Physical Sciences and Mathematics Commons^™

Concave Cubic Gold Nanocrystals With High-Index Facets, Jian Zhang, Mark R. Langille, Michelle L. Personick, Ke Zhang, Shuyou Li, Chad A. Mirkin

Department of Chemistry: Faculty Publications

A new class of gold nanostructures, concave nanocubes, enclosed by 24 high-index {720} facets, have been prepared in a monodisperse fashion by a modified seed-mediated synthetic method. The Cl− counterion in the surfactant plays an essential role in controlling the concave morphology of the final product. The concave nanocubes exhibit higher chemical activities compared with low-index {111}-faceted octahedra.

Includes Supporting Information.

Lattice Dynamical Probe Of Charge Order And Antipolar Bilayer Stacking In Lufe2o4, X. S. Xu, J. De Groot, Q.-C. Sun, B. C. Sales, D. Mandrus, M. Angst, A. P. Litvinchuk, J. L. Musfeldt

Xiaoshan Xu Papers

We investigated the infrared response of LuFe₂O₄ through the series of charge, magnetic, and structural transitions. All vibrational modes couple strongly to the charge order, whereas the LuO zone-folding modes are also sensitive to magnetic order and structural distortion. The dramatic splitting of the LuO₂ layer mode is attributed to charge-rich/poor proximity effects and its temperature dependence reveals the antipolar nature of the W layer pattern.

Tunable Band Gap In Bi(Fe1−Xmnx)O3 Films, X. S. Xu, J. F. Ihlefeld, J. H. Lee, O. K. Ezekoye, E. Vlahos, R. Ramesh, V. Gopalan, X. Q. Pan, D. G. Schlom, J. L. Musfeldt

Xiaoshan Xu Papers

In order to investigate band gap tunability in polar oxides, we measured the optical properties of a series of Bi(Fe_1−xMn_x)O₃ thin films. The absorption response of the mixed metal solid solutions is approximately a linear combination of the characteristics of the two end members, a result that demonstrates straightforward band gap tunability in this system.

Magnetodielectric Coupling Of Infrared Phonons In Single-Crystal Cu2oseo3, K. H. Miller, X. S. Xu, H. Berger, E. S. Knowles, D. J. Arenas, M. W. Meisel, D. B. Tanner

Xiaoshan Xu Papers

Reflection and transmission as a function of temperature (5–300 K) have been measured on a single crystal of the magnetoelectric ferrimagnetic compound Cu₂OSeO₃ utilizing light spanning the far infrared to the visible portions of the electromagnetic spectrum. The complex dielectric function and optical properties were obtained via Kramers-Kronig analysis and by fits to a Drude-Lortentz model. The fits of the infrared phonons show a magnetodielectric effect near the transition temperature (T_c~60 K). Assignments to strong far-infrared phonon modes have been made, especially those exhibiting anomalous behavior around the transition temperature.

Deposition Of High-Quality Hfo2 On Graphene And The Effect Of Remote Oxide Phonon Scattering, K. Zou, X. Hong, D. Keefer, J. Zhu

Xia Hong Publications

We demonstrate atomic layer deposition of high-quality dielectric HfO₂ films on graphene and determine the magnitude of remote oxide surface phonon scattering in dual-oxide structures. The carrier mobility in these HfO₂-covered graphene samples reaches 20 000 cm²/Vs at low temperature. Distinct contributions to the resistivity from surface optical phonons in the SiO₂ substrate and the HfO₂ overlayer are isolated. At 300 K, surface phonon modes of the HfO₂ film centered at 54 meV limit the mobility to approximately 20 000 cm²/Vs.

Unusual Resistance Hysteresis In N-Layer Graphene Field Effect Transistors Fabricated On Ferroelectric Pb(Zr0.2Ti0.8)O3, X. Hong, J. Hoffman, A. Posadas, K. Zou, C. H. Ahn, J. Zhu

Xia Hong Publications

We have fabricated n-layer graphene field effect transistors on epitaxial ferroelectric Pb(Zr_0.2Ti_0.8)O₃ (PZT) thin films. At low gate voltages, PZT behaves as a high-k dielectric with k up to 100. An unusual resistance hysteresis occurs in gate sweeps at high voltages, with its direction opposite to that expected from the polarization switching of PZT. The relaxation of the metastable state is thermally activated, with an activation barrier of 50–110 meV and a time constant of 6 h at 300 K. We attribute its origin to the slow dissociation/recombination dynamics of water molecules adsorbed at …

Semiclassical Complex-Time Method For Tunneling Ionization: Molecular Suppression And Orientational Dependence, Gordon A. Gallup, Ilya I. Fabrikant

Gordon Gallup Publications

We apply a previously developed semiclassical complex time method to the calculation of tunneling ionization of several diatomic molecules and CO₂.We investigate the presence or absence of the molecular suppression effect by calculating ionization rates of N₂ versus Ar, O₂ versus Xe, F₂ versus Ar, and CO versus Kr. Comparisons with other theories, including the molecular-orbital-Ammosov-Delone-Krainov (MO-ADK) model and the strong-field approximation, are given. We also analyze the dependence of the ionization rate on the angle θ_F between the molecular axis and the field direction. The theoretical results agree quite well with experiment for …

A Low-Voltage Retarding-Field Mott Polarimeter For Photocathode Characterization, J.L. Mccarter, M.L. Stutzman, K.W. Trantham, Timothy G. Anderson, A.M. Cook, Timothy J. Gay

Timothy J. Gay Publications

Nuclear physics experiments at Thomas Jefferson National Accelerator Facility’s CEBAF rely on high polarization electron beams. We describe a recently commissioned system for prequalifying and studying photocathodes for CEBAF with a load-locked, low-voltage polarized electron source coupled to a compact retarding-field Mott polarimeter. The polarimeter uses simplified electrode structures and operates from 5 to 30 kV. The effective Sherman function for this device has been calibrated by comparison with the CEBAF 5 MeV Mott polarimeter. For elastic scattering from a thick gold target at 20 keV, the effective Sherman function is 0.201(5). Its maximum efficiency at 20 keV, defined as …

Submillimeter-Resolution Radiography Of Shielded Structures With Laser-Accelerated Electron Beams, Viswanathan Ramanathan, Sudeep Banerjee, Nathan D. Powers, Nathaniel Cunningham, Nathan A. Chandler-Smith, Kun Zhao, Kevin J. Brown, Donald Umstadter, Shaun Clarke, Sara Pozzi, James Beene, Randy Vane, David Schultz

Donald Umstadter Publications

We investigate the use of energetic electron beams for high-resolution radiography of flaws embedded in thick solid objects. A bright, monoenergetic electron beam (with energy >100 MeV) was generated by the process of laser-wakefield acceleration through the interaction of 50-TW, 30-fs laser pulses with a supersonic helium jet. The high energy, low divergence, and small source size of these beams make them ideal for high-resolution radiographic studies of cracks or voids embedded in dense materials that are placed at a large distance from the source. We report radiographic imaging of steel with submillimeter resolution.

Magnetic And Optical Properties Of Multiferroic Gdmno3 Nanoparticles, X. L. Wang, D. Li, T. Y. Cui, Parashu Kharel, W. Liu, Z. D. Zhang

Department of Physics and Astronomy: Faculty Publications

The magnetic and optical properties of multiferroic GdMnO₃ nanoparticles synthesized by a polymerized complex method have been investigated. The GdMnO₃ nanoparticles crystallized in orthorhombic perovskite-type structure. The zero-field-cooled and field-cooled magnetizations show that complicated magnetic transitions occur in a temperature range from 2 to 60 K, which were confirmed by magnetic hysteresis loops. Three shoulder absorption peaks centered at about 2.0, 2.3, and 2.7 eV are attributed to the Mn (3d)-electronic transitions, while an absorption peak at around 4.1 eV corresponds to the charge-transfer transitions between O (2p) and Mn (3d) states. UV emission at about 396 and …

V371 Per — A Thick-Disk, Short-Period F/1o Cepheid, P. Wils, A. A. Henden, S. Kleidis, Edward G. Schmidt, D. L. Welch

Edward Schmidt Publications

V371 Per was found to be a double-mode Cepheid with a fundamental mode period of 1.738 days, the shortest among Galactic beat Cepheids, and an unusually high period ratio of 0.731, while the other Galactic beat Cepheids have period ratios between 0.697 and 0.713. The latter suggests that the star has a metallicity [Fe/H] between −1 and −0.7. The derived distance from the Galactic plane places it in the thick disk or the Halo, while all other Galactic beat Cepheids belong to the thin disk. There are indications from historical data that both the fundamental and first overtone periods have …

Electrically Driven Magnetism On A Pd Thin Film, Y. Sun, John D. Burton, Evgeny Y. Tsymbal

Evgeny Tsymbal Publications

Using first-principles density-functional calculations, we demonstrate that ferromagnetism can be induced and modulated on an otherwise paramagnetic Pd metal thin-film surface through application of an external electric field. As free charges are either accumulated or depleted at the Pd surface to screen the applied electric field, there is a corresponding change in the surface density of states. This change can be made sufficient for the Fermi-level density of states to satisfy the Stoner criterion, driving a transition locally at the surface from a paramagnetic state to an itinerant ferromagnetic state above a critical applied electric field, E_c. Furthermore, …

Effect Of Spin-Dependent Screening On Tunneling Electroresistance And Tunneling Magnetoresistance In Multiferroic Tunnel Junctions, M. Ye. Zhuravlev, S. Maekawa, Evgeny Y. Tsymbal

Evgeny Tsymbal Publications

Using a ferroelectric barrier as a functional material in a (magnetic) tunnel junction has recently attracted significant interest due to new functionalities not available in conventional tunnel junctions. Switching a ferroelectric polarization of the barrier alters conductance resulting in a tunneling electroresistance (TER) effect. Using a ferroelectric barrier in a magnetic tunnel junction makes it mutiferroic where TER coexists with tunneling magnetoresistance (TMR). Here we develop a simple model for a multiferroic tunnel junction (MFTJ) which consists of two ferromagnetic electrodes separated by a ferroelectric barrier layer. The model explicitly includes the spin-dependent screening potential and thus extends previously developed …

Ferroelectric Dead Layer Driven By A Polar Interface, Y. Wang, Manish K. Niranjan, K. Janicka, Julian P. Velev, Mikhail Ye Zhuravlev, Sitaram S. Jaswal, Evgeny Y. Tsymbal

Evgeny Tsymbal Publications

Based on first-principles and model calculations we investigate the effect of polar interfaces on the ferroelectric stability of thin-film ferroelectrics. As a representative model, we consider a TiO₂ -terminated BaTiO₃ film with LaO monolayers at the two interfaces that serve as doping layers. We find that the polar interfaces create an intrinsic electric field that is screened by the electron charge leaking into the BaTiO₃ layer. The amount of the leaking charge is controlled by the boundary conditions which are different for three heterostructures considered, namely, vacuum/LaO/BaTiO₃ /LaO, LaO/BaTiO₃ , and SrRuO₃ /LaO/BaTiO_{3 …}

Evolution Of The Band Alignment At Polar Oxide Interfaces, John D. Burton, Evgeny Y. Tsymbal

Evgeny Tsymbal Publications

First-principles calculations demonstrate the evolution of the band alignment at La_0.7A_0.3MnO₃ / La_1−xA_xO / TiO₂ / SrTiO₃ (001) heterointerfaces, where A=Ca, Sr, or Ba, as the interfacial A-site composition, La_1−xA_x, is varied from x=0.5 to x=1.0. This variation leads to a linear change in the SrTiO₃ valence-band offset with respect to the Fermi level of the La_0.7A_0.3MnO₃ metal electrode and hence to a linear change in the Schottky barrier height at this interface. The effect arises due to electrostatic …

Structural, Magnetic And Magneto-Transport Properties Of Pt-Alloyed Mnbi Thin Films, Parashu Kharel, Ralph Skomski, Roger D. Kirby, David J. Sellmyer

Ralph Skomski Publications

The structural, magnetic and magneto-transport properties of highly c-axis oriented Mn_55−xPt_xBi₄₅ (x=0, 1.5, 3, and 4.5) thin films have been investigated. The coercivity of the Pt-alloyed thin films increases and the saturation magnetization decreases as the Pt concentration increases. The anisotropy field H_o increases as a function of Pt concentration, too but the coercivity increases more rapidly than the anisotropy field. This indicates an enhanced domain-wall pinning, caused by increased interstitial disorder due to the occupancy of regular Mn sites by Pt. The same mechanism explains the reduced magnetization. All samples exhibit a large …

Interstitial-Nitrogen Effect On Phase Transition And Magnetocaloric Effect In Mn(As,Si) (Invited), W. B. Cui, X. K. Lv, F. Yang, Ralph Skomski, Y. Yu, X. G. Zhao, W. Liu, Z.D. Zhang

Ralph Skomski Publications

The effect of interstitial nitrogen on the phase transition and magnetocaloric behavior of MnAs_1−xSi_xN_δ (x=0.03, 0.06, and 0.09) is investigated. The interstitial nitrogen atoms cause the step-scanned x-ray diffraction peaks to shift toward lower angles and lower the Curie temperature, whereas silicon addition increases the Curie temperature to near room temperature. The thermal hysteresis is reduced to nearly 0 in MnAs_1−xSi_xN_δ, which is beneficial to practical applications. For a field change of 5 T, the largest magnetic entropy change and refrigerant capacity are 14.6 J kg⁻¹ K^{−1 …}

Vowel Recognition From Continuous Articulatory Movements For Speaker-Dependent Applications, Jun Wang, Jordan R. Green, Ashok Samal, Tom D. Carrell

Department of Special Education and Communication Disorders: Faculty Publications

A novel approach was developed to recognize vowels from continuous tongue and lip movements. Vowels were classified based on movement patterns (rather than on derived articulatory features, e.g., lip opening) using a machine learning approach. Recognition accuracy on a single-speaker dataset was 94.02% with a very short latency. Recognition accuracy was better for high vowels than for low vowels. This finding parallels previous empirical findings on tongue movements during vowels. The recognition algorithm was then used to drive an articulation-to-acoustics synthesizer. The synthesizer recognizes vowels from continuous input stream of tongue and lip movements and plays the corresponding sound samples …

Mechanical Sensorless Maximum Power Tracking Control For Direct-Drive Pmsg Wind Turbines, Xu Yang, Xiang Gong, Wei Qiao

Department of Electrical and Computer Engineering: Faculty Publications

Wind turbine generators (WTGs) are usually equipped with mechanical sensors to measure wind speed and rotor position for system control, monitoring, and protection. The use of mechanical sensors increases the cost and hardware complexity and reduces the reliability of the WTG systems. This paper proposes a mechanical sensorless maximum power tracking control for wind turbines directly driving permanent magnetic synchronous generators (PMSGs). In the proposed algorithm, the PMSG rotor position is estimated from the measured stator voltages and currents by using a sliding mode observer (SMO). The wind turbine shaft speed is estimated from the PMSG back electromotive force (EMF) …

Corrosion Of Steel Shipwrecks In The Marine Environment: Uss Arizona—Part 2, Donald L. Johnson, Brent M. Wilson, James D. Carr, Matthew A. Russell, Larry E. Murphy, David L. Conlin

Department of Chemistry: Faculty Publications

This article is a continuation of Part 1 (October 2006 MP) on the USS Arizona hull. It discusses additional methods being investigated for use in determining corrosion rates with a minimal impact on the existing structure. Marine biofouling (concretion) has accumulated on the hull. Concretion samples have been studied using x-ray diffraction, environmental electron microscopy, and corrosion potential (E_corr) to characterize the relationship between concretion and the steel substrate. The data presented in this study confirm the viability of concretion analysis as a minimum-impact procedure to estimate the corrosion rate of mild steel in seawater.

Corrosion Of Civil War Era Sub Marine Explorer—Part 2, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer was designed and built by Julius H. Kroehl, who was born in Prussia in 1820. After migrating to the United States in 1838 and becoming a citizen, he served in the Union Navy (United States Navy during the Civil War) as an underwater demolitions expert. He left the Navy in 1863 and began designing a “sub-marine” that would facilitate Union forces’ mine removal and obstruction clearance. At the end of the Civil War, he became an engineer for the Pacific Pearl Co., an organization interested in using the craft to recover pearls from deep sea oyster …

Corrosion Of Civil War Era Sub Marine Explorer—Part 1, Donald L. Johnson, James D. Carr, Brent M. Wilson, Larry E. Murphy, James P. Delgado

Department of Chemistry: Faculty Publications

The Sub Marine Explorer is one of five submersibles (submarines) constructed prior to 1870 that have survived either in museums or as in situ archaeological sites around the world. Since 1869, the wreck of Explorer has emerged at low tide on the beach of Isla San Telmo, Archipiélago de las Perlas, Panama, located ~75 km southwest of Panama City in the Bay of Panama. In 2001, James Delgado visited the site. Locals described the wreck as a World War II-era Japanese midget submarine. Delgado consulted with Richard Wills, an expert on American Civil War submarines, and confirmed that the well-preserved …

Method For Monitoring The Stereoselectivity And Relative Rate Of Organic Chemical Reactions, David R. Berkowitz, Sangeeta Dey, Kannan R. Karukurichi, Weijun Shen

Department of Chemistry: Faculty Publications

A method for monitoring the stereoselectivity of at least one organic chemical reaction and the relative rate of at least one organic chemical reaction, wherein the reaction produces a product that can exist as at least two stereoisomers, is provided herein. Also disclosed are methods for identifying and preparing catalysts for the above reactions.

Transition States In Ei Reactions, Charles A. Kingsbury

Department of Chemistry: Faculty Publications

The pyrolysis of amine oxides, sulfoxides, selenoxides, and esters to form alkenes is believed to be a concerted reaction with a cyclic transition state. Phosphine oxides, sulfones, and nitro compounds are unreactive. This study seeks to identify reasons for the lack of reactivity of the latter. Transition states were located for all substrates progressing from RHF/3-21G* to the MP2/6-31+G(d,p) level (in certain cases). For sulfones and nitro compounds, two possible reasons for lack of reactivity were considered: (1) Atoms approaching one another in the transition state may be considered to participate in a local n_O→σ*_{CH …}

Improved Arene Fluorination Methodology For I(Iii) Salts, Bijia Wang, Linlin Qin, Kiel D. Neumann, Shriharsha Uppaluri, Ronald Cerny, Stephen G. Dimagno

Ronald Cerny Publications

The use of low polarity aromatic solvents (benzene or toluene) and/or the removal of inorganic salts results in dramatically improved yields of fluorinated arenes from diaryliodonium salts. This methodology is shown to “scale down” to the conditions used typically for radiotracer synthesis.

Corrosion Behavior Of Copper Thin Films In Organic Hf-Containing Cleaning Solution For Semiconductor Applications, Nabil George Mistkawi, Makarem A. Hussein, Malgorzata Ziomek-Moroz, Shankar B. Rananavare

Chemistry Faculty Publications and Presentations

The corrosion behavior of electrochemically deposited copper thin films in deaerated and non-deaerated commercial cleaning solutions containing HF was investigated. Potentiodynamic polarization experiments were carried out to determine active, active–passive, passive, and transpassive regions. Corrosion rates were calculated from Tafel slopes. The addition of hydrogen peroxide to the solution and its influence on corrosion was also investigated by employing inductively coupled plasma-mass spectroscopy (ICP-MS) and X-ray photoelectron spectroscopy (XPS). The ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Surface analysis using atomic force microscopy and scanning electron microscopy, performed before and after the cleaning solution treatment, did not reveal …

Immobilization Of The Aminopeptidase From Aeromonas Proteolytica On Mg2+/Al3+ Layered Double Hydroxide Particles, Steven T. Frey, Stephanie L. Guilmet, Richard G. Egan Iii, Alyssa Bennett, Sarah R. Soltau, Richard C. Holz

Chemistry Faculty Research and Publications

A novel biomaterial formed by the immobilization of the Aminopeptidase from Aeromonas proteolytica (AAP) on synthetic Mg²⁺ and Al³⁺ ion-containing layered double hydroxide (LDH) particles was prepared. Immobilization of AAP on the LDH particles in a buffered, aqueous mixture is rapid such that the maximum loading capacity, 1 × 10⁻⁹ moles of AAP/mg LDH, is achieved in a few minutes. X-ray powder diffraction of LDH samples before and after treatment with AAP indicates that the enzyme does not intercalate between the layers of LDH, but instead binds to the surface. Treatment of AAP/LDH with various amounts of …

Regiospecific Reductive Elimination From Diaryliodonium Salts, Bijia Wang, Joseph W. Graskemper, Linlin Qin, Stephen G. Dimagno

Stephen DiMagno Papers

StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) is provided by the cyclophane substituent on iodine(III). Computational and experimental studies demonstrate that out of plane steric bulk strongly destabilizes the reductive elimination transition state, and leads to regiochemical control. This approach should be general for high valent main group and transition metal ions.

Enhanced Late Holocene Enso/Pdo Expression Along The Margins Of The Eastern North Pacific, John A. Barron, Lesleigh Anderson

United States Geological Survey: Staff Publications

Pacific climate is known to have varied during the Holocene, but spatial patterns remain poorly defined. This paper compiles terrestrial and marine proxy data from sites along the northeastern Pacific margins and proposes that they indicate 1) suppressed ENSO conditions during the middle Holocene between ~8000 and 4000 cal BP with a North Pacific that generally resembled a La Niña-like or more negative PDO phase and 2) a climate transition between ~4200 and 3000 cal BP that appears to be the teleconnected expression to a more modern-like ENSO Pacific. Compared to modern day conditions, the compiled data suggest that during …

Recent Advances In Global Lake Coring Hold Promise For Global Change Research In Paleolimnology, Walter E. Dean

United States Geological Survey: Staff Publications

Thank you, Antje, for your generous comments and I thank IPA for presenting me with this award along with three giants of paleolimnology! I am humbled and delighted to accept this award as a representative of all those in the Paleolimnology community whose creative insights continue to make Paleolimnology inspiring.