42.2707	journal	September 1969
Possibility of sulphur-oxygen substitution in YBa2Cu3O6+xSy analyzed by means of X-ray emission spectroscopy Yarmoshenko, Yu. M.; Trofimova, V. A.; Elokhina, L. V. Journal of Physics and Chemistry of Solids, Vol. 54, Issue 10 https://doi.org/10.1016/0022-3697(93)90169-R	journal	October 1993
X-ray emission spectra and valence state of sulphur atoms of YBa ₂ ((CuO) _1-x (NiS) _x ) ₃ O _{4- delta} Yarmoshenko, Yu M.; Trofimova, V. A.; Dolgih, V. E. Journal of Physics: Condensed Matter, Vol. 7, Issue 1 https://doi.org/10.1088/0953-8984/7/1/018	journal	January 1995
X-ray determination of effective charges on sulphur, phosphorus, silicon and chlorine atoms Dolenko, G. N. Journal of Molecular Structure, Vol. 291, Issue 1 https://doi.org/10.1016/0022-2860(93)80253-R	journal	January 1993
Electronic Structure of Sulfur Studied by X-ray Absorption and Emission Spectroscopy Alonso Mori, R.; Paris, E.; Giuli, G. Analytical Chemistry, Vol. 81, Issue 15 https://doi.org/10.1021/ac900970z	journal	August 2009
Sulfur K-edge XANES Spectroscopy as a Tool for Understanding Sulfur Dynamics in Soil Organic Matter Solomon, Dawit; Lehmann, Johannes; Martínez, Carmen Enid Soil Science Society of America Journal, Vol. 67, Issue 6 https://doi.org/10.2136/sssaj2003.1721	journal	November 2003
Quantitative analysis of all major forms of sulfur in coal by x-ray absorption fine structure spectroscopy Huffman, G. P.; Mitra, S.; Huggins, F. E. Energy & Fuels, Vol. 5, Issue 4 https://doi.org/10.1021/ef00028a008	journal	July 1991
Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity Jugo, Pedro J.; Wilke, Max; Botcharnikov, Roman E. Geochimica et Cosmochimica Acta, Vol. 74, Issue 20 https://doi.org/10.1016/j.gca.2010.07.022	journal	October 2010
Direct determination and quantification of sulfur forms in coals from the Argonne Premium Sample Program George, Graham N.; Gorbaty, Martin L.; Kelemen, Simon R. Energy & Fuels, Vol. 5, Issue 1 https://doi.org/10.1021/ef00025a016	journal	January 1991
Sulfur Speciation in Soil by S K -Edge XANES Spectroscopy: Comparison of Spectral Deconvolution and Linear Combination Fitting Prietzel, Jörg; Botzaki, Anna; Tyufekchieva, Nora Environmental Science & Technology, Vol. 45, Issue 7 https://doi.org/10.1021/es102180a	journal	April 2011
XANES calibrations for the oxidation state of iron in a silicate glass Berry, Andrew J.; O’Neill, Hugh St. C.; Jayasuriya, Kasthuri D. American Mineralogist, Vol. 88, Issue 7 https://doi.org/10.2138/am-2003-0704	journal	July 2003
The Interpretation of Sulfur K-Edge XANES Spectra: A Case Study on Thiophenic and Aliphatic Sulfur Compounds Mijovilovich, A.; Pettersson, L. G. M.; Mangold, S. The Journal of Physical Chemistry A, Vol. 113, Issue 12 https://doi.org/10.1021/jp806823c	journal	March 2009
Description of the Ground-State Covalencies of the Bis(dithiolato) Transition-Metal Complexes from X-ray Absorption Spectroscopy and Time-Dependent Density-Functional Calculations Ray, Kallol; DeBeer George, Serena; Solomon, Edward I. Chemistry - A European Journal, Vol. 13, Issue 10 https://doi.org/10.1002/chem.200601425	journal	March 2007
Dithiolene radicals: Sulfur K-edge X-ray absorption spectroscopy and Harry's intuition Sproules, Stephen; Wieghardt, Karl Coordination Chemistry Reviews, Vol. 255, Issue 7-8 https://doi.org/10.1016/j.ccr.2010.12.006	journal	April 2011
An X-Ray Emission Spectroscopic Investigation of the Chemical Bond of Sulfur. III. The Profile of S K β Band in Sulfur Compounds Takahashi, Yoshihito; Yabe, Katsumasa Bulletin of the Chemical Society of Japan, Vol. 42, Issue 11 https://doi.org/10.1246/bcsj.42.3064	journal	November 1969
X-ray emission spectra of YSr2Cu3O7−δ containing sulphate and phosphate groups Yarmoshenko, Yu. M.; Trofimova, V. A.; Kurmaev, E. Z. Physica C: Superconductivity, Vol. 224, Issue 3-4 https://doi.org/10.1016/0921-4534(94)90268-2	journal	May 1994
Electronic structure of cuprates containing sulfur and phosphorus oxyanions Yarmoshenko, Yu. M.; Korotin, M. A.; Trofimova, V. A. Physical Review B, Vol. 52, Issue 16 https://doi.org/10.1103/PhysRevB.52.11830	journal	October 1995
Sulfur $K β$ x-ray emission spectra and electronic structures of some metal sulfides Sugiura, Chikara; Gohshi, Yohichi; Suzuki, Isao Physical Review B, Vol. 10, Issue 2 https://doi.org/10.1103/PhysRevB.10.338	journal	July 1974
Sulfur K β X-Ray Emission Bands and Valence-Band Structures of Transition-Metal Disulfides Sugiura, Chikara; Suzuki, Isao; Kashiwakura, Jiro Journal of the Physical Society of Japan, Vol. 40, Issue 6 https://doi.org/10.1143/JPSJ.40.1720	journal	June 1976
Kβ X-Ray Emission and K X-Ray Absorption Spectra of Sulfur in Sulfate Compounds Sugiura, Chikara Japanese Journal of Applied Physics, Vol. 32, Issue Part 1, No. 8 https://doi.org/10.1143/JJAP.32.3509	journal	August 1993
K β X-Ray Emission Spectra and Chemical Environments of Phosphorus and Sulfur in Various Compounds Sugiura, Chikara Journal of the Physical Society of Japan, Vol. 64, Issue 10 https://doi.org/10.1143/JPSJ.64.3840	journal	October 1995
Sulfur K β X-Ray Emission Spectra and Valence-Band Structures of Metal Sulfides Sugiura, Chikara; Yorikawa, Hiroharu; Muramatsu, Shinji Journal of the Physical Society of Japan, Vol. 66, Issue 2 https://doi.org/10.1143/JPSJ.66.503	journal	February 1997
Design of a Double-Crystal X-Ray Vacuum Spectrometer Parratt, Lyman G. Physical Review, Vol. 41, Issue 5 https://doi.org/10.1103/PhysRev.41.553	journal	September 1932
A wide-range, single-axis, vacuum two-crystal spectrometer for fluorescent X-ray analysis Gohshi, Yohichi; Hukao, Yoshiro; Hori, Kohei Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 27, Issue 3 https://doi.org/10.1016/0584-8547(72)80016-8	journal	March 1972
Simple quasi‐two‐crystal x‐ray spectrometer Taniguchi, Kazuo Review of Scientific Instruments, Vol. 54, Issue 5 https://doi.org/10.1063/1.1137437	journal	May 1983
Molecular-Orbital Interpretation of the X-Ray K Spectra from α-Sulfur Sugiura, Chikara Journal of the Physical Society of Japan, Vol. 30, Issue 6 https://doi.org/10.1143/JPSJ.30.1766	journal	June 1971
Molecular Orbital Interpretation of X-Ray Emission Spectra II. Sulfur and chlorine Kβ spectra of some inorganic anions Karlsson, Göran; Manne, Rolf Physica Scripta, Vol. 4, Issue 3 https://doi.org/10.1088/0031-8949/4/3/007	journal	September 1971
Discrete Variational Xα Cluster Calculations. IV. Application to X-Ray Emission Study Adachi, Hirohiko; Taniguchi, Kazuo Journal of the Physical Society of Japan, Vol. 49, Issue 5 https://doi.org/10.1143/JPSJ.49.1944	journal	November 1980
Calculation of sulfur K ß X-ray spectra Eiichirou, Uda; Jun, Kawai; Uda, M. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 75, Issue 1-4 https://doi.org/10.1016/0168-583X(93)95604-4	journal	April 1993
Intensity analysis of S Kß emission spectra of Na2SO3 by the use of DV-Xα MO method Mogi, M.; Ota, A.; Ebihara, S. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 75, Issue 1-4 https://doi.org/10.1016/0168-583X(93)95603-3	journal	April 1993
Chemical speciation via X-ray emission spectroscopy in the tender X-ray range Petric, Marko; Kavčič, Matjaž Journal of Analytical Atomic Spectrometry, Vol. 31, Issue 2 https://doi.org/10.1039/C5JA00394F	journal	January 2016
Quantum Chemical Calculations of X-ray Emission Spectroscopy Wadey, Jack D.; Besley, Nicholas A. Journal of Chemical Theory and Computation, Vol. 10, Issue 10 https://doi.org/10.1021/ct500566k	journal	September 2014
Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory Zhang, Yu; Mukamel, Shaul; Khalil, Munira Journal of Chemical Theory and Computation, Vol. 11, Issue 12 https://doi.org/10.1021/acs.jctc.5b00763	journal	November 2015
Valence‐to‐Core X‐ray Emission Spectroscopy as a Probe of O−O Bond Activation in Cu ₂ O ₂ Complexes Cutsail, George E.; Gagnon, Nicole L.; Spaeth, Andrew D. Angewandte Chemie International Edition, Vol. 58, Issue 27 https://doi.org/10.1002/anie.201903749	journal	July 2019
Valence‐to‐core X‐ray emission spectroscopy of Ti, TiO, and TiO ₂ by means of a double full‐cylinder crystal von Hamos spectrometer Wansleben, Malte; Vinson, John; Holfelder, Ina X-Ray Spectrometry, Vol. 48, Issue 2 https://doi.org/10.1002/xrs.3000	journal	December 2018
Probing Transient Valence Orbital Changes with Picosecond Valence-to-Core X-ray Emission Spectroscopy March, Anne Marie; Assefa, Tadesse A.; Boemer, Christina The Journal of Physical Chemistry C, Vol. 121, Issue 5 https://doi.org/10.1021/acs.jpcc.6b12940	journal	January 2017
A Restricted Open Configuration Interaction with Singles Method To Calculate Valence-to-Core Resonant X-ray Emission Spectra: A Case Study Maganas, Dimitrios; DeBeer, Serena; Neese, Frank Inorganic Chemistry, Vol. 56, Issue 19 https://doi.org/10.1021/acs.inorgchem.7b01810	journal	September 2017
Effect of Molecular Guest Binding on the d–d Transitions of Ni ²⁺ of CPO-27-Ni: A Combined UV–Vis, Resonant-Valence-to-Core X-ray Emission Spectroscopy, and Theoretical Study Gallo, Erik; Gorelov, Evgeny; Guda, Alexander A. Inorganic Chemistry, Vol. 56, Issue 23 https://doi.org/10.1021/acs.inorgchem.7b01471	journal	October 2017
Kβ Valence to Core X-ray Emission Studies of Cu(I) Binding Proteins with Mixed Methionine – Histidine Coordination. Relevance to the Reactivity of the M- and H-sites of Peptidylglycine Monooxygenase Martin-Diaconescu, Vlad; Chacón, Kelly N.; Delgado-Jaime, Mario Ulises Inorganic Chemistry, Vol. 55, Issue 7 https://doi.org/10.1021/acs.inorgchem.5b02842	journal	March 2016
In search of metal hydrides: an X-ray absorption and emission study of [NiFe] hydrogenase model complexes Hugenbruch, Stefan; Shafaat, Hannah S.; Krämer, Tobias Physical Chemistry Chemical Physics, Vol. 18, Issue 16 https://doi.org/10.1039/C5CP07293J	journal	January 2016
Manganese Kβ X-ray Emission Spectroscopy As a Probe of Metal–Ligand Interactions Beckwith, Martha A.; Roemelt, Michael; Collomb, Marie-Noëlle Inorganic Chemistry, Vol. 50, Issue 17 https://doi.org/10.1021/ic200970t	journal	September 2011
Ligand-Sensitive But Not Ligand-Diagnostic: Evaluating Cr Valence-to-Core X-ray Emission Spectroscopy as a Probe of Inner-Sphere Coordination MacMillan, Samantha N.; Walroth, Richard C.; Perry, Demetra M. Inorganic Chemistry, Vol. 54, Issue 1 https://doi.org/10.1021/ic502152r	journal	December 2014
Study of Iron Dimers Reveals Angular Dependence of Valence-to-Core X-ray Emission Spectra Pollock, Christopher J.; Lancaster, Kyle M.; Finkelstein, Kenneth D. Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic501462y	journal	September 2014
HERFD-XAS and valence-to-core-XES: new tools to push the limits in research with hard X-rays? Bauer, Matthias Phys. Chem. Chem. Phys., Vol. 16, Issue 27 https://doi.org/10.1039/C4CP00904E	journal	January 2014
Valence-to-Core X-Ray Emission Spectroscopy of Iron-Carbonyl Complexes: Implications for the Examination of Catalytic Intermediates Delgado-Jaime, Mario Ulises; DeBeer , Serena; Bauer, Matthias Chemistry - A European Journal, Vol. 19, Issue 47 https://doi.org/10.1002/chem.201301913	journal	October 2013
Ligand Identification in Titanium Complexes Using X-ray Valence-to-Core Emission Spectroscopy Swarbrick, Janine C.; Kvashnin, Yaroslav; Schulte, Karina Inorganic Chemistry, Vol. 49, Issue 18 https://doi.org/10.1021/ic100755t	journal	September 2010
X-ray Emission Spectroscopy To Study Ligand Valence Orbitals in Mn Coordination Complexes Smolentsev, Grigory; Soldatov, Alexander V.; Messinger, Johannes Journal of the American Chemical Society, Vol. 131, Issue 36 https://doi.org/10.1021/ja808526m	journal	September 2009
Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations Bergmann, U.; Bendix, J.; Glatzel, P. The Journal of Chemical Physics, Vol. 116, Issue 5 https://doi.org/10.1063/1.1419062	journal	February 2002
On the sensitivity of hard X-ray spectroscopies to the chemical state of Br Bordage, Amélie; Pápai, Mátyás; Sas, Norbert S. Physical Chemistry Chemical Physics, Vol. 15, Issue 26 https://doi.org/10.1039/c3cp50367d	journal	January 2013
The X-Ray Emission Spectra of the Compounds of Third-period Elements. VI. The Relationship between the K α and K β Spectra Takahashi, Yoshihito Bulletin of the Chemical Society of Japan, Vol. 46, Issue 7 https://doi.org/10.1246/bcsj.46.2039	journal	July 1973
Chemical State Analysis of Phosphorus Performed by X-ray Emission Spectroscopy Petric, Marko; Bohinc, Rok; Bučar, Klemen Analytical Chemistry, Vol. 87, Issue 11 https://doi.org/10.1021/acs.analchem.5b00782	journal	May 2015
Chemical-state Analysis by Means of Soft X-Ray Spectroscopy. II. K β Spectra for Phosphorus, Sulfur, and Chlorine in Various Compounds Taniguchi, Kazuo Bulletin of the Chemical Society of Japan, Vol. 57, Issue 4 https://doi.org/10.1246/bcsj.57.915	journal	April 1984
A color x-ray camera for 2–6 keV using a mass produced back illuminated complementary metal oxide semiconductor sensor Holden, William M.; Hoidn, Oliver R.; Seidler, Gerald T. Review of Scientific Instruments, Vol. 89, Issue 9 https://doi.org/10.1063/1.5047934	journal	September 2018
Time-Dependent Density Functional Response Theory for Molecules Casida, Mark E. Recent Advances in Density Functional Methods https://doi.org/10.1142/9789812830586_0005	book	November 1995
An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules Stratmann, R. Eric; Scuseria, Gustavo E.; Frisch, Michael J. The Journal of Chemical Physics, Vol. 109, Issue 19 https://doi.org/10.1063/1.477483	journal	November 1998
Time-dependent density functional theory for radicals Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 302, Issue 5-6 https://doi.org/10.1016/S0009-2614(99)00137-2	journal	March 1999
Calibration of Scalar Relativistic Density Functional Theory for the Calculation of Sulfur K-Edge X-ray Absorption Spectra DeBeer George, Serena; Neese, Frank Inorganic Chemistry, Vol. 49, Issue 4 https://doi.org/10.1021/ic902202s	journal	February 2010
Molecular structure and stability of dissolved lithium polysulfide species Vijayakumar, M.; Govind, Niranjan; Walter, Eric Phys. Chem. Chem. Phys., Vol. 16, Issue 22 https://doi.org/10.1039/C4CP00889H	journal	January 2014
Structure and Dynamics of Polysulfide Clusters in a Nonaqueous Solvent Mixture of 1,3-Dioxolane and 1,2-Dimethoxyethane Andersen, Amity; Rajput, Nav Nidhi; Han, Kee Sung Chemistry of Materials, Vol. 31, Issue 7 https://doi.org/10.1021/acs.chemmater.8b03944	journal	February 2019
Time-dependent density functional calculations of ligand K-edge X-ray absorption spectra DeBeer George, Serena; Petrenko, Taras; Neese, Frank Inorganica Chimica Acta, Vol. 361, Issue 4 https://doi.org/10.1016/j.ica.2007.05.046	journal	March 2008
Prediction of Iron K-Edge Absorption Spectra Using Time-Dependent Density Functional Theory ^† DeBeer George, Serena; Petrenko, Taras; Neese, Frank The Journal of Physical Chemistry A, Vol. 112, Issue 50 https://doi.org/10.1021/jp803174m	journal	December 2008
Time-Dependent Density Functional Theory Study of the X-ray Absorption Spectroscopy of Acetylene, Ethylene, and Benzene on Si(100) Besley, Nicholas A.; Noble, Adam The Journal of Physical Chemistry C, Vol. 111, Issue 8 https://doi.org/10.1021/jp065160x	journal	January 2007
Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption Lopata, K.; Van Kuiken, B. E.; Khalil, M. Journal of Chemical Theory and Computation, Vol. 8, Issue 9 https://doi.org/10.1021/ct3005613	journal	August 2012
Quantitatively Probing the Al Distribution in Zeolites Vjunov, Aleksei; Fulton, John L.; Huthwelker, Thomas Journal of the American Chemical Society, Vol. 136, Issue 23 https://doi.org/10.1021/ja501361v	journal	May 2014
Core and valence excitations in resonant X-ray spectroscopy using restricted excitation window time-dependent density functional theory Zhang, Yu; Biggs, Jason D.; Healion, Daniel The Journal of Chemical Physics, Vol. 137, Issue 19 https://doi.org/10.1063/1.4766356	journal	November 2012
Simulating Ru L ₃ -Edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L. The Journal of Physical Chemistry A, Vol. 117, Issue 21 https://doi.org/10.1021/jp401020j	journal	May 2013
Tracking the Chemical Transformations at the Brønsted Acid Site upon Water-Induced Deprotonation in a Zeolite Pore Vjunov, Aleksei; Wang, Meng; Govind, Niranjan Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02133	journal	October 2017
Electronic and Chemical State of Aluminum from the Single- (K) and Double-Electron Excitation (KL _II&III , KL _I ) X-ray Absorption Near-Edge Spectra of α-Alumina, Sodium Aluminate, Aqueous Al ³⁺ ·(H ₂ O) ₆ , and Aqueous Al(OH) ₄ ^– Fulton, John L.; Govind, Niranjan; Huthwelker, Thomas The Journal of Physical Chemistry B, Vol. 119, Issue 26 https://doi.org/10.1021/jp511602n	journal	June 2015
Comprehensive Experimental and Computational Spectroscopic Study of Hexacyanoferrate Complexes in Water: From Infrared to X-ray Wavelengths Ross, Matthew; Andersen, Amity; Fox, Zachary W. The Journal of Physical Chemistry B, Vol. 122, Issue 19 https://doi.org/10.1021/acs.jpcb.7b12532	journal	April 2018
Unraveling the spectral signatures of solvent ordering in K-edge XANES of aqueous Na + Galib, M.; Schenter, G. K.; Mundy, C. J. The Journal of Chemical Physics, Vol. 149, Issue 12 https://doi.org/10.1063/1.5024568	journal	September 2018
Revisiting the hydration structure of aqueous Na ⁺ Galib, M.; Baer, M. D.; Skinner, L. B. The Journal of Chemical Physics, Vol. 146, Issue 8 https://doi.org/10.1063/1.4975608	journal	February 2017
Supersaturated calcium carbonate solutions are classical Henzler, Katja; Fetisov, Evgenii O.; Galib, Mirza Science Advances, Vol. 4, Issue 1 https://doi.org/10.1126/sciadv.aao6283	journal	January 2018
Carbon-supported Pt during aqueous phenol hydrogenation with and without applied electrical potential: X-ray absorption and theoretical studies of structure and adsorbates Singh, Nirala; Nguyen, Manh-Thuong; Cantu, David C. Journal of Catalysis, Vol. 368 https://doi.org/10.1016/j.jcat.2018.09.021	journal	December 2018
Time-dependent density functional theory within the Tamm–Dancoff approximation Hirata, So; Head-Gordon, Martin Chemical Physics Letters, Vol. 314, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)01149-5	journal	December 1999
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations Valiev, M.; Bylaska, E. J.; Govind, N. Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489 https://doi.org/10.1016/j.cpc.2010.04.018	journal	September 2010
Maximum Overlap Atomic and Molecular Orbitals Lykos, Peter G.; Schmeising, Howard N. The Journal of Chemical Physics, Vol. 35, Issue 1 https://doi.org/10.1063/1.1731901	journal	July 1961
Corresponding Orbitals and the Nonorthogonality Problem in Molecular Quantum Mechanics King, Harry F.; Stanton, Richard E.; Kim, Hojing The Journal of Chemical Physics, Vol. 47, Issue 6 https://doi.org/10.1063/1.1712221	journal	September 1967
Chemical-effect variation of Kβ/Kα X-ray intensity ratios in 3d elements Sogut, Omer; Büyükkasap, Erdoğan; Erdoğan, Hasan Radiation Physics and Chemistry, Vol. 64, Issue 5-6 https://doi.org/10.1016/S0969-806X(01)00644-2	journal	August 2002
PubChem 2019 update: improved access to chemical data Kim, Sunghwan; Chen, Jie; Cheng, Tiejun Nucleic Acids Research, Vol. 47, Issue D1 https://doi.org/10.1093/nar/gky1033	journal	October 2018
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements Francl, Michelle M.; Pietro, William J.; Hehre, Warren J. The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665 https://doi.org/10.1063/1.444267	journal	October 1982
Self-consistent molecular-orbital methods. 22. Small split-valence basis sets for second-row elements Gordon, Mark S.; Binkley, J. Stephen; Pople, John A. Journal of the American Chemical Society, Vol. 104, Issue 10 https://doi.org/10.1021/ja00374a017	journal	May 1982
The influence of polarization functions on molecular orbital hydrogenation energies Hariharan, P. C.; Pople, J. A. Theoretica Chimica Acta, Vol. 28, Issue 3 https://doi.org/10.1007/BF00533485	journal	January 1973
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules Hehre, W. J.; Ditchfield, R.; Pople, J. A. The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261 https://doi.org/10.1063/1.1677527	journal	March 1972
Self‐consistent molecular orbital methods. XX. A basis set for correlated wave functions Krishnan, R.; Binkley, J. S.; Seeger, R. The Journal of Chemical Physics, Vol. 72, Issue 1 https://doi.org/10.1063/1.438955	journal	January 1980
Contracted Gaussian basis sets for molecular calculations. I. Second row atoms, Z=11–18 McLean, A. D.; Chandler, G. S. The Journal of Chemical Physics, Vol. 72, Issue 10, p. 5639-5648 https://doi.org/10.1063/1.438980	journal	May 1980
Segmented contracted basis sets for atoms H through Xe: Sapporo-(DK)-nZP sets (n = D, T, Q) Noro, Takeshi; Sekiya, Masahiro; Koga, Toshikatsu Theoretical Chemistry Accounts, Vol. 131, Issue 2 https://doi.org/10.1007/s00214-012-1124-z	journal	February 2012
Toward reliable density functional methods without adjustable parameters: The PBE0 model Adamo, Carlo; Barone, Vincenzo The Journal of Chemical Physics, Vol. 110, Issue 13 https://doi.org/10.1063/1.478522	journal	April 1999
Refinement of the crystal structures of realgar, AsS and orpiment, As ₂ S ₃ * Mullen, D. J. E.; Nowacki, W. Zeitschrift für Kristallographie, Vol. 136, Issue 1-2 https://doi.org/10.1524/zkri.1972.136.1-2.48	journal	October 1972
First-principles thousand-atom quantum dot calculations Wang, Lin-Wang; Li, Jingbo Physical Review B, Vol. 69, Issue 15 https://doi.org/10.1103/PhysRevB.69.153302	journal	April 2004
Visible Light Absorption of N-Doped TiO ₂ Rutile Using (LR/RT)-TDDFT and Active Space EOMCCSD Calculations Govind, N.; Lopata, K.; Rousseau, R. The Journal of Physical Chemistry Letters, Vol. 2, Issue 21 https://doi.org/10.1021/jz201118r	journal	October 2011
Ab initio effective core potentials for molecular calculations. Potentials for main group elements Na to Bi Wadt, Willard R.; Hay, P. Jeffrey The Journal of Chemical Physics, Vol. 82, Issue 1 https://doi.org/10.1063/1.448800	journal	January 1985
Ab initio effective core potentials for molecular calculations. Potentials for K to Au including the outermost core orbitals Hay, P. Jeffrey; Wadt, Willard R. The Journal of Chemical Physics, Vol. 82, Issue 1, p. 299-310 https://doi.org/10.1063/1.448975	journal	January 1985
Energy‐adjusted a b i n i t i o pseudopotentials for the first row transition elements Dolg, M.; Wedig, U.; Stoll, H. The Journal of Chemical Physics, Vol. 86, Issue 2 https://doi.org/10.1063/1.452288	journal	January 1987
Correlation consistent valence basis sets for use with the Stuttgart–Dresden–Bonn relativistic effective core potentials: The atoms Ga–Kr and In–Xe Martin, Jan M. L.; Sundermann, Andreas The Journal of Chemical Physics, Vol. 114, Issue 8 https://doi.org/10.1063/1.1337864	journal	February 2001
Ab initio energy-adjusted pseudopotentials for elements of groups 13–17 Bergner, Andreas; Dolg, Michael; Küchle, Wolfgang Molecular Physics, Vol. 80, Issue 6 https://doi.org/10.1080/00268979300103121	journal	December 1993
X-ray transition energies: new approach to a comprehensive evaluation Deslattes, Richard D.; Kessler, Ernest G.; Indelicato, P. Reviews of Modern Physics, Vol. 75, Issue 1 https://doi.org/10.1103/RevModPhys.75.35	journal	January 2003
The anisotropy of X-ray emission spectra for 2H-MoS2 single crystals Yarmoshenko, Yu. M.; Cherkashenko, V. M.; Kurmaev, E. Z. Journal of Electron Spectroscopy and Related Phenomena, Vol. 32, Issue 2 https://doi.org/10.1016/0368-2048(83)85088-9	journal	January 1983
Polarized X-Ray Emission Spectra of Single Crystals Dräger, G.; Brümmer, O. physica status solidi (b), Vol. 124, Issue 1 https://doi.org/10.1002/pssb.2221240102	journal	July 1984
Electronic structure of black phosphorus studied by polarized soft-x-ray emission and absorption spectroscopy Hayasi, Y.; Takahashi, T.; Asahina, H. Physical Review B, Vol. 30, Issue 4 https://doi.org/10.1103/PhysRevB.30.1891	journal	August 1984
Partial densities of states with polarized oxygen Kα X-ray emission of YBa2Cu3O7−δ Kottmann, A.; Burgäzy, F.; Lam, D. J. Physica C: Superconductivity, Vol. 178, Issue 1-3 https://doi.org/10.1016/0921-4534(91)90167-W	journal	July 1991
Polarized x-ray emission studies of methyl chloride and the chlorofluoromethanes Lindle, D. W.; Cowan, P. L.; Jach, T. Physical Review A, Vol. 43, Issue 5 https://doi.org/10.1103/PhysRevA.43.2353	journal	March 1991
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information Glatzel, Pieter; Bergmann, Uwe Coordination Chemistry Reviews, Vol. 249, Issue 1-2 https://doi.org/10.1016/j.ccr.2004.04.011	journal	January 2005
Polarized x-ray-absorption spectroscopy of the uranyl ion: Comparison of experiment and theory Hudson, E. A.; Allen, P. G.; Terminello, L. J. Physical Review B, Vol. 54, Issue 1 https://doi.org/10.1103/PhysRevB.54.156	journal	July 1996
Role of inversion symmetry and multipole effects in nonresonant x-ray Raman scattering from icosahedral $B_{4} C$ Feng, Yejun; Seidler, G. T.; Cross, J. O. Physical Review B, Vol. 69, Issue 12 https://doi.org/10.1103/PhysRevB.69.125402	journal	March 2004
The electronic transitions of dibenzothiophene: linear dichroism spectroscopy and quantum chemical calculations Spanget-Larsen, Jens; Thulstrup, Erik W. Journal of Molecular Structure, Vol. 661-662 https://doi.org/10.1016/S0022-2860(03)00509-X	journal	December 2003
Electronic transitions of fluorene, dibenzofuran, carbazole, and dibenzothiophene: From the onset of absorption to the ionization threshold Nguyen, Duy Duc; Trunk, John; Nakhimovsky, Lina Journal of Molecular Spectroscopy, Vol. 264, Issue 1 https://doi.org/10.1016/j.jms.2010.08.009	journal	November 2010

Similar Records

Valence-to-core X-ray emission spectroscopy of vanadium oxide and lithiated vanadyl phosphate materials

Journal Article · Wed Jul 22 00:00:00 EDT 2020 · Journal of Materials Chemistry. A · OSTI ID:1646827

Jahrman, Evan P.; Holden, William M.; Govind, Niranjan; +7 more

Simulating Valence-to-Core X-ray Emission Spectroscopy of Transition Metal Complexes with Time-Dependent Density Functional Theory

Journal Article · Mon Nov 09 00:00:00 EST 2015 · Journal of Chemical Theory and Computation · OSTI ID:1646827

Zhang, Yu; Mukamel, Shaul; Khalil, Munira; +1 more

Observing pre-edge

K

-shell resonances in Kr, Xe, and

{XeF}_{2}

Journal Article · Fri Aug 09 00:00:00 EDT 2019 · Physical Review A · OSTI ID:1646827

Southworth, S. H.; Dunford, R. W.; Ray, D.; +11 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
x-rays
sulfur
oxidation state
energy
chemical calculations

Title: Probing Sulfur Chemical and Electronic Structure with Experimental Observation and Quantitative Theoretical Prediction of Kα and Valence-to-Core Kβ X-ray Emission Spectroscopy

Citation Formats

References (146)

Similar Records

Related Subjects