Physical Sciences and Mathematics Commons^™

Controllable Co2 Electrocatalytic Reduction Via Ferroelectric Switching On Single Atom Anchored In2se3 Monolayer, Lin Ju, Xin Tan, Xin Mao, Yuantong Gu, Sean Smith, Aijun Du, Zhongfang Chen, Changfeng Chen, Liangzhi Kou

Physics & Astronomy Faculty Research

Efficient and selective CO2 electroreduction into chemical fuels promises to alleviate environmental pollution and energy crisis, but it relies on catalysts with controllable product selectivity and reaction path. Here, by means of first-principles calculations, we identify six ferroelectric catalysts comprising transition-metal atoms anchored on In2Se3 monolayer, whose catalytic performance can be controlled by ferroelectric switching based on adjusted d-band center and occupation of supported metal atoms. The polarization dependent activation allows effective control of the limiting potential of CO2 reduction on TM@In2Se3 (TM = Ni, Pd, Rh, Nb, and Re) as well as the reaction paths and final products on …

Singlet Fission In Acene Blends, Katharina Broch, Clemens Zeiser, Chad Cruz, Luca Moretti, Margherita Maiuri, Eric Chronister, David Reichman, Roel Tempelaar, Giulio Cerullo, Christopher Bardeen

Chemistry and Biochemistry Faculty Research

Singlet fission (SF), the photophysical process converting an excited singlet exciton into two triplet excitons, is a promising approach to boost solar cell efficiencies. It is controlled by various parameters such as intermolecular interactions, energetics, entropy and vibronic coupling and a controlled modification of these parameters is key to a fundamental understanding. Blends of organic semiconductors present an interesting alternative to established methods of chemical functionalization and their potential for the study of SF pathways will be discussed using acene blends as example. Mixed thin films of SF chromophores and weakly interacting, high-bandgap spacer molecules allow one to study the …

Recovery Of High Specific Activity Molybdenum-99 From Accelerator-Induced Fission On Low-Enriched Uranium For Technetium-99m Generators, M. Alex Brown, Nathan Johnson, Artem V. Gelis, Milan Stika, Anna G. Servis, Alex Bakken, Christine Krizmanich, Kristin Shannon, Peter Kozak, Amanda Barnhart, Chad Denbrock, Nicolas Luciani, Terry Grimm, Peter Tkac

Chemistry and Biochemistry Faculty Research

A new process was developed to recover high specific activity (no carrier added) 99Mo from electron-accelerator irradiated U3O8 or uranyl sulfate targets. The process leverages a novel solvent extraction scheme to recover Mo using di(2-ethylhexyl) phosphoric acid following uranium and transuranics removal with tri-n-butyl phosphate. An anion-exchange concentration column step provides a final purification, generating pure 99Mo intended for making 99Mo/99mTc generators. The process was demonstrated with irradiated uranium targets resulting in more than 95% 99Mo recovery and without presence of fission products or actinides in the product.

Β -Technetium: An Allotrope With A Nonstandard Volume-Pressure Relationship, Emily Siska, Dean Smith, Christian Childs, Daniel Koury, Paul M. Forster, Keith V. Lawler, Ashkan Salamat

Chemistry and Biochemistry Faculty Research

We report the synthesis and structure of the second allotrope of technetium, β-Tc. Transformative pathways are accessed at extreme conditions using the laser-heated diamond anvil cell and confirmed with in situ synchrotron x-ray diffraction and Raman spectroscopy. β-Tc is fully recoverable to ambient conditions, although counter to our DFT calculations predicting a face-centered-cubic lattice, we observe a tetragonal structure (I4/mmm) that exhibits further tetragonal distortion with pressure. β-Tc has an expanded volume relative to the hcp ground state phase, that when doped with nitrogen has an unexpected volume lowering. Such anomalous behavior is possibly indicative of a rare electronic phase …

Colossal Density-Driven Resistance Response In The Negative Charge Transfer Insulator Mns2, Dylan Durkee, Nathan Dasenbrock-Gammon, G. Alexander Smith, Elliot Snider, Dean Smith, Christian Childs, Simon A.J. Kimber, Keith V. Lawler, Ranga P. Dias, Ashkan Salamat

Chemistry and Biochemistry Faculty Research

A reversible density driven insulator to metal to insulator transition in high-spin MnS2 is experimentally observed, leading with a colossal electrical resistance drop of 108 ω by 12 GPa. Density functional theory simulations reveal the metallization to be unexpectedly driven by previously unoccupied S22- σ3p∗ antibonding states crossing the Fermi level. This is a unique variant of the charge transfer insulator to metal transition for negative charge transfer insulators having anions with an unsaturated valence. By 36 GPa the emergence of the low-spin insulating arsenopyrite (P21/c) is confirmed, and the bulk metallicity is broken with the system returning to an …

Poly(Pyridinium Salt)S Containing 2,7-Diamino-9,9'-Dioctylfluorene Moieties With Various Organic Counterions Exhibiting Both Lyotropic Liquid-Crystalline And Light-Emitting Properties, Pradip K. Bhowmik, Tae S. Jo, Jung J. Koh, Jongwon Park, Bidyut Biswas, Ronald Carlo G. Principe, Haesook Han, András F. Wacha, Matti Knaapila

Chemistry and Biochemistry Faculty Research

A series of poly(pyridinium salt)s-fluorene main-chain ionic polymers with various organic counterions were synthesized by using ring-transmutation polymerization and metathesis reactions. Their chemical structures were characterized by Fourier Transform Infrared (FTIR), proton (1H), and fluorine 19 (19F) nuclear magnetic resonance (NMR) spectrometers. These polymers showed a number-average molecular weight (Mns) between 96.5 and 107.8 kg/mol and polydispersity index (PDI) in the range of 1.12-1.88. They exhibited fully-grown lyotropic phases in polar protic and aprotic solvents at different critical concentrations. Small-angle X-ray scattering for one polymer example indicates lyotropic structure formation for 60-80% solvent fraction. A lyotropic smectic phase contains 10 …

Coexistence Of Metamagnetism And Slow Relaxation Of Magnetization In Ammonium Hexafluoridorhenate, James Louis-Jean, Samundeeswari M. Balasekaran, Keith V. Lawler, Adrián Sanchis-Perucho, José Martínez-Lillo, Dean Smith, Paul M. Forster, Ashkan Salamat, Frederic Poineau

Chemistry and Biochemistry Faculty Research

© The Royal Society of Chemistry 2021. The (NH4)2[ReF6] (1) salt was studied by X-ray diffraction, Raman spectroscopy, theoretical calculations, and magnetic measurements.1crystallizes in the trigonal space groupP3̄m1 (Re-F = 1.958(5) Å). In the Raman spectrum of1, splitting of the observed peaks was observed and correlated to the valence frequencies of vibration of the [ReF6]2−anion. The study of the magnetic properties of1, through DC and AC magnetic susceptibility measurements, reveals the coexistence of metamagnetism and slow relaxation of magnetization at low temperature, which is unusual in the molecular systems based on the paramagnetic 5d metal ions reported so far.

Nanopatterned Silk Fibroin Films With High Transparency And High Haze For Optical Applications, Corey Malinowski, Fengjie He, Yihong Zhao, Ivan Chang, David W. Hatchett, Shengjie Zhai, Hui Zhao

Chemistry and Biochemistry Faculty Research

Simultaneous high transparency and high haze are necessary for high-efficiency optical, photonic, and optoelectronic applications. However, a typical highly transparent film lacks high optical haze or vice versa. Here, we report a silk fibroin-based optical film that exhibits both ultrahigh optical transparency... (See article for full abstract).

Stereodynamical Control Of A Quantum Scattering Resonance In Cold Molecular Collisions, Pablo G. Jambrina, James F.E. Croft, Hua Guo, Mark Brouard, Balakrishnan Naduvalath, F. Javier Aoiz

Chemistry and Biochemistry Faculty Research

Cold collisions of light molecules are often dominated by a single partial wave resonance. For the rotational quenching of HD (v=1, j=2) by collisions with ground state para-H2, the process is dominated by a single L=2 partial wave resonance centered around 0.1 K. Here, we show that this resonance can be switched on or off simply by appropriate alignment of the HD rotational angular momentum relative to the initial velocity vector, thereby enabling complete control of the collision outcome.

Pressure-Induced Phase Transition In 1,3,5-Triamino-2,4,6-Trinitrobenzene (Tatb), Brad A. Steele, Samantha M. Clarke, Matthew P. Kroonblawd, I-Feng W. Kuo, Philip F. Pagoria, Sergey N. Tkachev, Jesse S. Smith, Sorin Bastea, Laurence E. Fried, Joseph M. Zaug, Elissaios Stavrou, Oliver Tschauner

Geoscience Faculty Publications

Determining the unreacted equation of state of 1,3, 5-triamino-2,4,6-trinitrobenzene (TATB) is challenging because it exhibits low crystal symmetry and low X-ray scattering strength. Here, we present the first high-pressure single-crystal X-ray diffraction (SXD) study of this material. Our SXD results reveal a previously unknown transition to a monoclinic phase above 4 GPa. No abrupt change of the volume occurs but the compressibility changes. Concomitant first principles evolutionary crystal structure prediction USPEX calculations confirm this transition and show that it involves a pressure-induced in-plane shift of the layers of TATB molecules with respect to the ambient-pressure phase.

Controlling Rotational Quenching Rates In Cold Molecular Collisions, James F.E. Croft, Balakrishnan Naduvalath

Chemistry and Biochemistry Faculty Research

The relative orientation and alignment of colliding molecules plays a key role in determining the rates of chemical processes. Here, we examine in detail a prototypical example: rotational quenching of HD in cold collisions with H2. We show that the rotational quenching rate from j = 2 → 0, in the v = 1 vibrational level, can be maximized by aligning the HD along the collision axis and can be minimized by aligning the HD at the so called magic angle. This follows from quite general helicity considerations and suggests that quenching rates for other similar systems can also be …

K-Shell X-Ray Spectroscopy Of Atomic Nitrogen, M. M. Sant'anna, Gunnar Ohrwall, Wayne C. Stolte, Alfred S. Schlachter, Dennis W. Lindle, B. M. Mclaughlin

Chemistry and Biochemistry Faculty Research

Absolute K-shell photoionization cross sections for atomic nitrogen have been obtained from both experiment and state-of-the-art theoretical techniques. Because of the difficulty of creating a target of neutral atomic nitrogen, no high-resolution K-edge spectroscopy measurements have been reported for this important atom. Interplay between theory and experiment enabled identification and characterization of the strong 1s → np resonance features throughout the threshold region. An experimental value of 409.64 ± 0.02 eV was determined for the K-shell binding energy.

Jahn-Teller Coupling And Fragmentation After Core-Shell Excitation Ini Cf4 Investigated By Partial-Ion-Yield Spectroscopy, Renaud Guillemin, Wayne C. Stolte, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigate fragmentation processes induced by core-level photoexcitation in CF4 at both the carbon and fluorine K edges by means of partial-ion-yield spectroscopy. The molecule CF₄ is a textbook example of systems in which Jahn-Teller coupling strongly manifests itself in the photoabsorption spectrum. Spectral features related to Jahn-Teller and quasi-Jahn-Teller splitting are observed, and important differences in the fragmentation pathways are revealed depending on the symmetries of the core-excited states. We interpret these experimental observations on the grounds of symmetry lowering from the Td to the C3v point group as well as preferential orientation with respect …

Full Multiple Scattering Analysis Of Xanes At The Cd L 3- And O K- Edges In Cdo Films Combined With A Soft-X-Ray Emission Investigation, I. N. Demchenko, J. D. Denlinger, M. Chernyshova, K. M. Yu, D. T. Speaks, P. Olalde-Velasco, Oliver Hemmers, W. Walukiewicz, A. Derkachova, K. Lawniczak-Jablonska

Environmental Studies Faculty Publications

X-ray absorption near edge structure (XANES) at the cadmium L3 and oxygen K edges for CdO thin films grown by pulsed laser deposition method, is interpreted within the real-space multiple scattering formalism, FEFF code. The features in the experimental spectra are well reproduced by calculations for a cluster of about six and ten coordination shells around the absorber for L3 edge of Cd and K edge of O, respectively. The calculated projected electronic density of states is found to be in good agreement with unoccupied electronic states in experimental data and allows to conclude that the orbital character of the …

Sulfur K-Edge Photo-Fragmentation Of Ethylene Sulfide, Wayne C. Stolte, Gunnar Ohrwall

Chemistry and Biochemistry Faculty Research

We have investigated the photofragmentation properties of the three-membered ring heterocyclic molecule ethylene sulfide or thiirane, C₂H₄S, by time-of-flight mass spectroscopy. Positive ions have been collected as a function of photon energy around the S K ionization threshold. Branching ratios were derived for all detected ions, which are informative of the decay dynamics and photofragmentation patterns of the core-excited species. We present a new assignment of the spectral features around the S K-edge.

Fragmentation Properties Of Three-Membered Ring Heterocyclic Molecules By Partial Ion Yield Spectroscopy: C2h4o And C2h4s, Wayne C. Stolte, I. Dumitriu, S-W Yu, Gunnar Ohrwall, Maria Novella Piancastelli, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We investigated the photofragmentation properties of two three-membered ring heterocyclic molecules, C₂H₄O and C₂H₄S, by total and partial ion yield spectroscopy. Positive and negative ions have been collected as a function of photon energy around the C 1s and O 1s ionization thresholds in C₂H₄O, and around the S 2p and C 1s thresholds in C₂H₄S. We underline similarities and differences between these two analogous systems. We present a new assignment of the spectral features around the C K-edge and the sulfur L_{2 …}

Experimental And Theoretical Investigation Of Molecular Field Effects By Polarization-Resolved Resonant Inelastic X-Ray Scattering, Stephane Carniato, Renaud Guillemin, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

We present a combined theoretical and experimental study of molecular field effects on molecular core levels. Polarization-dependent resonant inelastic x-ray scattering is observed experimentally after resonant K-shell excitation of CF₃Cl and HCl. We explain the linear dichroism observed in spin-orbit level intensities as due to molecular field effects, including singlet-triplet exchange, and interpret this behavior in terms of population differences in the 2p_x,y,z inner-shell orbitals. We investigate theoretically the different factors that can affect the electronic populations and the dynamical R dependence of the spin-orbit ratio. Finally, the results obtained are used to interpret the L-shell …

Partial Ion Yield Sspectroscopy Around The Cl 2p And C 1s Ionization Thresholds In Cf3cl, D. Ceolin, Maria Novella Piancastelli, Wayne C. Stolte, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

We present a partial ion yield experiment on freon 13, CF₃Cl, excited in the vicinity of the C 1s and Cl 2p ionization thresholds. We have collected a large amount of cationic fragments and a few anionic fragments at both edges. We have observed a strong intensity dependence of Rydberg transitions with ion fragment size for the CF_nCl⁺ and CF_n⁺/F⁺ (n=0–3) series at both the Cl 2p and C 1s ionization edges. Selectivity in the fragmentation processes involving the C–Cl and C–F bonds are highlighted by the intensities of the C …

Yttrium And Hydrogen Superstructure And Correlation Of Lattice Expansion And Proton Conductivity In The Bazr0.9y0.1o2.95 Proton Conductor, A. Braun, A. Ovalle, V. Pomjakushin, A. Cervellino, S. Erat, Wayne C. Stolte, T. Graule

Chemistry and Biochemistry Faculty Research

Bragg reflections in Y-resonant x-ray diffractograms of BaZr_0.9Y_0.1O_2.95 (BZY10) reveal that Y is organized in a superstructure. Comparison with neutron diffraction superstructure reflections in protonated/deuterated BZY10 suggests that both superstructures are linked, and that protons move in the landscape imposed by the Y. The thermal lattice expansion decreases abruptly for protonated BZY10 at T≥648±20 K, coinciding with the onset of lateral proton diffusion and suggesting a correlation of structural changes and proton conductivity. The chemical shift in the Y L₁-shell x-ray absorption spectra reveals a reduction from Y³⁺ toward Y²⁺ upon …

Linear Dichroism In Resonant Inelastic X-Ray Scattering To Molecular Spin-Orbit States, Renaud Guillemin, Stephane Carniato, Wayne C. Stolte, Loic Journel, Richard Taieb, Dennis W. Lindle, Marc Simon

Chemistry and Biochemistry Faculty Research

Polarization-dependent resonant inelastic x-ray scattering (RIXS) is shown to be a new probe of molecular-field effects on the electronic structure of isolated molecules. A combined experimental and theoretical analysis explains the linear dichroism observed in Cl 2p RIXS following Cl 1s excitation in HCl and CF₃Cl as due to molecular-field effects, including singlet-triplet exchange, indicating polarized-RIXS provides a direct probe of spin-orbit-state populations applicable to any molecule.

Stability And Equation Of State Of A Nanocrystalline Ga-Ge Mullite In A Vitroceramic Composite: A Synchrotron X-Ray Iffraction Study, Kristina E. Lipinska-Kalita, Patricia Kalita, Cedric Gobin, Oliver Hemmers, Thomas Hartmann, Gino Mariotto

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond anvil cell techniques were used to characterize the phase transformations and to evaluate the structural stability at elevated pressures of a developed nanocrystalline composite. The optically transparent material was built of a germanium oxide-based amorphous host matrix with homogeneously dispersed 13±3 nm Ga-Ge mullite-type nanocrystals, which had a structure similar to the conventional Al₂O₃-SiO₂ mullite. The equation of state of the nanocrystals and the overall structural integrity of the nanocomposite were investigated in quasihydrostatic conditions on compression to 36 GPa and on the following decompression to ambient conditions. The overall …

Equation Of State Of Gallium Oxide To 70 Gpa: Comparison Of Quasihydrostatic And Nonhydrostatic Compression, Kristina E. Lipinska-Kalita, Patricia Kalita, Oliver Hemmers, Thomas Hartmann

Environmental Studies Faculty Publications

Synchrotron x-ray diffraction and diamond-anvil cell techniques were used to characterize pressure induced structural modifications in gallium oxide. Gallium oxide was studied on compression up to 70 GPa and on the following decompression. The effect of the pressure-transmitting medium on the structural transformations was investigated in two sets of compression and decompression runs, one with nitrogen as a quasihydrostatic pressure-transmitting medium and the other in nonhydrostatic pressure conditions. The x-ray diffraction data showed gradual phase transition from a low-density, monoclinic β-Ga₂O₃ to a high-density, rhombohedral α-Ga₂O₃. With the use of nitrogen as a …

Immobilization Of Fission Iodine By Reaction With A Fullerene Containing Carbon Compound And Insoluble Natural Matrix, Spencer M. Steinberg, Gary Cerefice, David W. Emerson

Separations Campaign (TRP)

Observations related to the oxidation of iodide to iodine (I₂) or hypoiodic acid (HIO) by MnO₂ were continued. The formation of triiodide presumable involves the adsorption of iodide onto the MnO₂ surface (perhaps displacing a surface hydroxyl group). The iodide should be subsequently oxidized and released back into solution as IOH or I₂, which rapidly forms I₃ ^-. The kinetic data has been modeled as a first order process. First order rate constants have been obtained for the formation of iodine in the presence of MnO₂. The increase in iodide …

Evaluation Of Fluorapatite As A Waste-Form Material, Dennis W. Lindle, Oliver Hemmers, Dale L. Perry

Separations Campaign (TRP)

Argonne National Laboratory has proposed a new extraction procedure to handle TRISO-coated fuels, the Fluoride Extraction Process (FLEX). The FLEX process is designed to separate the uranium in the fuel from the actinides and most fission products by taking advantage of the unique properties of uranium hexafluoride (UF₆). In the FLEX process, the used TRISO fuel is reacted with zirconium fluoride salt, forming UF₆ and the fluoride salts of the actinides and fission products. At process temperatures, the UF₆ volatizes into a gas, and is released from the molten salt mixture. This leaves behind the actinides …

Electrochemical Separation Of Curium And Americium, David W. Hatchett, Kenneth Czerwinski

Separations Campaign (TRP)

The objective was to use electrochemical techniques to develop a thermodynamic understanding of actinide and lanthanide species in RTIL solutions, and use this data to effectively separate species with very similar chemical properties.

In consultation with a DOE collaborator, electrochemical methods and materials were evaluated and used to exploit the thermodynamic differences between similar chemical species enhancing the ability to selectively target and sequester individual species from mixtures. This project, in its third year, successfully completed phases 1, 2. Phase 3 was partially completed. The project expanded to include phase 4.

The following were specific goals for 2007-2008:

• To …

Fundamental Chemistry Of U And Pu In The Tbp-Dodecane-Nitric Acid System, Kenneth Czerwinski

Separations Campaign (TRP)

The research objective is to experimentally evaluate the fundamental speciation of Pu and U in the TBP-dodecane-nitric acid- AHA system and the effect of pertechnetate, specifically:

• To determine the influence of nitrate on the speciation of U and Pu in the TBP-dodecane-nitric acid system. The aqueous and organic speciation of U and Pu are examined as a function of the nitric acid concentration, nitrate concentration, actinide ion concentration, temperature, and time.

• To determine the speciation of U and Pu with AHA in the presence and absence of TBP-dodecane organic phase. The aqueous and organic speciation of U and …

Evaluation Of Fundamental Radionuclide Extraction Data For Urex, Kenneth Czerwinski

Separations Campaign (TRP)

The speciation of technetium and actinides in advanced solvent extraction systems is the basis for their manipulation in separations. The ability to understand and predict radionuclide speciation is paramount to successful modeling of proposed separation systems. This project will examine the speciation of radionuclides in different stages of the uranium extraction (UREX) separation scheme, providing data useful to modeling. The areas to be examined include the speciation of uranium and plutonium with tributylphosphate and the kinetics and thermodynamics of lanthanides and actinides in the TALSPEAK (Trivalent actinide lanthanide separation by phosphorous reagent extraction from aqueous complexes) system. The complexation constants …

Criticality Studies For Urex Processes, Denis Beller

Separations Campaign (TRP)

The completion of criticality experiments for mixtures of transuranic actinides (TRU; includes neptunium, plutonium, americium, and curium) that will be created during the separation of used nuclear fuel may be a requirement in order to construct prototype plants for the Global Nuclear Energy Partnership (GNEP). In this program and the Advanced Fuel Cycle Research and Development (AFC R&D) program that supports it, economic and environmental methods are being developed to reduce the impact of waste from commercial nuclear fuel cycles.

Recycling of used fuel by chemically separating it into U, fission products, and TRU would be the first step in …

F-Element Electrochemistry In Rtil Solutions: Electrochemical Separation Of Lanthanides And Actinides, David W. Hatchett

Separations Campaign (TRP)

Electrochemical methods can be used to effectively separate actinide and lanthanide species from complex mixtures. This is based on the unique electrochemical properties of each specific target species. In studies it has been found that, with the exception of Ce, aqueous solutions provide unsuitable electrochemical windows to effectively evaluate the thermodynamic properties that are useful for chemical separations. Therefore, a more novel approach was examined which eliminated the aqueous solution with a room temperature ionic liquid (RTIL) solution. RTIL solutions do not suffer from the side reactions that are prominent in aqueous environments. In addition, the potential window is much …

Interaction Between Metal Fission Products And Triso Coating Materials, Clemens Heske

Fuels Campaign (TRP)

This project focuses on the chemical bonding and interface formation of metal fission products with the coating materials used in tri-isotropic (TRISO) fuel particles for gas-cooled reactors. By combining surface- and bulk-sensitive spectroscopic and microscopic methods, intermediate chemical phases at the interface, intermixing/diffusion behavior, and the electronic interface structure for different coating materials and metals are examined.

In detail, the project studies the interface formation of Pd, Cs, and Ag with SiC and pyrolytic carbon. Using SiC single crystals and highly-ordered pyrolytic carbon (HOPG) as substrates, interfaces are prepared under controlled conditions in an ultra-high vacuum environment and are studied …