Atomic orbital-based SOS-MP2 with tensor hypercontraction. II. Local tensor hypercontraction

NASA Astrophysics Data System (ADS)

Song, Chenchen; Martínez, Todd J.

2017-01-01

In the first paper of the series [Paper I, C. Song and T. J. Martinez, J. Chem. Phys. 144, 174111 (2016)], we showed how tensor-hypercontracted (THC) SOS-MP2 could be accelerated by exploiting sparsity in the atomic orbitals and using graphical processing units (GPUs). This reduced the formal scaling of the SOS-MP2 energy calculation to cubic with respect to system size. The computational bottleneck then becomes the THC metric matrix inversion, which scales cubically with a large prefactor. In this work, the local THC approximation is proposed to reduce the computational cost of inverting the THC metric matrix to linear scaling with respect to molecular size. By doing so, we have removed the primary bottleneck to THC-SOS-MP2 calculations on large molecules with O(1000) atoms. The errors introduced by the local THC approximation are less than 0.6 kcal/mol for molecules with up to 200 atoms and 3300 basis functions. Together with the graphical processing unit techniques and locality-exploiting approaches introduced in previous work, the scaled opposite spin MP2 (SOS-MP2) calculations exhibit O(N2.5) scaling in practice up to 10 000 basis functions. The new algorithms make it feasible to carry out SOS-MP2 calculations on small proteins like ubiquitin (1231 atoms/10 294 atomic basis functions) on a single node in less than a day.

Atomic orbital-based SOS-MP2 with tensor hypercontraction. II. Local tensor hypercontraction.

PubMed

Song, Chenchen; Martínez, Todd J

2017-01-21

In the first paper of the series [Paper I, C. Song and T. J. Martinez, J. Chem. Phys. 144, 174111 (2016)], we showed how tensor-hypercontracted (THC) SOS-MP2 could be accelerated by exploiting sparsity in the atomic orbitals and using graphical processing units (GPUs). This reduced the formal scaling of the SOS-MP2 energy calculation to cubic with respect to system size. The computational bottleneck then becomes the THC metric matrix inversion, which scales cubically with a large prefactor. In this work, the local THC approximation is proposed to reduce the computational cost of inverting the THC metric matrix to linear scaling with respect to molecular size. By doing so, we have removed the primary bottleneck to THC-SOS-MP2 calculations on large molecules with O(1000) atoms. The errors introduced by the local THC approximation are less than 0.6 kcal/mol for molecules with up to 200 atoms and 3300 basis functions. Together with the graphical processing unit techniques and locality-exploiting approaches introduced in previous work, the scaled opposite spin MP2 (SOS-MP2) calculations exhibit O(N 2.5 ) scaling in practice up to 10 000 basis functions. The new algorithms make it feasible to carry out SOS-MP2 calculations on small proteins like ubiquitin (1231 atoms/10 294 atomic basis functions) on a single node in less than a day.

Correlation in photon pairs generated using four-wave mixing in a cold atomic ensemble

NASA Astrophysics Data System (ADS)

Ferdinand, Andrew Richard; Manjavacas, Alejandro; Becerra, Francisco Elohim

2017-04-01

Spontaneous four-wave mixing (FWM) in atomic ensembles can be used to generate narrowband entangled photon pairs at or near atomic resonances. While extensive research has been done to investigate the quantum correlations in the time and polarization of such photon pairs, the study and control of high dimensional quantum correlations contained in their spatial degrees of freedom has not been fully explored. In our work we experimentally investigate the generation of correlated light from FWM in a cold ensemble of cesium atoms as a function of the frequencies of the pump fields in the FWM process. In addition, we theoretically study the spatial correlations of the photon pairs generated in the FWM process, specifically the joint distribution of their orbital angular momentum (OAM). We investigate the width of the distribution of the OAM modes, known as the spiral bandwidth, and the purity of OAM correlations as a function of the properties of the pump fields, collected photons, and the atomic ensemble. These studies will guide experiments involving high dimensional entanglement of photons generated from this FWM process and OAM-based quantum communication with atomic ensembles. This work is supported by AFORS Grant FA9550-14-1-0300.

The Difference a Single Atom Can Make: Synthesis and Design at the Chemistry–Biology Interface

PubMed Central

2017-01-01

A Perspective of work in our laboratory on the examination of biologically active compounds, especially natural products, is presented. In the context of individual programs and along with a summary of our work, selected cases are presented that illustrate the impact single atom changes can have on the biological properties of the compounds. The examples were chosen to highlight single heavy atom changes that improve activity, rather than those that involve informative alterations that reduce or abolish activity. The examples were also chosen to illustrate that the impact of such single-atom changes can originate from steric, electronic, conformational, or H-bonding effects, from changes in functional reactivity, from fundamental intermolecular interactions with a biological target, from introduction of a new or altered functionalization site, or from features as simple as improvements in stability or physical properties. Nearly all the examples highlighted represent not only unusual instances of productive deep-seated natural product modifications and were introduced through total synthesis but are also remarkable in that they are derived from only a single heavy atom change in the structure. PMID:28945374

Theoretical study on the photocatalytic properties of graphene oxide with single Au atom adsorption

NASA Astrophysics Data System (ADS)

Ju, Lin; Dai, Ying; Wei, Wei; Li, Mengmeng; Jin, Cui; Huang, Baibiao

2018-03-01

The photocatalytic properties of graphene oxide (GO) with single Au atom adsorption are studied via the first-principles calculations based on the density functional theory. The present study addresses the origin of enhancement in photocatalytic efficiency of GO derived from single Au atom depositing. Compared with the clean one, the work function of the single Au atom adsorbed GO is lowered due to the charge transfer from Au to GO, indicating enhanced surface activity. The Au atom plays as an electron trapping center and a mediating role in charge transfer from photon excited GO to target species. The photogenerated electron-hole pairs can be separated effectively. For the GO configuration with atomic Au dispersion, there are some states introduced in the band gap, which are predominantly composed of Au 6s states. Through the in-gap state, the photo-generated electron transfer from the valence band of clean GO to the conductive band more easily. In addition, the reduction of the gap in the system is also presented in the current work, which indicates that the single Au atom adsorption improves light absorption for the GO based photocatalyst. These theoretical results are valuable for the future applications of GO materials as photocatalyst for water splitting.

Correlation energy, correlated electron density, and exchange-correlation potential in some spherically confined atoms.

PubMed

Vyboishchikov, Sergei F

2016-12-05

We report correlation energies, electron densities, and exchange-correlation potentials obtained from configuration interaction and density functional calculations on spherically confined He, Be, Be 2+ , and Ne atoms. The variation of the correlation energy with the confinement radius R c is relatively small for the He, Be 2+ , and Ne systems. Curiously, the Lee-Yang-Parr (LYP) functional works well for weak confinements but fails completely for small R c . However, in the neutral beryllium atom the CI correlation energy increases markedly with decreasing R c . This effect is less pronounced at the density-functional theory level. The LYP functional performs very well for the unconfined Be atom, but fails badly for small R c . The standard exchange-correlation potentials exhibit significant deviation from the "exact" potential obtained by inversion of Kohn-Sham equation. The LYP correlation potential behaves erratically at strong confinements. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Feasibility study of oxygen-dispensing emitters for thermionic converters, phase 1

NASA Technical Reports Server (NTRS)

Desteese, J. G.

1972-01-01

A metal/ceramic Marchuk tube was used to measure work functions of oxygen-doped tantalum, to determine applicability of the material to plasma-mode thermionic converters. Oxygen-doped tantalum was shown to increase in work function monotonically with oxygen doping in the range 0.1 to 0.3 atomic percent. Oxygenated test emitters were run at an average temperature of 2165 K and a T/T sub Cs ratio -5.8 to observe the influence of oxygen depletion. Bare work function decreased with outgassing of oxygen. Projections were made based on outgassing kinetics and area/volume ratios to calculate the longevity of oxygen doping in a practical converter. Calculations indicated that the program goal of 10,000 hr could be achieved at 1800 K with an initial oxygen doping of 1 atomic percent and a practical emitter area/volume ratio.

Effect of the cesium and potassium doping of multiwalled carbon nanotubes grown in an electrical arc on their emission characteristics

NASA Astrophysics Data System (ADS)

Izrael'yants, K. R.; Orlov, A. P.; Ormont, A. B.; Chirkova, E. G.

2017-04-01

The effect of cesium and potassium atoms deposited onto multiwalled carbon nanotubes grown in an electrical arc on their emission characteristics was studied. The current-voltage characteristics of the field electron emission of specimens with cesium or potassium doped multiwalled carbon nanotubes of this type were revealed to retain their linear character in the Fowler-Nordheim coordinates within several orders of magnitude of change in the emission current. The deposition of cesium and potassium atoms was shown to lead to a considerable increase in the emission current and a decrease in the work function φ of studied emitters with multiwalled nanotubes. The work function was established to decrease to φ 3.1 eV at an optimal thickness of coating with cesium atoms and to φ 2.9 eV in the case of doping with potassium atoms. Cesium and potassium deposition conditions optimal for the attainment of a maximum emission current were found.

Adsorption of O_{2} on Ag(111): Evidence of Local Oxide Formation.

PubMed

Andryushechkin, B V; Shevlyuga, V M; Pavlova, T V; Zhidomirov, G M; Eltsov, K N

2016-07-29

The atomic structure of the disordered phase formed by oxygen on Ag(111) at low coverage is determined by a combination of low-temperature scanning tunneling microscopy and density functional theory. We demonstrate that the previous assignment of the dark objects in STM to chemisorbed oxygen atoms is incorrect and incompatible with trefoil-like structures observed in atomic-resolution images in current work. In our model, each object is an oxidelike ring formed by six oxygen atoms around the vacancy in Ag(111).

Bonding reactivity descriptor from conceptual density functional theory and its applications to elucidate bonding formation

NASA Astrophysics Data System (ADS)

Zhou, Pan-Pan; Liu, Shubin; Ayers, Paul W.; Zhang, Rui-Qin

2017-10-01

Condensed-to-atom Fukui functions which reflect the atomic reactivity like the tendency susceptible to either nucleophilic or electrophilic attack demonstrate the bonding trend of an atom in a molecule. Accordingly, Fukui functions based concepts, that is, bonding reactivity descriptors which reveal the bonding properties of molecules in the reaction were put forward and then applied to pericyclic and cluster reactions to confirm their effectiveness and reliability. In terms of the results from the bonding descriptors, a covalent bond can readily be predicted between two atoms with large Fukui functions (i.e., one governs nucleophilic attack while the other one governs electrophilic attack, or both of them govern radical attacks) for pericyclic reactions. For SinOm clusters' reactions, the clusters with a low O atom ratio readily form a bond between two Si atoms with big values of their Fukui functions in which they respectively govern nucleophilic and electrophilic attacks or both govern radical attacks. Also, our results from bonding descriptors show that Si—Si bonds can be formed via the radical mechanism between two Si atoms, and formations of Si—O and O—O bonds are possible when the O content is high. These results conform with experimental findings and can help experimentalists design appropriate clusters to synthesize Si nanowires with high yields. The approach established in this work could be generalized and applied to study reactivity properties for other systems.

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

2006-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.

Single-photon nonlinearities in the propagation of focused beams through dense atomic clouds

NASA Astrophysics Data System (ADS)

Wang, Yidan; Gorshkov, Alexey; Gullans, Michael

2017-04-01

We theoretically study single-photon nonlinearities realized when a highly focused Gaussian beam passes through a dense atomic cloud. In this system, strong dipole-dipole interactions arise between closely spaced atoms and significantly affect light propagation. We find that the highly focused Gaussian beam can be treated as an effective one-dimensional waveguide, which simplifies the calculation of photon transmission and correlation functions. The formalism we develop is also applicable to the case where additional atom-atom interactions, such as interactions between Rydberg atoms, are involved. This work was supported by the ARL, NSF PFC at the JQI, AFOSR, NSF PIF, ARO, and AFOSR MURI.

The local work function: Concept and implications

NASA Astrophysics Data System (ADS)

Wandelt, K.

1997-02-01

The term 'local work function' is now widely applied. The present work discusses the common physical basis of 'photoemission of adsorbed xenon (PAX)' and 'two-photon photonemissionspectroscopy of image potential states' as local work function probes. New examples with bimetallic and defective surfaces are presented which demonstrate the capability of PAX measurements for the characterization of heterogeneous surfaces on an atomic scale. Finally, implications of the existence of short-range variations of the surface potential at surface steps are addressed. In particular, dynamical work function change measurements are a sensitive probe for the step-density at surfaces and, as such, a powerful in-situ method to monitor film growth.

Amorphous transparent conducting oxides in context: Work function survey, trends, and facile modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeh, T. C.; Zhu, Q.; Buchholz, D. B.

2015-03-01

The work functions of various amorphous and crystalline transparent conducting oxides (TCO5) were measured using Kelvin probe. The films, made by pulsed laser deposition, exhibited varying work functions dependent on the composition and deposition parameters. Tin oxide showed the largest work functions of the oxides measured, while zinc oxide showed the lowest. Binary and ternary combinations of the basis TCOs showed intermediate work functions dependent on the endpoint components. Amorphous TCO5, important in OPV and other technological applications, exhibited similar work functions to their crystalline counterparts. UV/ozone treatment of TCOs temporarily increased the work function, consistent with proposed defect mechanismsmore » associated with near-surface changes in carrier content and Fermi level. Finally, a method for facile adjustment of the work function of commercial TCOs by atomic layer deposition (ALD) capping layers was presented, illustrated by the growth of zinc oxide layers on commercial crystalline ITO films.« less

Amorphous transparent conducting oxides in context: Work function survey, trends, and facile modification

NASA Astrophysics Data System (ADS)

Yeh, T. C.; Zhu, Q.; Buchholz, D. B.; Martinson, A. B.; Chang, R. P. H.; Mason, T. O.

2015-03-01

The work functions of various amorphous and crystalline transparent conducting oxides (TCOs) were measured using Kelvin probe. The films, made by pulsed laser deposition, exhibited varying work functions dependent on the composition and deposition parameters. Tin oxide showed the largest work functions of the oxides measured, while zinc oxide showed the lowest. Binary and ternary combinations of the basis TCOs showed intermediate work functions dependent on the endpoint components. Amorphous TCOs, important in OPV and other technological applications, exhibited similar work functions to their crystalline counterparts. UV/ozone treatment of TCOs temporarily increased the work function, consistent with proposed defect mechanisms associated with near-surface changes in carrier content and Fermi level. Finally, a method for facile adjustment of the work function of commercial TCOs by atomic layer deposition (ALD) capping layers was presented, illustrated by the growth of zinc oxide layers on commercial crystalline ITO films.

Efficient Means of Detecting Neutral Atoms in Space

NASA Astrophysics Data System (ADS)

Zinicola, W. N.

2006-12-01

This summer, The Society of Physics Students granted me the opportunity to participate in an internship for The National Aeronautics and Space Administration (NASA) and The University of Maryland. Our chief interest was analyzing low energy neutral atoms that were created from random interactions of ions in space plasma. From detecting these neutrals one can project a image of what the plasma's composition is, and how this plasma changes through interactions with the solar wind. Presently, low energy neutral atom detectors have poor efficiency, typically in the range of 1%. Our goal was to increase this efficiency. To detect low energy neutrals we must first convert them from neutral molecules to negatively charged ions. Once converted, these "new" negatively charged ions can be easily detected and completely analyzed giving us information about their energy, mass, and instantaneous direction. The efficiency of the detector is drastically affected by the surface used for converting these neutrals. My job was first to create thin metal conversion surfaces. Then, using an X-ray photoelectron spectrometer, analyze atomic surface composition and gather work function values. Once the work function values were known we placed the surfaces in our neutral detector and measured their conversion efficiencies. Finally, a relation between the work function of the metal surface an its conversion efficiency was generated. With this relationship accurately measured one could use this information to help give suggestions on what surface would be the best to increase our detection efficiency. If we could increase the efficiency of these low energy neutral atom detectors by even 1% we would be able to decrease the size of the detector therefore making it cheaper and more applicable for space exploration.* * A special thanks to Dr. Michael Coplan of the University of Maryland for his support and guidance through all my research.

Identification and Characterization of Molecular Bonding Structures by ab initio Quasi-Atomic Orbital Analyses.

PubMed

West, Aaron C; Duchimaza-Heredia, Juan J; Gordon, Mark S; Ruedenberg, Klaus

2017-11-22

The quasi-atomic analysis of ab initio electronic wave functions in full valence spaces, which was developed in preceding papers, yields oriented quasi-atomic orbitals in terms of which the ab initio molecular wave function and energy can be expressed. These oriented quasi-atomic orbitals are the rigorous ab initio counterparts to the conceptual bond forming atomic hybrid orbitals of qualitative chemical reasoning. In the present work, the quasi-atomic orbitals are identified as bonding orbitals, lone pair orbitals, radical orbitals, vacant orbitals and orbitals with intermediate character. A program determines the bonding characteristics of all quasi-atomic orbitals in a molecule on the basis of their occupations, bond orders, kinetic bond orders, hybridizations and local symmetries. These data are collected in a record and provide the information for a comprehensive understanding of the synergism that generates the bonding structure that holds the molecule together. Applications to a series of molecules exhibit the complete bonding structures that are embedded in their ab initio wave functions. For the strong bonds in a molecule, the quasi-atomic orbitals provide quantitative ab initio amplifications of the Lewis dot symbols. Beyond characterizing strong bonds, the quasi-atomic analysis also yields an understanding of the weak interactions, such as vicinal, hyperconjugative and radical stabilizations, which can make substantial contributions to the molecular bonding structure.

Solid-State Diffusional Behaviors of Functional Metal Oxides at Atomic Scale.

PubMed

Chen, Jui-Yuan; Huang, Chun-Wei; Wu, Wen-Wei

2018-02-01

Metal/metal oxides have attracted extensive research interest because of their combination of functional properties and compatibility with industry. Diffusion and thermal reliability have become essential issues that require detailed study to develop atomic-scaled functional devices. In this work, the diffusional reaction behavior that transforms piezoelectric ZnO into magnetic Fe 3 O 4 is investigated at the atomic scale. The growth kinetics of metal oxides are systematically studied through macro- and microanalyses. The growth rates are evaluated by morphology changes, which determine whether the growth behavior was a diffusion- or reaction-controlled process. Furthermore, atom attachment on the kink step is observed at the atomic scale, which has important implications for the thermodynamics of functional metal oxides. Faster growth planes simultaneously decrease, which result in the predominance of low surface energy planes. These results directly reveal the atomic formation process of metal oxide via solid-state diffusion. In addition, the nanofabricated method provides a novel approach to investigate metal oxide evolution and sheds light on diffusional reaction behavior. More importantly, the results and phenomena of this study provide considerable inspiration to enhance the material stability and reliability of metal/oxide-based devices. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density Functional Theory Study of Leaching Performance of Different Acids on Pyrochlore (100) Surface

NASA Astrophysics Data System (ADS)

Yang, Xiuli; Fang, Qing; Ouyang, Hui

2018-04-01

Pyrochlore leaching using hydrofluoric, sulfuric, and hydrochloric acids has been studied via experimental methods for years, but the interactions between niobium atoms on the pyrochlore surface and different acids have not been investigated. In this work, first-principles calculations based on density functional theory were used to elucidate the leaching performance of these three acids from the viewpoint of geometrical and electronic structures. The calculation results indicate that sulfate, chloride, and fluoride anions influence the geometric structure of pyrochlore (100) to different extents, decreasing in the order: sulfate, fluoride, chloride. Orbitals of O1 and O2 atoms of sulfate hybridized with those of surface niobium atom. Fluorine orbitals hybridized with those of surface niobium atoms. However, no obvious overlap exists between any orbitals of chlorine and surface niobium, revealing that chlorine does not interact chemically with surface niobium atoms.

Density Functional Theory Study of Leaching Performance of Different Acids on Pyrochlore (100) Surface

NASA Astrophysics Data System (ADS)

Yang, Xiuli; Fang, Qing; Ouyang, Hui

2018-06-01

Pyrochlore leaching using hydrofluoric, sulfuric, and hydrochloric acids has been studied via experimental methods for years, but the interactions between niobium atoms on the pyrochlore surface and different acids have not been investigated. In this work, first-principles calculations based on density functional theory were used to elucidate the leaching performance of these three acids from the viewpoint of geometrical and electronic structures. The calculation results indicate that sulfate, chloride, and fluoride anions influence the geometric structure of pyrochlore (100) to different extents, decreasing in the order: sulfate, fluoride, chloride. Orbitals of O1 and O2 atoms of sulfate hybridized with those of surface niobium atom. Fluorine orbitals hybridized with those of surface niobium atoms. However, no obvious overlap exists between any orbitals of chlorine and surface niobium, revealing that chlorine does not interact chemically with surface niobium atoms.

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

1997-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+(sub n), MNO+, and MCO+(sub 2). The DFT works well for frequencies and geometries, even in cases with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of the successes as well as failures of DFT will be given.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Zhe-Chen; Bierbaum, Veronica M.

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominatesmore » but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.« less

Toward the identification of molecular cogs.

PubMed

Dziubiński, Maciej; Lesyng, Bogdan

2016-04-05

Computer simulations of molecular systems allow determination of microscopic interactions between individual atoms or groups of atoms, as well as studies of intramolecular motions. Nevertheless, description of structural transformations at the mezoscopic level and identification of causal relations associated with these transformations is very difficult. Structural and functional properties are related to free energy changes. Therefore, to better understand structural and functional properties of molecular systems, it is required to deepen our knowledge of free energy contributions arising from molecular subsystems in the course of structural transformations. The method presented in this work quantifies the energetic contribution of each pair of atoms to the total free energy change along a given collective variable. Next, with the help of a genetic clustering algorithm, the method proposes a division of the system into two groups of atoms referred to as molecular cogs. Atoms which cooperate to push the system forward along a collective variable are referred to as forward cogs, and those which work in the opposite direction as reverse cogs. The procedure was tested on several small molecules for which the genetic clustering algorithm successfully found optimal partitionings into molecular cogs. The primary result of the method is a plot depicting the energetic contributions of the identified molecular cogs to the total Potential of Mean Force (PMF) change. Case-studies presented in this work should help better understand the implications of our approach, and were intended to pave the way to a future, publicly available implementation. © 2015 Wiley Periodicals, Inc.

Minima in generalized oscillator strengths for initially excited hydrogen-like atoms

NASA Technical Reports Server (NTRS)

Matsuzawa, M.; Omidvar, K.; Inokuti, M.

1976-01-01

Generalized oscillator strengths for transitions from an initially excited state of a hydrogenic atom to final states (either discrete or continuum) have complicated structures, including minima and shoulders, as functions of the momentum transfer. Extensive calculations carried out in the present work have revealed certain systematics of these structures. Some implications of the minima to the energy dependence of the inner-shell ionization cross section of heavy atoms by proton impact are discussed.

The importance of multi-level Rydberg interaction in electric field tuned Förster resonances

NASA Astrophysics Data System (ADS)

Kondo, Jorge; Booth, Donald; Gonçalves, Luis; Shaffer, James; Marcassa, Luis

2016-05-01

Many-body physics has been investigated in ultracold Rydberg atom systems, mainly because important parameters, such as density and interaction strength, can be controlled. Several puzzling experimental observations on Förster resonances have been associated to many-body effects, usually by comparison to complex theoretical models. In this work, we investigate the dc electric field dependence of 2 Förster resonant processes in ultracold 85 Rb, 37D5 / 2 + 37D5 / 2 --> 35 L(L = O , Q) + 39P3 / 2 , as a function of the atomic density in an optical dipole trap. At low densities, the 39 P yield as a function of electric field exhibits resonances. With increasing density, the linewidths increase until the peaks merge. Even under these extreme conditions, where many-body effects were expected to play a role, the 39 P population depends quadratically on the total Rydberg atom population. In order to explain our results, we implement a theoretical model which takes into account the multi-level character of the interactions and Rydberg atom blockade process using only atom pair interactions. The comparison between the experimental data and the model is very good, suggesting that the Förster resonant processes are dominated by 2-body interactions. This work is supported by FAPESP, AFOSR, NSF, INCT-IQ and CNPq.

Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

NASA Astrophysics Data System (ADS)

Wang, Zhe-Chen; Bierbaum, Veronica M.

2016-06-01

The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

Performance of the density matrix functional theory in the quantum theory of atoms in molecules.

PubMed

García-Revilla, Marco; Francisco, E; Costales, A; Martín Pendás, A

2012-02-02

The generalization to arbitrary molecular geometries of the energetic partitioning provided by the atomic virial theorem of the quantum theory of atoms in molecules (QTAIM) leads to an exact and chemically intuitive energy partitioning scheme, the interacting quantum atoms (IQA) approach, that depends on the availability of second-order reduced density matrices (2-RDMs). This work explores the performance of this approach in particular and of the QTAIM in general with approximate 2-RDMs obtained from the density matrix functional theory (DMFT), which rests on the natural expansion (natural orbitals and their corresponding occupation numbers) of the first-order reduced density matrix (1-RDM). A number of these functionals have been implemented in the promolden code and used to perform QTAIM and IQA analyses on several representative molecules and model chemical reactions. Total energies, covalent intra- and interbasin exchange-correlation interactions, as well as localization and delocalization indices have been determined with these functionals from 1-RDMs obtained at different levels of theory. Results are compared to the values computed from the exact 2-RDMs, whenever possible.

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

DOE PAGES

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs; ...

2018-05-25

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy

NASA Astrophysics Data System (ADS)

Timoshenko, Janis; Anspoks, Andris; Cintins, Arturs; Kuzmin, Alexei; Purans, Juris; Frenkel, Anatoly I.

2018-06-01

The knowledge of the coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use an artificial neural network approach to extract the information on the local structure and its in situ changes directly from the x-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic and austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from a body-centered to a face-centered cubic arrangement of iron atoms. This method is attractive for a broad range of materials and experimental conditions.

Variation in the thermionic work function of semiconductor powders exposed to electromagnetic radiation

NASA Technical Reports Server (NTRS)

Bourasseau, S.; Martin, J. R.; Juillet, F.; Teichner, S. J.

1977-01-01

The study of the variation of thermoelectronic work function potential of TiO2 in the presence of isobutane shows that this gas is not adsorbed on this solid, in either the presence or the absence of ultraviolet radiation. These results, as well as those obtained in a previous work, lead to the mechanism of the photo-oxidation of isobutane at room temperature, in which excited atomic oxygen is the active species.

Stretching of short monatomic gold chains-some model calculations

NASA Astrophysics Data System (ADS)

Sumali, Priyanka, Verma, Veena; Dharamvir, Keya

2012-06-01

The Mechanical properties of zig-zag monatomic gold chains containing 5 and 7 atoms were studied using the Siesta Code (SC), which works within the framework of DFT formalism and Gupta Potential (GP), which is an effective atom-atom potential. The zig-zag chains were stretched by keeping the end atoms fixed while rest of the atoms were relaxed till minimum energy is obtained. Energy, Force and Young's Modulus found using GP and SC were plotted as functions of total length. It is found that the breaking force in case of GP is of order of 1.6nN while for SIESTA is of the order of 2.9nN for both the chains.

Energetics and structural properties of twist grain boundaries in Cu

NASA Technical Reports Server (NTRS)

Karimi, Majid

1992-01-01

Structural and energetics properties of atoms near a grain boundary are of great importance from theoretical and experimental standpoints. From various experimental work it is concluded that diffusion at low temperatures at polycrystalline materials take place near grain boundary. Experimental and theoretical results also indicate changes of up to 70 percent in physical properties near a grain boundary. The Embedded Atom Method (EAM) calculations on structural properties of Au twist grain boundaries are in quite good agreement with their experimental counterparts. The EAM is believed to predict reliable values for the single vacancy formation energy as well as migration energy. However, it is not clear whether the EAM functions which are fitted to the bulk properties of a perfect crystalline solid can produce reliable results on grain boundaries. One of the objectives of this work is to construct the EAM functions for Cu and use them in conjunction with the molecular static simulation to study structures and energetics of atoms near twist grain boundaries in Cu. This provides tests of the EAM functions near a grain boundary. In particular, we determine structure, single vacancy formation energy, migration energy, single vacancy activation energy, and interlayer spacing as a function of distance from grain boundary. Our results are compared with the available experimental and theoretical results from grain boundaries and bulk.

Finite-temperature stress calculations in atomic models using moments of position.

PubMed

Parthasarathy, Ranganathan; Misra, Anil; Ouyang, Lizhi

2018-07-04

Continuum modeling of finite temperature mechanical behavior of atomic systems requires refined description of atomic motions. In this paper, we identify additional kinematical quantities that are relevant for a more accurate continuum description as the system is subjected to step-wise loading. The presented formalism avoids the necessity for atomic trajectory mapping with deformation, provides the definitions of the kinematic variables and their conjugates in real space, and simplifies local work conjugacy. The total work done on an atom under deformation is decomposed into the work corresponding to changing its equilibrium position and work corresponding to changing its second moment about equilibrium position. Correspondingly, we define two kinematic variables: a deformation gradient tensor and a vibration tensor, and derive their stress conjugates, termed here as static and vibration stresses, respectively. The proposed approach is validated using MD simulation in NVT ensembles for fcc aluminum subjected to uniaxial extension. The observed evolution of second moments in the MD simulation with macroscopic deformation is not directly related to the transformation of atomic trajectories through the deformation gradient using generator functions. However, it is noteworthy that deformation leads to a change in the second moment of the trajectories. Correspondingly, the vibration part of the Piola stress becomes particularly significant at high temperature and high tensile strain as the crystal approaches the softening limit. In contrast to the eigenvectors of the deformation gradient, the eigenvectors of the vibration tensor show strong spatial heterogeneity in the vicinity of softening. More importantly, the elliptic distribution of local atomic density transitions to a dumbbell shape, before significant non-affinity in equilibrium positions has occurred.

Finite-temperature stress calculations in atomic models using moments of position

NASA Astrophysics Data System (ADS)

Parthasarathy, Ranganathan; Misra, Anil; Ouyang, Lizhi

2018-07-01

Continuum modeling of finite temperature mechanical behavior of atomic systems requires refined description of atomic motions. In this paper, we identify additional kinematical quantities that are relevant for a more accurate continuum description as the system is subjected to step-wise loading. The presented formalism avoids the necessity for atomic trajectory mapping with deformation, provides the definitions of the kinematic variables and their conjugates in real space, and simplifies local work conjugacy. The total work done on an atom under deformation is decomposed into the work corresponding to changing its equilibrium position and work corresponding to changing its second moment about equilibrium position. Correspondingly, we define two kinematic variables: a deformation gradient tensor and a vibration tensor, and derive their stress conjugates, termed here as static and vibration stresses, respectively. The proposed approach is validated using MD simulation in NVT ensembles for fcc aluminum subjected to uniaxial extension. The observed evolution of second moments in the MD simulation with macroscopic deformation is not directly related to the transformation of atomic trajectories through the deformation gradient using generator functions. However, it is noteworthy that deformation leads to a change in the second moment of the trajectories. Correspondingly, the vibration part of the Piola stress becomes particularly significant at high temperature and high tensile strain as the crystal approaches the softening limit. In contrast to the eigenvectors of the deformation gradient, the eigenvectors of the vibration tensor show strong spatial heterogeneity in the vicinity of softening. More importantly, the elliptic distribution of local atomic density transitions to a dumbbell shape, before significant non-affinity in equilibrium positions has occurred.

Atomistic Interrogation of B–N Co-dopant Structures and Their Electronic Effects in Graphene

DOE PAGES

Schiros, Theanne; Nordlund, Dennis; Palova, Lucia; ...

2016-06-21

Chemical doping has been demonstrated to be an effective method for producing high-quality, large-area graphene with controlled carrier concentrations and an atomically tailored work function. Furthermore, the emergent optoelectronic properties and surface reactivity of carbon nanostructures are dictated by the microstructure of atomic dopants. Co-doping of graphene with boron and nitrogen offers the possibility to further tune the electronic properties of graphene at the atomic level, potentially creating p- and n-type domains in a single carbon sheet, opening a gap between valence and conduction bands in the 2-D semimetal. When using a suite of high-resolution synchrotron-based X-ray techniques, scanning tunnelingmore » microscopy, and density functional theory based computation we visualize and characterize B–N dopant bond structures and their electronic effects at the atomic level in single-layer graphene grown on a copper substrate. We find there is a thermodynamic driving force for B and N atoms to cluster into BNC structures in graphene, rather than randomly distribute into isolated B and N graphitic dopants, although under the present growth conditions, kinetics limit segregation of large B–N domains. We also observe that the doping effect of these BNC structures, which open a small band gap in graphene, follows the B:N ratio (B > N, p-type; B < N, n-type; B=N, neutral). We attribute this to the comparable electron-withdrawing and -donating effects, respectively, of individual graphitic B and N dopants, although local electrostatics also play a role in the work function change.« less

Dynamics of metal-induced crystallization of ultrathin Ge films by rapid thermal annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Yuanxun; Huang, Shujuan; Shrestha, Santosh

2015-12-07

Though Ge crystallization has been widely studied, few works investigate metal-induced crystallization of ultrathin Ge films. For 2 nm Ge films in oxide matrix, crystallization becomes challenging due to easy oxidation and low mobility of Ge atoms. Introducing metal atoms may alleviate these problems, but the functions and the behaviours of metal atoms need to be clarified. This paper investigates the crystallization dynamics of a multilayer structure 1.9 nm Ge/0.5 nm Al/1.5 nm Al{sub 2}O{sub 3} under rapid thermal annealing (RTA). The functions of metal atoms, like effective anti-oxidation, downshifting Raman peaks, and incapability to decrease crystallization temperature, are found and explained. The metalmore » behaviours, such as inter-diffusion and defect generation, are supported with direct evidences, Al-Ge nanobicrystals, and Al cluster in Ge atoms. With these understandings, a two-step RTA process achieves high-quality 2 nm nanocrystal Ge films with Raman peak at 298 cm{sup −1} of FWHM 10.3 cm{sup −1} and atomic smooth interfaces.« less

On the importance of local orbitals using second energy derivatives for d and f electrons

NASA Astrophysics Data System (ADS)

Karsai, Ferenc; Tran, Fabien; Blaha, Peter

2017-11-01

The all-electron linearized augmented plane wave (LAPW) methods are among the most accurate to solve the Kohn-Sham equations of density functional theory for periodic solids. In the LAPW methods, the unit cell is partitioned into spheres surrounding the atoms, inside which the wave functions are expanded into spherical harmonics, and the interstitial region, where the wave functions are expanded in Fourier series. Recently, Michalicek et al. (2013) reported an analysis of the so-called linearization error, which is inherent to the basis functions inside the spheres, and advocated the use of local orbital basis functions involving the second energy derivative of the radial part (HDLO). In the present work, we report the implementation of such basis functions into the WIEN2k code, and discuss in detail the improvement in terms of accuracy. From our tests, which involve atoms from the whole periodic table, it is concluded that for ground-state properties (e.g., equilibrium volume) the use of HDLO is necessary only for atoms with d or f electrons in the valence and large atomic spheres. For unoccupied states which are not too high above the Fermi energy, HDLO systematically improve the band structure, which may be of importance for the calculation of optical properties.

Enhancement of the Stability of Fluorine Atoms on Defective Graphene and at Graphene/Fluorographene Interface.

PubMed

Ao, Zhimin; Jiang, Quanguo; Li, Shuang; Liu, Hao; Peeters, Francois M; Li, Sean; Wang, Guoxiu

2015-09-09

Fluorinated graphene is one of the most important derivatives of graphene and has been found to have great potential in optoelectronic and photonic nanodevices. However, the stability of F atoms on fluorinated graphene under different conditions, which is essential to maintain the desired properties of fluorinated graphene, is still unclear. In this work, we investigate the diffusion of F atoms on pristine graphene, graphene with defects, and at graphene/fluorographene interfaces by using density functional theory calculations. We find that an isolated F atom diffuses easily on graphene, but those F atoms can be localized by inducing vacancies or absorbates in graphene and by creating graphene/fluorographene interfaces, which would strengthen the binding energy of F atoms on graphene and increase the diffusion energy barrier of F atoms remarkably.

Surface atoms in Sc-O/W(1 0 0) system as Schottky emitter at high temperature

NASA Astrophysics Data System (ADS)

Tsujita, T.; Iida, S.; Nagatomi, T.; Takai, Y.

2003-12-01

The chemical bonding state of surface atoms in the Sc-O/W(1 0 0) system as a Schottky emitter was investigated at high temperature using a profile of Auger electron peaks to elucidate the mechanism of the marked reduction of the work function of the Sc-O/W(1 0 0) Schottky emitter. For this, Sc-deposited W(1 0 0), oxygen-exposed W(1 0 0) and Sc surfaces were prepared as reference surfaces. A comparison of the profiles of the Auger electron peaks from the Sc-O/W(1 0 0) surface with those from the reference surfaces has revealed that oxygen and Sc atoms on the Sc-O/W(1 0 0) surface form the Sc-O complexes at the operating temperature of the Sc-O/W(1 0 0) emitter of 1400 K. In addition, the ratio of the number of Sc atoms to that of oxygen atoms is estimated as 1:1 by the quantitative analysis of the AES peaks. The present results strongly suggest that the work function of the Sc-O/W(1 0 0) emitter is caused by the formation of Sc-O electric dipoles aligning into the p(2 × 1)-p(1 × 2) double-domain structure [Surf. Sci. 523 (2003) L37] on the Sc-O/W(1 0 0) surface at the operating temperature.

A computational study on the electronic and field emission properties of Mg and Si doped AlN nanocones

NASA Astrophysics Data System (ADS)

Saedi, Leila; Soleymanabadi, Hamed; Panahyab, Ataollah

2018-05-01

Following an experimental work, we explored the effect of replacing an Al atom of an AlN nanocone by Si or Mg atom on its electronic and field emission properties using density functional theory calculations. We found that both Si-doping and Mg-doping increase the electrical conductivity of AlN nanocone, but their influences on the filed emission properties are significantly different. The Si-doping increases the electron concentration of AlN nanocone and results in a large electron mobility and a low work function, whereas Mg-doping leads to a high hole concentration below the conduction level and increases the work function in agreement with the experimental results. It is predicted that Si-doped AlN nanocones show excellent filed emission performance with higher emitted electron current density compared to the pristine AlN nanocone. But the Mg-doping meaningfully decreases the emitted electron current density from the surface of AlN nanocone. The Mg-doping can increase the work function about 41.9% and the Si-doping can decrease it about 6.3%. The Mg-doping and Si-doping convert the AlN nanocone to a p-type and n-type semiconductors, respectively. Our results explain in a molecular level what observed in the experiment.

VizieR Online Data Catalog: Partition functions for molecules and atoms (Barklem+, 2016)

NASA Astrophysics Data System (ADS)

Barklem, P. S.; Collet, R.

2016-02-01

The results and input data are presented in the following files. Table 1 contains dissociation energies from the literature, and final adopted values, for 291 molecules. The literature values are from the compilations of Huber & Herzberg (1979, Constants of Diatomic Molecules (Van Nostrand Reinhold), Luo (2007, Comprehensive Handbook of Chemical Bond Energies (CRC Press)) and G2 theory calculations of Curtiss et al. (1991, J. Chem. Phys., 94, 7221). Table 2 contains the input data for the molecular calculations including adopted dissociation energy, nuclear spins, molecular spectroscopic constants and their sources. There are 291 files, one for each molecule, labelled by the molecule name. The various molecular spectroscopic constants are as defined in the paper. Table 4 contains the first, second and third ionisation energies for all chemical elements from H to U. The data comes from the CRC Handbook of Chemistry and Physics (Haynes, W.M. 2010, CRC Handbook of Chemistry and Physics, 91st edn. (CRC Press, Taylor and Francis Group)). Table 5a contains a list of keys to bibliographic references for the atomic energy level data that was extracted from NIST Atomic Spectra Database and used in the present work to compute atomic partition functions. The citation keys are abbreviations of the full bibliographic references which are made available in Table 5b in BibTeX format. Table 5b contains the full bibliographic references for the atomic energy level data that was extracted from the NIST Atomic Spectra Database. Table 6 contains tabulated partition function data as a function of temperature for 291 molecules. Table 7 contains tabulated equilibrium constant data as a function of temperature for 291 molecules. Table 8 contains tabulated partition function data as a function of temperature for 284 atoms and ions. The paper should be consulted for further details. (10 data files).

Electron work function-a promising guiding parameter for material design.

PubMed

Lu, Hao; Liu, Ziran; Yan, Xianguo; Li, Dongyang; Parent, Leo; Tian, Harry

2016-04-14

Using nickel added X70 steel as a sample material, we demonstrate that electron work function (EWF), which largely reflects the electron behavior of materials, could be used as a guide parameter for material modification or design. Adding Ni having a higher electron work function to X70 steel brings more "free" electrons to the steel, leading to increased overall work function, accompanied with enhanced e(-)-nuclei interactions or higher atomic bond strength. Young's modulus and hardness increase correspondingly. However, the free electron density and work function decrease as the Ni content is continuously increased, accompanied with the formation of a second phase, FeNi3, which is softer with a lower work function. The decrease in the overall work function corresponds to deterioration of the mechanical strength of the steel. It is expected that EWF, a simple but fundamental parameter, may lead to new methodologies or supplementary approaches for metallic materials design or tailoring on a feasible electronic base.

Diffraction and quantum control of wave functions in nonresonant two-photon absorption

NASA Astrophysics Data System (ADS)

Li, Baihong; Pang, Huafeng; Wang, Doudou; Zhang, Tao; Dong, Ruifang; Li, Yongfang

2018-03-01

In this study, the nonresonant two-photon absorption process in a two-level atom, induced by a weak chirped pulse, is theoretically investigated in the frequency domain. An analytical expression of the wave function expressed by Fresnel functions is obtained, and the two-photon transition probability (TPTP) versus the integral bandwidth, spectral width, and chirp parameter is analyzed. The results indicate that the oscillation evolution of the TPTP result from quantum diffraction of the wave function, which can be explained by analogy with Fresnel diffraction from a wide slit in the spatial domain. Moreover, the ratio between the real and imaginary parts of the excited state wave function and, hence, the atomic polarization, can be controlled by the initial phase of the excitation pulse. In some special initial phase of the excitation pulse, the wave functions with purely real or imaginary parts can be obtained by measuring the population probability. This work provides a novel perspective for understanding the physical details of the interactions between atoms and chirped light pulses in the multiphoton process.

Electronic structure of stoichiometric and reduced ZnO from periodic relativistic all electron hybrid density functional calculations using numeric atom-centered orbitals.

PubMed

Viñes, Francesc; Illas, Francesc

2017-03-30

The atomic and electronic structure of stoichiometric and reduced ZnO wurtzite has been studied using a periodic relativistic all electron hybrid density functional (PBE0) approach and numeric atom-centered orbital basis set with quality equivalent to aug-cc-pVDZ. To assess the importance of relativistic effects, calculations were carried out without and with explicit inclusion of relativistic effects through the zero order regular approximation. The calculated band gap is ∼0.2 eV smaller than experiment, close to previous PBE0 results including relativistic calculation through the pseudopotential and ∼0.25 eV smaller than equivalent nonrelativistic all electron PBE0 calculations indicating possible sources of error in nonrelativistic all electron density functional calculations for systems containing elements with relatively high atomic number. The oxygen vacancy formation energy converges rather fast with the supercell size, the predicted value agrees with previously hybrid density functional calculations and analysis of the electronic structure evidences the presence of localized electrons at the vacancy site with a concomitant well localized peak in the density of states ∼0.5 eV above the top of the valence band and a significant relaxation of the Zn atoms near to the oxygen vacancy. Finally, present work shows that accurate results can be obtained in systems involving large supercells containing up to ∼450 atoms using a numeric atomic-centered orbital basis set within a full all electron description including scalar relativistic effects at an affordable cost. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Substrate Dependent Ad-Atom Migration on Graphene and the Impact on Electron-Beam Sculpting Functional Nanopores.

PubMed

Freedman, Kevin J; Goyal, Gaurav; Ahn, Chi Won; Kim, Min Jun

2017-05-10

The use of atomically thin graphene for molecular sensing has attracted tremendous attention over the years and, in some instances, could displace the use of classical thin films. For nanopore sensing, graphene must be suspended over an aperture so that a single pore can be formed in the free-standing region. Nanopores are typically drilled using an electron beam (e-beam) which is tightly focused until a desired pore size is obtained. E-beam sculpting of graphene however is not just dependent on the ability to displace atoms but also the ability to hinder the migration of ad-atoms on the surface of graphene. Using relatively lower e-beam fluxes from a thermionic electron source, the C-atom knockout rate seems to be comparable to the rate of carbon ad-atom attraction and accumulation at the e-beam/graphene interface (i.e., R knockout ≈ R accumulation ). Working at this unique regime has allowed the study of carbon ad-atom migration as well as the influence of various substrate materials on e-beam sculpting of graphene. We also show that this information was pivotal to fabricating functional graphene nanopores for studying DNA with increased spatial resolution which is attributed to atomically thin membranes.

Simulating the Effect of Contact Atomic Structure on the Spin-Dependent Transport Properties of Gold Nanowires

NASA Astrophysics Data System (ADS)

Ansarino, Masoud; Ravan, Bahram Abedi

Some experimental research works report on the superb magnetoresistance properties of magnetically contacted gold nanowires. With the intention of trying to understand the spin-dependent transport mechanism of these structures, in this work we have used first-principles density functional theory methods to investigate effects of interface structure on the spintronic characteristics of Au nanowires. Monatomic chains of gold are sandwiched between two ferromagnetic electrodes of Fe and by substituting the interfacial Fe atoms with some other transition metal elements (including Cr, Mn, Co and Ni) the occurrence of possible enhancement in the electronic conductance and magnetoresistance characteristics of the device are investigated. It is observed that replacing the interfacial atoms with Ni raises the junction’s magnetoresistance ratio to as high as 2000%.

Electron work function–a promising guiding parameter for material design

PubMed Central

Lu, Hao; Liu, Ziran; Yan, Xianguo; Li, Dongyang; Parent, Leo; Tian, Harry

2016-01-01

Using nickel added X70 steel as a sample material, we demonstrate that electron work function (EWF), which largely reflects the electron behavior of materials, could be used as a guide parameter for material modification or design. Adding Ni having a higher electron work function to X70 steel brings more “free” electrons to the steel, leading to increased overall work function, accompanied with enhanced e−–nuclei interactions or higher atomic bond strength. Young’s modulus and hardness increase correspondingly. However, the free electron density and work function decrease as the Ni content is continuously increased, accompanied with the formation of a second phase, FeNi3, which is softer with a lower work function. The decrease in the overall work function corresponds to deterioration of the mechanical strength of the steel. It is expected that EWF, a simple but fundamental parameter, may lead to new methodologies or supplementary approaches for metallic materials design or tailoring on a feasible electronic base. PMID:27074974

Scalable quantum information processing with atomic ensembles and flying photons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mei Feng; Yu Yafei; Feng Mang

2009-10-15

We present a scheme for scalable quantum information processing with atomic ensembles and flying photons. Using the Rydberg blockade, we encode the qubits in the collective atomic states, which could be manipulated fast and easily due to the enhanced interaction in comparison to the single-atom case. We demonstrate that our proposed gating could be applied to generation of two-dimensional cluster states for measurement-based quantum computation. Moreover, the atomic ensembles also function as quantum repeaters useful for long-distance quantum state transfer. We show the possibility of our scheme to work in bad cavity or in weak coupling regime, which could muchmore » relax the experimental requirement. The efficient coherent operations on the ensemble qubits enable our scheme to be switchable between quantum computation and quantum communication using atomic ensembles.« less

First-principles study of Au-decorated carbon nanotubes

NASA Astrophysics Data System (ADS)

Ju, Weiwei; Li, Tongwei; Zhou, Qingxiao; Li, Haisheng; Li, Xiaohong

2018-07-01

The electronic structures and spin-orbit (SO) coupling of carbon nanotubes with adsorbed Au atoms are investigated based on density functional theory. Three kinds of zigzag single-walled CNT (8,0), (10,0) and (12,0) are selected. The Au atoms prefer to adsorb on the top of C atoms. The adsorption of Au atoms can introduce impurity states in the band gap, modifying the electronic properties of systems. Furthermore, the influence of SO coupling on these impurity states is also explored. Considerable SO splitting (∼130 meV) can be obtained. We find that the SO splitting decreases with the increase of the concentration of Au atoms, which can be ascribed to the interaction between Au atoms, suppressing the SO splitting. Our work provides imperative understanding on the electronic properties and SO coupling effect in Au-decorated CNTs.

Hamiltonian adaptive resolution molecular dynamics simulation of infrared dielectric functions of liquids

NASA Astrophysics Data System (ADS)

Wang, C. C.; Tan, J. Y.; Liu, L. H.

2018-05-01

Hamiltonian adaptive resolution scheme (H-AdResS), which allows to simulate materials by treating different domains of the system at different levels of resolution, is a recently proposed atomistic/coarse-grained multiscale model. In this work, a scheme to calculate the dielectric functions of liquids on account of H-AdResS is presented. In the proposed H-AdResS dielectric-function calculation scheme (DielectFunctCalS), the corrected molecular dipole moments are calculated by multiplying molecular dipole moment by the weighting fraction of the molecular mapping point. As the widths of all-atom and hybrid regions show different degrees of influence on the dielectric functions, a prefactor is multiplied to eliminate the effects of all-atom and hybrid region widths. Since one goal of using the H-AdResS method is to reduce computational costs, widths of the all-atom region and the hybrid region can be reduced considering that the coarse-grained simulation is much more timesaving compared to atomistic simulation. Liquid water and ethanol are taken as test cases to validate the DielectFunctCalS. The H-AdResS DielectFunctCalS results are in good agreement with all-atom molecular dynamics simulations. The accuracy of the H-AdResS results, together with all-atom molecular dynamics results, depends heavily on the choice of the force field and force field parameters. The H-AdResS DielectFunctCalS allows us to calculate the dielectric functions of macromolecule systems with high efficiency and makes the dielectric function calculations of large biomolecular systems possible.

Potential Energy Curves and Collisions Integrals of Air Components. 2; Interactions Involving Ionized Atoms

NASA Technical Reports Server (NTRS)

Stallcop, James R.; Partridge, Harry; Levin, Eugene; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

Collision integrals are fundamental quantities required to determine the transport properties of the environment surrounding aerospace vehicles in the upper atmosphere. These collision integrals can be determined as a function of temperature from the potential energy curves describing the atomic and molecular collisions. Ab initio calculations provide a practical method of computing the required interaction potentials. In this work we will discuss recent advances in scattering calculations with an emphasis on the accuracy that is obtainable. Results for interactions of the atoms and ionized atoms of nitrogen and oxygen will be reviewed and their application to the determination of transport properties, such as diffusion and viscosity coefficients, will be examined.

Adiabatic corrections to density functional theory energies and wave functions.

PubMed

Mohallem, José R; Coura, Thiago de O; Diniz, Leonardo G; de Castro, Gustavo; Assafrão, Denise; Heine, Thomas

2008-09-25

The adiabatic finite-nuclear-mass-correction (FNMC) to the electronic energies and wave functions of atoms and molecules is formulated for density-functional theory and implemented in the deMon code. The approach is tested for a series of local and gradient corrected density functionals, using MP2 results and diagonal-Born-Oppenheimer corrections from the literature for comparison. In the evaluation of absolute energy corrections of nonorganic molecules the LDA PZ81 functional works surprisingly better than the others. For organic molecules the GGA BLYP functional has the best performance. FNMC with GGA functionals, mainly BLYP, show a good performance in the evaluation of relative corrections, except for nonorganic molecules containing H atoms. The PW86 functional stands out with the best evaluation of the barrier of linearity of H2O and the isotopic dipole moment of HDO. In general, DFT functionals display an accuracy superior than the common belief and because the corrections are based on a change of the electronic kinetic energy they are here ranked in a new appropriate way. The approach is applied to obtain the adiabatic correction for full atomization of alcanes C(n)H(2n+2), n = 4-10. The barrier of 1 mHartree is approached for adiabatic corrections, justifying its insertion into DFT.

Theoretical insight into an empirical rule about organic corrosion inhibitors containing nitrogen, oxygen, and sulfur atoms

NASA Astrophysics Data System (ADS)

Guo, Lei; Obot, Ime Bassey; Zheng, Xingwen; Shen, Xun; Qiang, Yujie; Kaya, Savaş; Kaya, Cemal

2017-06-01

Steel is an important material in industry. Adding heterocyclic organic compounds have proved to be very efficient for steel protection. There exists an empirical rule that the general trend in the inhibition efficiencies of molecules containing heteroatoms is such that O < N < S. However, an atomic-level insight into the inhibition mechanism is still lacked. Thus, in this work, density functional theory calculations was used to investigate the adsorption of three typical heterocyclic molecules, i.e., pyrrole, furan, and thiophene, on Fe(110) surface. The approach is illustrated by carrying out geometric optimization of inhibitors on the stable and most exposed plane of α-Fe. Some salient features such as charge density difference, changes of work function, density of states were detailedly described. The present study is helpful to understand the afore-mentioned experiment rule.

New contributions to physics by Prof. C. N. Yang: 2009-2011

NASA Astrophysics Data System (ADS)

Ma, Zhong-Qi

2016-01-01

In a seminal paper of 1967, Professor Chen Ning Yang found the full solution of the one-dimensional Fermi gas with a repulsive delta function interaction by using the Bethe ansatz and group theory. This work with a brilliant discovery of the Yang-Baxter equation has been inspiring new developments in mathematical physics, statistical physics, and many-body physics. Based on experimental developments in simulating many-body physics of one-dimensional systems of ultracold atoms, during a period from 2009 to 2011, Prof. Yang published seven papers on the exact properties of the ground state of bosonic and fermionic atoms with the repulsive delta function interaction and a confined potential to one dimension. Here I would like to share my experience in doing research work fortunately under the direct supervision of Prof. Yang in that period.

New Contributions to Physics by Prof. C. N. Yang: 2009-2011

NASA Astrophysics Data System (ADS)

Ma, Zhong-Qi

In a seminal paper of 1967, Professor Chen Ning Yang found the full solution of the one-dimensional Fermi gas with a repulsive delta function interaction by using the Bethe ansatz and group theory. This work with a brilliant discovery of the Yang-Baxter equation has been inspiring new developments in mathematical physics, statistical physics, and many-body physics. Based on experimental developments in simulating many-body physics of one-dimensional systems of ultracold atoms, during a period from 2009 to 2011, Prof. Yang published seven papers on the exact properties of the ground state of bosonic and fermionic atoms with the repulsive delta function interaction and a confined potential to one dimension. Here I would like to share my experience in doing research work fortunately under the direct supervision of Prof. Yang in that period.

Support effects on adsorption and catalytic activation of O2 in single atom iron catalysts with graphene-based substrates.

PubMed

Gao, Zheng-Yang; Yang, Wei-Jie; Ding, Xun-Lei; Lv, Gang; Yan, Wei-Ping

2018-03-07

The adsorption and catalytic activation of O 2 on single atom iron catalysts with graphene-based substrates were investigated systematically by density functional theory calculation. It is found that the support effects of graphene-based substrates have a significant influence on the stability of the single atom catalysts, the adsorption configuration, the electron transfer mechanism, the adsorption energy and the energy barrier. The differences in the stable adsorption configuration of O 2 on single atom iron catalysts with different graphene-based substrates can be well understood by the symmetrical matching principle based on frontier molecular orbital analysis. There are two different mechanisms of electron transfer, in which the Fe atom acts as the electron donor in single vacancy graphene-based substrates while the Fe atom mainly acts as the bridge for electron transfer in double vacancy graphene-based substrates. The Fermi softness and work function are good descriptors of the adsorption energy and they can well reveal the relationship between electronic structure and adsorption energy. This single atom iron catalyst with single vacancy graphene modified by three nitrogen atoms is a promising non-noble metal single atom catalyst in the adsorption and catalytic oxidation of O 2 . Furthermore, the findings can lay the foundation for the further study of graphene-based support effects and provide a guideline for the development and design of new non-noble-metal single atom catalysts.

XZP + 1d and XZP + 1d-DKH basis sets for second-row elements: application to CCSD(T) zero-point vibrational energy and atomization energy calculations.

PubMed

Campos, Cesar T; Jorge, Francisco E; Alves, Júlia M A

2012-09-01

Recently, segmented all-electron contracted double, triple, quadruple, quintuple, and sextuple zeta valence plus polarization function (XZP, X = D, T, Q, 5, and 6) basis sets for the elements from H to Ar were constructed for use in conjunction with nonrelativistic and Douglas-Kroll-Hess Hamiltonians. In this work, in order to obtain a better description of some molecular properties, the XZP sets for the second-row elements were augmented with high-exponent d "inner polarization functions," which were optimized in the molecular environment at the second-order Møller-Plesset level. At the coupled cluster level of theory, the inclusion of tight d functions for these elements was found to be essential to improve the agreement between theoretical and experimental zero-point vibrational energies (ZPVEs) and atomization energies. For all of the molecules studied, the ZPVE errors were always smaller than 0.5 %. The atomization energies were also improved by applying corrections due to core/valence correlation and atomic spin-orbit effects. This led to estimates for the atomization energies of various compounds in the gaseous phase. The largest error (1.2 kcal mol(-1)) was found for SiH(4).

On the question of fractal packing structure in metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Jun; Asta, Mark; Ritchie, Robert O.

2017-07-25

This work addresses the long-standing debate over fractal models of packing structure in metallic glasses (MGs). Through detailed fractal and percolation analyses of MG structures, derived from simulations spanning a range of compositions and quenching rates, we conclude that there is no fractal atomic-level structure associated with the packing of all atoms or solute-centered clusters. The results are in contradiction with conclusions derived from previous studies based on analyses of shifts in radial distribution function and structure factor peaks associated with volume changes induced by pressure and compositional variations. Here in this paper, the interpretation of such shifts is shownmore » to be challenged by the heterogeneous nature of MG structure and deformation at the atomic scale. Moreover, our analysis in the present work illustrates clearly the percolation theory applied to MGs, for example, the percolation threshold and characteristics of percolation clusters formed by subsets of atoms, which can have important consequences for structure–property relationships in these amorphous materials.« less

Work function variation of MoS{sub 2} atomic layers grown with chemical vapor deposition: The effects of thickness and the adsorption of water/oxygen molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jong Hun; Kim, Jae Hyeon; Park, Jeong Young, E-mail: peterlee@skku.edu, E-mail: jeongypark@kaist.ac.kr

2015-06-22

The electrical properties of two-dimensional atomic sheets exhibit remarkable dependences on layer thickness and surface chemistry. Here, we investigated the variation of the work function properties of MoS{sub 2} films prepared with chemical vapor deposition (CVD) on SiO{sub 2} substrates with the number of film layers. Wafer-scale CVD MoS{sub 2} films with 2, 4, and 12 layers were fabricated on SiO{sub 2}, and their properties were evaluated by using Raman and photoluminescence spectroscopies. In accordance with our X-ray photoelectron spectroscopy results, our Kelvin probe force microscopy investigation found that the surface potential of the MoS{sub 2} films increases by ∼0.15 eVmore » when the number of layers is increased from 2 to 12. Photoemission spectroscopy (PES) with in-situ annealing under ultra high vacuum conditions was used to directly demonstrate that this work function shift is associated with the screening effects of oxygen or water molecules adsorbed on the film surface. After annealing, it was found with PES that the surface potential decreases by ∼0.2 eV upon the removal of the adsorbed layers, which confirms that adsorbed species have a role in the variation in the work function.« less

From the Orbital Implementation of the Kinetic Theory to the Polarization Propagator Method in the Study of Energy Deposition Problems

NASA Astrophysics Data System (ADS)

Cabrera-Trujillo, R.; Cruz, S. A.; Soullard, J.

The energy deposited by swift atomic-ion projectiles when colliding with a given target material has been a topic of special scientific interest for the last century due to the variety of applications of ion beams in modern materials technology as well as in medical physics. In this work, we summarize our contributions in this field as a consequence of fruitful discussions and enlightening ideas put forward by one of the main protagonists in stopping power theory during the last three decades: Jens Oddershede. Our review, mainly motivated by Jens' work, evolves from the extension of the orbital implementation of the kinetic theory of stopping through the orbital local plasma approximation, its use in studies of orbital and total mean excitation energies for the study of atomic and molecular stopping until the advances on generalized oscillator strength and sum rules in the study of stopping cross sections. Finally, as a tribute to Jens' work on the orbital implementation of the kinetic theory of stopping, in this work we present new results on the use of the Thomas-Fermi-Dirac-Weizsäcker density functional for the calculation of orbital and total atomic mean excitation energies. The results are applied to free-atoms and and extension is done to confined atoms - taking Si as an example - whereby target pressure effects on stopping are derived. Hence, evidence of the far-yield of Jens' ideas is given.

Scanning Tunneling Microscopy Studies of Diamond Films and Optoelectronic Materials

NASA Technical Reports Server (NTRS)

Perez, Jose M.

1996-01-01

We present a summary of the research, citations of publications resulting from the research and abstracts of such publications. We have made no inventions in the performance of the work in this project. The main goals of the project were to set up a Chemical Vapor Deposition (CVD) diamond growth system attached to an UltraHigh Vacuum (UHV) atomic resolution Scanning Tunneling Microscopy (STM) system and carry out experiments aimed at studying the properties and growth of diamond films using atomic resolution UHV STM. We successfully achieved these goals. We observed, for the first time, the atomic structure of the surface of CVD grown epitaxial diamond (100) films using UHV STM. We studied the effects of atomic hydrogen on the CVD diamond growth process. We studied the electronic properties of the diamond (100) (2x1) surface, and the effect of alkali metal adsorbates such as Cs on the work function of this surface using UHV STM spectroscopy techniques. We also studied, using STM, new electronic materials such as carbon nanotubes and gold nanostructures. This work resulted in four publications in refereed scientific journals and five publications in refereed conference proceedings.

Towards an Optimal Gradient-dependent Energy Functional of the PZ-SIC Form

DOE PAGES

Jónsson, Elvar Örn; Lehtola, Susi; Jónsson, Hannes

2015-06-01

Results of Perdew–Zunger self-interaction corrected (PZ-SIC) density functional theory calculations of the atomization energy of 35 molecules are compared to those of high-level quantum chemistry calculations. While the PBE functional, which is commonly used in calculations of condensed matter, is known to predict on average too high atomization energy (overbinding of the molecules), the application of PZ-SIC gives a large overcorrection and leads to significant underestimation of the atomization energy. The exchange enhancement factor that is optimal for the generalized gradient approximation within the Kohn-Sham (KS) approach may not be optimal for the self-interaction corrected functional. The PBEsol functional, wheremore » the exchange enhancement factor was optimized for solids, gives poor results for molecules in KS but turns out to work better than PBE in PZ-SIC calculations. The exchange enhancement is weaker in PBEsol and the functional is closer to the local density approximation. Furthermore, the drop in the exchange enhancement factor for increasing reduced gradient in the PW91 functional gives more accurate results than the plateaued enhancement in the PBE functional. A step towards an optimal exchange enhancement factor for a gradient dependent functional of the PZ-SIC form is taken by constructing an exchange enhancement factor that mimics PBEsol for small values of the reduced gradient, and PW91 for large values. The average atomization energy is then in closer agreement with the high-level quantum chemistry calculations, but the variance is still large, the F 2 molecule being a notable outlier.« less

Effects of doping Na and Cl atom on electronic structure of silicene: Density functional theory calculation

NASA Astrophysics Data System (ADS)

Pamungkas, Mauludi Ariesto; Sobirin, Kafi; Abdurrouf

2018-04-01

Silicene is a material in which silicon atoms are packed in two-dimensional hexagonal lattice, similar to that of graphene. Compared to graphene, silicene has promising potential to be applied in microelectronic technology because of its compatibility with silicon comonly used in semiconducting devices. Natrium and chlorine are easy to extract and can be used as dopants in FET (Field Effect Transistor). In this work, the effects of adsorption energy and electronic structure of silicene to both natrium and chlorine atoms are calculated with Density Functional Theory (DFT). The results show that dopings of Na transform silicene which is initially semimetal into a metal. Then dopings of Cl Top-site transform silicene into a semiconducting material and doping of Na and Cl simultaneously transfoms silicene into a conducting material.

Study on the structural transition of CoNi nanoclusters using molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Xia, J. H.; Gao, Xue-Mei

2018-04-01

In this work, the segregation and structural transitions of CoNi clusters, between 1500 and 300 K, have been investigated using molecular dynamics simulations with the embedded atom method potential. The radial distribution function was used to analyze the segregation during the cooling processes. It is found that Co atoms segregate to the inside and Ni atoms preferably to the surface during the cooling processes, the Co147Ni414 cluster becomes a core-shell structure. We discuss the structural transition according to the pair-correction function and pair-analysis technique, and finally the liquid Co147Ni414 crystallizes into the coexistence of hcp and fcc structure at 300 K. At the same time, it is found that the frozen structure of CoNi cluster is strongly related to the Co concentration.

An X-Ray Analysis Database of Photoionization Cross Sections Including Variable Ionization

NASA Technical Reports Server (NTRS)

Wang, Ping; Cohen, David H.; MacFarlane, Joseph J.; Cassinelli, Joseph P.

1997-01-01

Results of research efforts in the following areas are discussed: review of the major theoretical and experimental data of subshell photoionization cross sections and ionization edges of atomic ions to assess the accuracy of the data, and to compile the most reliable of these data in our own database; detailed atomic physics calculations to complement the database for all ions of 17 cosmically abundant elements; reconciling the data from various sources and our own calculations; and fitting cross sections with functional approximations and incorporating these functions into a compact computer code.Also, efforts included adapting an ionization equilibrium code, tabulating results, and incorporating them into the overall program and testing the code (both ionization equilibrium and opacity codes) with existing observational data. The background and scientific applications of this work are discussed. Atomic physics cross section models and calculations are described. Calculation results are compared with available experimental data and other theoretical data. The functional approximations used for fitting cross sections are outlined and applications of the database are discussed.

Positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Olenga, Antoine; Weiss, A. H.

2013-03-01

The process by which oxide layers are formed on metal surfaces is still not well understood. In this work we present the results of theoretical studies of positron states and annihilation characteristics of surface-trapped positrons at the oxidized Cu(110) surface. An ab-initio investigation of stability and associated electronic properties of different adsorption phases of oxygen on Cu(110) has been performed on the basis of density functional theory and using DMOl3 code. The changes in the positron work function and the surface dipole moment when oxygen atoms occupy on-surface and sub-surface sites have been attributed to charge redistribution within the first two layers, buckling effects within each layer and interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, elemental content, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidized transition metal surfaces using positron annihilation induced Auger electron spectroscopy. This work was supported in part by the National Science Foundation Grant DMR-0907679.

Atomic-Scale Structure of the Hematite α-Fe2O3(11̅02) “R-Cut” Surface

PubMed Central

2017-01-01

The α-Fe2O3(11̅02) surface (also known as the hematite r-cut or (012) surface) was studied using low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), scanning tunneling microscopy (STM), noncontact atomic force microscopy (nc-AFM), and ab initio density functional theory (DFT)+U calculations. Two surface structures are stable under ultrahigh vacuum (UHV) conditions; a stoichiometric (1 × 1) surface can be prepared by annealing at 450 °C in ≈10–6 mbar O2, and a reduced (2 × 1) reconstruction is formed by UHV annealing at 540 °C. The (1 × 1) surface is close to an ideal bulk termination, and the undercoordinated surface Fe atoms reduce the surface bandgap by ≈0.2 eV with respect to the bulk. The work function is measured to be 5.7 ± 0.2 eV, and the VBM is located 1.5 ± 0.1 eV below EF. The images obtained from the (2 × 1) reconstruction cannot be reconciled with previously proposed models, and a new “alternating trench” structure is proposed based on an ordered removal of lattice oxygen atoms. DFT+U calculations show that this surface is favored in reducing conditions and that 4-fold-coordinated Fe2+ cations at the surface introduce gap states approximately 1 eV below EF. The work function on the (2 × 1) termination is 5.4 ± 0.2 eV. PMID:29492182

Electronic and magnetic properties of small rhodium clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

2015-04-24

We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework.more » The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.« less

Electronic states of Ca/PC61BM: Mechanism of low work function metal as interfacial material

NASA Astrophysics Data System (ADS)

Du, Ying-Ying; Chen, Guang-Hua; Li, Wen-Jie; Bai, Xin-Yuan; Lin, De-Qu; Ju, Huanxin; Hu, Shanwei; Xu, Qian; Wang, Yan; Li, Xiong; Zhu, Junfa; Li, Hong-Nian

2018-03-01

We have studied the electronic states at Ca/PC61BM interface using photoemission spectroscopy. It is found that the state of unoccupied molecular orbitals of the top molecular layer (TML) becomes occupied by the electrons transferred from the Ca atoms. The work function of the heavily doped TML of PC61BM film is smaller than that of metal Ca, and thus the contact between the TML and metal Ca is Ohmic. A transition layer (TL) of several molecular layers forms beneath the TML due to the diffusion of the Ca atoms. The TL is conductive and aligns its Fermi level with the negative integer charge transfer level of the interior PC61BM. The built-in electric field in the TL facilitates the electron transport from the interior of the PC61BM film to the TML.

Ab initio simulations of subatomic resolution images in noncontact atomic force microscopy

NASA Astrophysics Data System (ADS)

Kim, Minjung; Chelikowsky, James R.

2015-03-01

Direct imaging of polycyclic aromatic molecules with a subatomic resolution has recently been achieved with noncontact atomic force microscopy (nc-AFM). Specifically, nc-AFM employing a CO functionalized tip has provided details of the chemical bond in aromatic molecules, including the discrimination of bond order. However, the underlying physics of such high resolution imaging remains problematic. By employing new, efficient algorithms based on real space pseudopotentials, we calculate the forces between the nc-AFM tip and specimen. We simulate images of planar organic molecules with two different approaches: 1) with a chemically inert tip and 2) with a CO functionalized tip. We find dramatic differences in the resulting images, which are consistent with recent experimental work. Our work is supported by the DOE under DOE/DE-FG02-06ER46286 and by the Welch Foundation under Grant F-1837. Computational resources were provided by NERSC and XSEDE.

Immobilization of single argon atoms in nano-cages of two-dimensional zeolite model systems.

PubMed

Zhong, Jian-Qiang; Wang, Mengen; Akter, Nusnin; Kestell, John D; Boscoboinik, Alejandro M; Kim, Taejin; Stacchiola, Dario J; Lu, Deyu; Boscoboinik, J Anibal

2017-07-17

The confinement of noble gases on nanostructured surfaces, in contrast to bulk materials, at non-cryogenic temperatures represents a formidable challenge. In this work, individual Ar atoms are trapped at 300 K in nano-cages consisting of (alumino)silicate hexagonal prisms forming a two-dimensional array on a planar surface. The trapping of Ar atoms is detected in situ using synchrotron-based ambient pressure X-ray photoelectron spectroscopy. The atoms remain in the cages upon heating to 400 K. The trapping and release of Ar is studied combining surface science methods and density functional theory calculations. While the frameworks stay intact with the inclusion of Ar atoms, the permeability of gasses (for example, CO) through them is significantly affected, making these structures also interesting candidates for tunable atomic and molecular sieves. These findings enable the study of individually confined noble gas atoms using surface science methods, opening up new opportunities for fundamental research.

The physical properties of Li-doped g-C{sub 3}N{sub 4} monolayer sheet investigated by the first-principles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruan, Linwei; Xu, Gengsheng; Gu, Lina

2015-06-15

Highlights: • Systematically research on Li-doped g-C{sub 3}N{sub 4} monolayer sheets by first-principles calculation. • Optimal dopant concentration for optical absorption is 7.12%. • Thermodynamics stability of the doped substrate g-C{sub 3}N{sub 4} decreased with Li dopant concentration increasing. • The values of work function Φ decreased monotonously with the increasing of Li dopant concentration. - Abstract: The geometric, electronic, optical properties, thermodynamic stability, and work function of Li-doped g-C{sub 3}N{sub 4} monolayer were investigated by the first-principles calculation. It was found that the Li atoms were preferentially substituted the open-hollow sites of g-C{sub 3}N{sub 4}. Interestingly, the “odd” numbermore » of Li doped g-C{sub 3}N{sub 4} showed metallic properties, while the “even” number of Li atoms widened the band gap of g-C{sub 3}N{sub 4}. The HOMO and LUMO distributions reveal that the active sites located at edge N and C atoms for both pristine and the Li-doped g-C{sub 3}N{sub 4}. In addition, thermodynamic analysis showed that the doped Li atoms reduced the thermodynamic stability of g-C{sub 3}N{sub 4} monolayer sheets.« less

Quantitative secondary electron imaging for work function extraction at atomic level and layer identification of graphene

PubMed Central

Zhou, Yangbo; Fox, Daniel S; Maguire, Pierce; O’Connell, Robert; Masters, Robert; Rodenburg, Cornelia; Wu, Hanchun; Dapor, Maurizio; Chen, Ying; Zhang, Hongzhou

2016-01-01

Two-dimensional (2D) materials usually have a layer-dependent work function, which require fast and accurate detection for the evaluation of their device performance. A detection technique with high throughput and high spatial resolution has not yet been explored. Using a scanning electron microscope, we have developed and implemented a quantitative analytical technique which allows effective extraction of the work function of graphene. This technique uses the secondary electron contrast and has nanometre-resolved layer information. The measurement of few-layer graphene flakes shows the variation of work function between graphene layers with a precision of less than 10 meV. It is expected that this technique will prove extremely useful for researchers in a broad range of fields due to its revolutionary throughput and accuracy. PMID:26878907

Superradiant Quantum Heat Engine.

PubMed

Hardal, Ali Ü C; Müstecaplıoğlu, Özgür E

2015-08-11

Quantum physics revolutionized classical disciplines of mechanics, statistical physics, and electrodynamics. One branch of scientific knowledge however seems untouched: thermodynamics. Major motivation behind thermodynamics is to develop efficient heat engines. Technology has a trend to miniaturize engines, reaching to quantum regimes. Development of quantum heat engines (QHEs) requires emerging field of quantum thermodynamics. Studies of QHEs debate whether quantum coherence can be used as a resource. We explore an alternative where it can function as an effective catalyst. We propose a QHE which consists of a photon gas inside an optical cavity as the working fluid and quantum coherent atomic clusters as the fuel. Utilizing the superradiance, where a cluster can radiate quadratically faster than a single atom, we show that the work output becomes proportional to the square of the number of the atoms. In addition to practical value of cranking up QHE, our result is a fundamental difference of a quantum fuel from its classical counterpart.

In situ electrochemical high-energy X-ray diffraction using a capillary working electrode cell geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Bedford, Nicholas M.; Jiang, Naisheng

The ability to generate new electrochemically active materials for energy generation and storage with improved properties will likely be derived from an understanding of atomic-scale structure/function relationships during electrochemical events. Here, the design and implementation of a new capillary electrochemical cell designed specifically forin situhigh-energy X-ray diffraction measurements is described. By increasing the amount of electrochemically active material in the X-ray path while implementing low-Zcell materials with anisotropic scattering profiles, an order of magnitude enhancement in diffracted X-ray signal over traditional cell geometries for multiple electrochemically active materials is demonstrated. This signal improvement is crucial for high-energy X-ray diffraction measurementsmore » and subsequent Fourier transformation into atomic pair distribution functions for atomic-scale structural analysis. As an example, clear structural changes in LiCoO 2under reductive and oxidative conditions using the capillary cell are demonstrated, which agree with prior studies. Accurate modeling of the LiCoO 2diffraction data using reverse Monte Carlo simulations further verifies accurate background subtraction and strong signal from the electrochemically active material, enabled by the capillary working electrode geometry.« less

Watching the Real-time Evolution of a Laser Modified Atom Using Attosecond Pulses

NASA Astrophysics Data System (ADS)

Shivaram, Niranjan; Timmers, Henry; Tong, Xiao-Min; Sandhu, Arvinder

2011-10-01

In the presence of even moderately strong laser fields, atomic states are heavily modified and develop rich structure. Such a laser dressed atom can be described using the Floquet theory in which the laser dressed states called Floquet states are composed of different Fourier components. In this work we use XUV attosecond pulses to excite a He atom from its ground state to near-infrared (NIR) laser dressed Floquet states, which are ionized by the dressing laser field. Quantum interferences between Fourier components of these Floquet states lead to oscillations in He ion yield as a function of time-delay between the XUV and NIR pulses. From the ion yield signal we measure the quantum phase difference between transition matrix elements to two different Fourier components as a function of both time-delay (instantaneous NIR intensity) and NIR pulse peak intensity. These measurements along with information from time-dependent Schrodinger equation simulations enable us to observe the real-time evolution of the laser modified atom as the dominant Floquet state mediating the ionization changes from the 5p Floquet state to the 2p Floquet state with increasing NIR intensity.

Atomic and electronic basis for the serrations of refractory high-entropy alloys

NASA Astrophysics Data System (ADS)

Wang, William Yi; Shang, Shun Li; Wang, Yi; Han, Fengbo; Darling, Kristopher A.; Wu, Yidong; Xie, Xie; Senkov, Oleg N.; Li, Jinshan; Hui, Xi Dong; Dahmen, Karin A.; Liaw, Peter K.; Kecskes, Laszlo J.; Liu, Zi-Kui

2017-06-01

Refractory high-entropy alloys present attractive mechanical properties, i.e., high yield strength and fracture toughness, making them potential candidates for structural applications. Understandings of atomic and electronic interactions are important to reveal the origins for the formation of high-entropy alloys and their structure-dominated mechanical properties, thus enabling the development of a predictive approach for rapidly designing advanced materials. Here, we report the atomic and electronic basis for the valence-electron-concentration-categorized principles and the observed serration behavior in high-entropy alloys and high-entropy metallic glass, including MoNbTaW, MoNbVW, MoTaVW, HfNbTiZr, and Vitreloy-1 MG (Zr41Ti14Cu12.5Ni10Be22.5). We find that the yield strengths of high-entropy alloys and high-entropy metallic glass are a power-law function of the electron-work function, which is dominated by local atomic arrangements. Further, a reliance on the bonding-charge density provides a groundbreaking insight into the nature of loosely bonded spots in materials. The presence of strongly bonded clusters and weakly bonded glue atoms imply a serrated deformation of high-entropy alloys, resulting in intermittent avalanches of defects movement.

Relativistic calculations of atomic properties

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Sahoo, B. K.; Arora, Bindiya

2017-04-01

Singly charged ions are engaging candidates in many areas of Physics. They are especially important in astrophysics for evaluating the radiative properties of stellar objects, in optical frequency standards and for fundamental physics studies such as searches for permanent electric dipole moments and atomic parity violation. Interpretation of these experiments often requires a knowledge of their transition wavelengths and electric dipole amplitudes. In this work, we discuss the calculation of various properties of alkaline earth ions. The relativistic all-order SD method in which all single and double excitations of the Dirac-Fock wave function are included, is used to calculate these atomic properties. We use this method for evaluation of electric dipole matrix elements of alkaline earth ions. Combination of these matrix elements with experimental energies allow to obtain the polarizabilities of ground and excited states of ions. We discuss the applications of estimated polarizabiities as a function of imaginary frequencies in the calculations of long-range atom-ion interactions. We have also located the magic wavelengths for nS1 / 2 - nD3 / 2 , 5 / 2 transitions of alkaline earth ions. These calculated properties will be highly valuable to atomic and astrophysics community. UGC-BSR Grant No. F.7-273/2009/BSR.

Unraveling protein catalysis through neutron diffraction

NASA Astrophysics Data System (ADS)

Myles, Dean

Neutron scattering and diffraction are exquisitely sensitive to the location, concentration and dynamics of hydrogen atoms in materials and provide a powerful tool for the characterization of structure-function and interfacial relationships in biological systems. Modern neutron scattering facilities offer access to a sophisticated, non-destructive suite of instruments for biophysical characterization that provide spatial and dynamic information spanning from Angstroms to microns and from picoseconds to microseconds, respectively. Applications range from atomic-resolution analysis of individual hydrogen atoms in enzymes, through to multi-scale analysis of hierarchical structures and assemblies in biological complexes, membranes and in living cells. Here we describe how the precise location of protein and water hydrogen atoms using neutron diffraction provides a more complete description of the atomic and electronic structures of proteins, enabling key questions concerning enzyme reaction mechanisms, molecular recognition and binding and protein-water interactions to be addressed. Current work is focused on understanding how molecular structure and dynamics control function in photosynthetic, cell signaling and DNA repair proteins. We will highlight recent studies that provide detailed understanding of the physiochemical mechanisms through which proteins recognize ligands and catalyze reactions, and help to define and understand the key principles involved.

First-principles calculation of the polarization-dependent force driving the Eg mode in bismuth under optical excitation.

NASA Astrophysics Data System (ADS)

Murray, Eamonn; Fahy, Stephen

2014-03-01

Using first principles electronic structure methods, we calculate the induced force on the Eg (zone centre transverse optical) phonon mode in bismuth immediately after absorption of polarized light. When radiation with polarization perpendicular to the c-axis is absorbed in bismuth, the distribution of excited electrons and holes breaks the three-fold rotational symmetry and leads to a net force on the atoms in the direction perpendicular to the axis. We calculate the initial excited electronic distribution as a function of photon energy and polarization and find the resulting transverse and longitudinal forces experienced by the atoms. Using the measured, temperature-dependent rate of decay of the transverse force[2], we predict the approximate amplitude of induced atomic motion in the Eg mode as a function of temperature and optical fluence. This work is supported by Science Foundation Ireland and a Marie Curie International Incoming Fellowship.

Ground-state energies and highest occupied eigenvalues of atoms in exchange-only density-functional theory

NASA Astrophysics Data System (ADS)

Li, Yan; Harbola, Manoj K.; Krieger, J. B.; Sahni, Viraht

1989-11-01

The exchange-correlation potential of the Kohn-Sham density-functional theory has recently been interpreted as the work required to move an electron against the electric field of its Fermi-Coulomb hole charge distribution. In this paper we present self-consistent results for ground-state total energies and highest occupied eigenvalues of closed subshell atoms as obtained by this formalism in the exchange-only approximation. The total energies, which are an upper bound, lie within 50 ppm of Hartree-Fock theory for atoms heavier than Be. The highest occupied eigenvalues, as a consequence of this interpretation, approximate well the experimental ionization potentials. In addition, the self-consistently calculated exchange potentials are very close to those of Talman and co-workers [J. D. Talman and W. F. Shadwick, Phys. Rev. A 14, 36 (1976); K. Aashamar, T. M. Luke, and J. D. Talman, At. Data Nucl. Data Tables 22, 443 (1978)].

Equilibrium vortex lattices of a binary rotating atomic Bose–Einstein condensate with unequal atomic masses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Biao; Wang, Lin-Xue; Chen, Guang-Ping

We perform a detailed numerical study of the equilibrium ground-state structures of a binary rotating Bose–Einstein condensate with unequal atomic masses. Our results show that the ground-state distribution and its related vortex configurations are complex events that differ markedly depending strongly on the strength of rotation frequency, as well as on the ratio of atomic masses. We also discuss the structures and radii of the clouds, the number and the size of the core region of the vortices, as a function of the rotation frequency, and of the ratio of atomic masses, and the analytical results agree well with ourmore » numerical simulations. This work may open an alternate way in the quantum control of the binary rotating quantum gases with unequal atomic masses. - Highlights: • A binary quantum gases with unequal atomic masses is considered. • Effects of the ratio of atomic masses and rotation frequency are discussed in full parameter space. • The detailed information about both the cloud and vortices are also discussed.« less

Molecule-specific determination of atomic polarizabilities with the polarizable atomic multipole model.

PubMed

Woo Kim, Hyun; Rhee, Young Min

2012-07-30

Recently, many polarizable force fields have been devised to describe induction effects between molecules. In popular polarizable models based on induced dipole moments, atomic polarizabilities are the essential parameters and should be derived carefully. Here, we present a parameterization scheme for atomic polarizabilities using a minimization target function containing both molecular and atomic information. The main idea is to adopt reference data only from quantum chemical calculations, to perform atomic polarizability parameterizations even when relevant experimental data are scarce as in the case of electronically excited molecules. Specifically, our scheme assigns the atomic polarizabilities of any given molecule in such a way that its molecular polarizability tensor is well reproduced. We show that our scheme successfully works for various molecules in mimicking dipole responses not only in ground states but also in valence excited states. The electrostatic potential around a molecule with an externally perturbing nearby charge also exhibits a near-quantitative agreement with the reference data from quantum chemical calculations. The limitation of the model with isotropic atoms is also discussed to examine the scope of its applicability. Copyright © 2012 Wiley Periodicals, Inc.

Deciphering chemical order/disorder and material properties at the single-atom level.

PubMed

Yang, Yongsoo; Chen, Chien-Chun; Scott, M C; Ophus, Colin; Xu, Rui; Pryor, Alan; Wu, Li; Sun, Fan; Theis, Wolfgang; Zhou, Jihan; Eisenbach, Markus; Kent, Paul R C; Sabirianov, Renat F; Zeng, Hao; Ercius, Peter; Miao, Jianwei

2017-02-01

Perfect crystals are rare in nature. Real materials often contain crystal defects and chemical order/disorder such as grain boundaries, dislocations, interfaces, surface reconstructions and point defects. Such disruption in periodicity strongly affects material properties and functionality. Despite rapid development of quantitative material characterization methods, correlating three-dimensional (3D) atomic arrangements of chemical order/disorder and crystal defects with material properties remains a challenge. On a parallel front, quantum mechanics calculations such as density functional theory (DFT) have progressed from the modelling of ideal bulk systems to modelling 'real' materials with dopants, dislocations, grain boundaries and interfaces; but these calculations rely heavily on average atomic models extracted from crystallography. To improve the predictive power of first-principles calculations, there is a pressing need to use atomic coordinates of real systems beyond average crystallographic measurements. Here we determine the 3D coordinates of 6,569 iron and 16,627 platinum atoms in an iron-platinum nanoparticle, and correlate chemical order/disorder and crystal defects with material properties at the single-atom level. We identify rich structural variety with unprecedented 3D detail including atomic composition, grain boundaries, anti-phase boundaries, anti-site point defects and swap defects. We show that the experimentally measured coordinates and chemical species with 22 picometre precision can be used as direct input for DFT calculations of material properties such as atomic spin and orbital magnetic moments and local magnetocrystalline anisotropy. This work combines 3D atomic structure determination of crystal defects with DFT calculations, which is expected to advance our understanding of structure-property relationships at the fundamental level.

Growth of Ni nanoclusters on irradiated graphene: a molecular dynamics study.

PubMed

Valencia, F J; Hernandez-Vazquez, E E; Bringa, E M; Moran-Lopez, J L; Rogan, J; Gonzalez, R I; Munoz, F

2018-04-23

We studied the soft landing of Ni atoms on a previously damaged graphene sheet by means of molecular dynamics simulations. We found a monotonic decrease of the cluster frequency as a function of its size, but few big clusters comprise an appreciable fraction of the total number of Ni atoms. The aggregation of Ni atoms is also modeled by means of a simple phenomenological model. The results are in clear contrast with the case of hard or energetic landing of metal atoms, where there is a tendency to form mono-disperse metal clusters. This behavior is attributed to the high diffusion of unattached Ni atoms, together with vacancies acting as capture centers. The findings of this work show that a simple study of the energetics of the system is not enough in the soft landing regime, where it is unavoidable to also consider the growth process of metal clusters.

Effect of reactor loading on atomic oxygen concentration as measured by NO chemiluminescence

NASA Technical Reports Server (NTRS)

Lerner, N. R.

1989-01-01

It has previously been observed that the etch rate of polyethylene samples in the afterglow of an RF discharge in oxygen increases with reactor loading. This enhancement of the etch rate is attributed to reactive gas phase products of the polymer etching. In the present work, emission spectroscopy is employed to examine the species present in the gas phase during etching of polyethylene. In particular, the concentration of atomic oxygen downstream from the polyethylene samples is studied as a function of the reactor loading. It is found that the concentration of atomic oxygen increases as the reactor loading is increased. The increase of etch rate with increased reactor loading is attributed to the increase of atomic oxygen concentration in the vicinity of the sample.

Atomic and Ionic Radii of Elements 1-96.

PubMed

Rahm, Martin; Hoffmann, Roald; Ashcroft, N W

2016-10-04

Atomic and cationic radii have been calculated for the first 96 elements, together with selected anionic radii. The metric adopted is the average distance from the nucleus where the electron density falls to 0.001 electrons per bohr(3) , following earlier work by Boyd. Our radii are derived using relativistic all-electron density functional theory calculations, close to the basis set limit. They offer a systematic quantitative measure of the sizes of non-interacting atoms, commonly invoked in the rationalization of chemical bonding, structure, and different properties. Remarkably, the atomic radii as defined in this way correlate well with van der Waals radii derived from crystal structures. A rationalization for trends and exceptions in those correlations is provided. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Machine Learning Estimation of Atom Condensed Fukui Functions.

PubMed

Zhang, Qingyou; Zheng, Fangfang; Zhao, Tanfeng; Qu, Xiaohui; Aires-de-Sousa, João

2016-02-01

To enable the fast estimation of atom condensed Fukui functions, machine learning algorithms were trained with databases of DFT pre-calculated values for ca. 23,000 atoms in organic molecules. The problem was approached as the ranking of atom types with the Bradley-Terry (BT) model, and as the regression of the Fukui function. Random Forests (RF) were trained to predict the condensed Fukui function, to rank atoms in a molecule, and to classify atoms as high/low Fukui function. Atomic descriptors were based on counts of atom types in spheres around the kernel atom. The BT coefficients assigned to atom types enabled the identification (93-94 % accuracy) of the atom with the highest Fukui function in pairs of atoms in the same molecule with differences ≥0.1. In whole molecules, the atom with the top Fukui function could be recognized in ca. 50 % of the cases and, on the average, about 3 of the top 4 atoms could be recognized in a shortlist of 4. Regression RF yielded predictions for test sets with R(2) =0.68-0.69, improving the ability of BT coefficients to rank atoms in a molecule. Atom classification (as high/low Fukui function) was obtained with RF with sensitivity of 55-61 % and specificity of 94-95 %. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coverage and velocity dependent sticking coefficient and particle emission kinetics in the Cl2gas + Ksolid reaction

NASA Astrophysics Data System (ADS)

Hellberg, Lars; Kasemo, Bengt

Some strongly exothermic and non-adiabatic surface adsorption events, especially those where electronegative molecules adsorb on very electropositive (low work function) surfaces, are accompanied by emission of (exo)electrons, photons, excited atoms and negative ions. The reaction of halogen molecules with halogen surfaces constitute an efficient model system for such studies. We have previously reported data for the emission of negative particles and photons in the zero coverage limit for a range of velocities of Cl2 molecules impinging on cold potassium surfaces as well as the mechanism behind these emission processes. In the present work, we focus on measurements of the kinetics, i.e. the exposure/coverage dependence, of these processes for the same system. Specifically, we present data for, (i) the separated contributions from electrons and Cl- ions of the emitted negative particles, (ii) the photon emission stemming both from excited Potassium atoms and from the equivalent process causing electron emission, (iii) the change of the work function during the initial exposure and, finally, (iv) the sticking coefficient for different Cl2 velocities and exposures.

Diagnostics of Carbon Nanotube Formation in a Laser Produced Plume: An Investigation of the Metal Catalyst by Laser Ablation Atomic Fluorescence Spectroscopy

NASA Technical Reports Server (NTRS)

deBoer, Gary; Scott, Carl

2003-01-01

Carbon nanotubes, elongated molecular tubes with diameters of nanometers and lengths in microns, hold great promise for material science. Hopes for super strong light-weight material to be used in spacecraft design is the driving force behind nanotube work at JSC. The molecular nature of these materials requires the appropriate tools for investigation of their structure, properties, and formation. The mechanism of nanotube formation is of particular interest because it may hold keys to controlling the formation of different types of nanotubes and allow them to be produced in much greater quantities at less cost than is currently available. This summer's work involved the interpretation of data taken last summer and analyzed over the academic year. The work involved diagnostic studies of carbon nanotube formation processes occurring in a laser-produced plume. Laser ablation of metal doped graphite to produce a plasma plume in which carbon nanotubes self assemble is one method of making carbon nanotube. The laser ablation method is amenable to applying the techniques of laser spectroscopy, a powerful tool for probing the energies and dynamics of atomic and molecular species. The experimental work performed last summer involved probing one of the metal catalysts, nickel, by laser induced fluorescence. The nickel atom was studied as a function of oven temperature, probe laser wavelength, time after ablation, and position in the laser produced plume. This data along with previously obtained data on carbon was analyzed over the academic year. Interpretations of the data were developed this summer along with discussions of future work. The temperature of the oven in which the target is ablated greatly influences the amount of material ablated and the propagation of the plume. The ablation conditions and the time scale of atomic and molecular lifetimes suggest that initial ablation of the metal doped carbon target results in atomic and small molecular species. The metal atoms survive for several milliseconds while the gaseous carbon atoms and small molecules nucleate more rapidly. Additional experiments and the development of in situ methods for carbon nanotube detection would allow these results to be interpreted from the perspective of carbon nanotube formation.

Gaussian-input Gaussian mixture model for representing density maps and atomic models.

PubMed

Kawabata, Takeshi

2018-07-01

A new Gaussian mixture model (GMM) has been developed for better representations of both atomic models and electron microscopy 3D density maps. The standard GMM algorithm employs an EM algorithm to determine the parameters. It accepted a set of 3D points with weights, corresponding to voxel or atomic centers. Although the standard algorithm worked reasonably well; however, it had three problems. First, it ignored the size (voxel width or atomic radius) of the input, and thus it could lead to a GMM with a smaller spread than the input. Second, the algorithm had a singularity problem, as it sometimes stopped the iterative procedure due to a Gaussian function with almost zero variance. Third, a map with a large number of voxels required a long computation time for conversion to a GMM. To solve these problems, we have introduced a Gaussian-input GMM algorithm, which considers the input atoms or voxels as a set of Gaussian functions. The standard EM algorithm of GMM was extended to optimize the new GMM. The new GMM has identical radius of gyration to the input, and does not suddenly stop due to the singularity problem. For fast computation, we have introduced a down-sampled Gaussian functions (DSG) by merging neighboring voxels into an anisotropic Gaussian function. It provides a GMM with thousands of Gaussian functions in a short computation time. We also have introduced a DSG-input GMM: the Gaussian-input GMM with the DSG as the input. This new algorithm is much faster than the standard algorithm. Copyright © 2018 The Author(s). Published by Elsevier Inc. All rights reserved.

Average-atom treatment of relaxation time in x-ray Thomson scattering from warm dense matter.

PubMed

Johnson, W R; Nilsen, J

2016-03-01

The influence of finite relaxation times on Thomson scattering from warm dense plasmas is examined within the framework of the average-atom approximation. Presently most calculations use the collision-free Lindhard dielectric function to evaluate the free-electron contribution to the Thomson cross section. In this work, we use the Mermin dielectric function, which includes relaxation time explicitly. The relaxation time is evaluated by treating the average atom as an impurity in a uniform electron gas and depends critically on the transport cross section. The calculated relaxation rates agree well with values inferred from the Ziman formula for the static conductivity and also with rates inferred from a fit to the frequency-dependent conductivity. Transport cross sections determined by the phase-shift analysis in the average-atom potential are compared with those evaluated in the commonly used Born approximation. The Born approximation converges to the exact cross sections at high energies; however, differences that occur at low energies lead to corresponding differences in relaxation rates. The relative importance of including relaxation time when modeling x-ray Thomson scattering spectra is examined by comparing calculations of the free-electron dynamic structure function for Thomson scattering using Lindhard and Mermin dielectric functions. Applications are given to warm dense Be plasmas, with temperatures ranging from 2 to 32 eV and densities ranging from 2 to 64 g/cc.

Average-atom treatment of relaxation time in x-ray Thomson scattering from warm dense matter

DOE PAGES

Johnson, W. R.; Nilsen, J.

2016-03-14

Here, the influence of finite relaxation times on Thomson scattering from warm dense plasmas is examined within the framework of the average-atom approximation. Presently most calculations use the collision-free Lindhard dielectric function to evaluate the free-electron contribution to the Thomson cross section. In this work, we use the Mermin dielectric function, which includes relaxation time explicitly. The relaxation time is evaluated by treating the average atom as an impurity in a uniform electron gas and depends critically on the transport cross section. The calculated relaxation rates agree well with values inferred from the Ziman formula for the static conductivity andmore » also with rates inferred from a fit to the frequency-dependent conductivity. Transport cross sections determined by the phase-shift analysis in the average-atom potential are compared with those evaluated in the commonly used Born approximation. The Born approximation converges to the exact cross sections at high energies; however, differences that occur at low energies lead to corresponding differences in relaxation rates. The relative importance of including relaxation time when modeling x-ray Thomson scattering spectra is examined by comparing calculations of the free-electron dynamic structure function for Thomson scattering using Lindhard and Mermin dielectric functions. Applications are given to warm dense Be plasmas, with temperatures ranging from 2 to 32 eV and densities ranging from 2 to 64 g/cc.« less

Recent progress of atomic layer deposition on polymeric materials.

PubMed

Guo, Hong Chen; Ye, Enyi; Li, Zibiao; Han, Ming-Yong; Loh, Xian Jun

2017-01-01

As a very promising surface coating technology, atomic layer deposition (ALD) can be used to modify the surfaces of polymeric materials for improving their functions and expanding their application areas. Polymeric materials vary in surface functional groups (number and type), surface morphology and internal structure, and thus ALD deposition conditions that typically work on a normal solid surface, usually do not work on a polymeric material surface. To date, a large variety of research has been carried out to investigate ALD deposition on various polymeric materials. This paper aims to provide an in-depth review of ALD deposition on polymeric materials and its applications. Through this review, we will provide a better understanding of surface chemistry and reaction mechanism for controlled surface modification of polymeric materials by ALD. The integrated knowledge can aid in devising an improved way in the reaction between reactant precursors and polymer functional groups/polymer backbones, which will in turn open new opportunities in processing ALD materials for better inorganic/organic film integration and potential applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Halogen bond: a long overlooked interaction.

PubMed

Cavallo, Gabriella; Metrangolo, Pierangelo; Pilati, Tullio; Resnati, Giuseppe; Terraneo, Giancarlo

2015-01-01

Because of their high electronegativity, halogen atoms are typically considered, in most of their derivatives, as sites of high electron density and it is commonly accepted that they can form attractive interactions by functioning as the electron donor site (nucleophilic site). This is the case when they work as hydrogen bond acceptor sites. However, the electron density in covalently bound halogens is anisotropically distributed. There is a region of higher electron density, accounting for the ability of halogens to function as electron donor sites in attractive interactions, and a region of lower electron density where the electrostatic potential is frequently positive (mainly in the heavier halogens). This latter region is responsible for the ability of halogen atoms to function as the electron-acceptor site (electrophilic site) in attractive interactions formed with a variety of lone pair-possessing atoms, anions, and π-systems. This ability is quite general and is shown by a wide diversity of halogenated compounds (e.g., organohalogen derivatives and dihalogens). According to the definition proposed by the International Union of Pure and Applied Chemistry, any attractive interactions wherein the halogen atom is the electrophile is named halogen bond (XB). In this chapter, it is discussed how the practice and the concept of XB developed and a brief history of the interaction is presented. Papers (either from the primary or secondary literature) which have reported major experimental findings in the field or which have given important theoretical contributions for the development of the concept are recollected in order to trace how a unifying and comprehensive categorization emerged encompassing all interactions wherein halogen atoms function as the electrophilic site.

Strategy for designing stable and powerful nitrogen-rich high-energy materials by introducing boron atoms.

PubMed

Wu, Wen-Jie; Chi, Wei-Jie; Li, Quan-Song; Li, Ze-Sheng

2017-06-01

One of the most important aims in the development of high-energy materials is to improve their stability and thus ensure that they are safe to manufacture and transport. In this work, we theoretically investigated open-chain N 4 B 2 isomers using density functional theory in order to find the best way of stabilizing nitrogen-rich molecules. The results show that the boron atoms in these isomers are aligned linearly with their neighboring atoms, which facilitates close packing in the crystals of these materials. Upon comparing the energies of nine N 4 B 2 isomers, we found that the structure with alternating N and B atoms had the lowest energy. Structures with more than one nitrogen atom between two boron atoms had higher energies. The energy of N 4 B 2 increases by about 50 kcal/mol each time it is rearranged to include an extra nitrogen atom between the two boron atoms. More importantly, our results also show that boron atoms stabilize nitrogen-rich molecules more efficiently than carbon atoms do. Also, the combustion of any isomer of N 4 B 2 releases more heat than the corresponding isomer of N 4 C 2 does under well-oxygenated conditions. Our study suggests that the three most stable N 4 B 2 isomers (BN13, BN24, and BN34) are good candidates for high-energy molecules, and it outlines a new strategy for designing stable boron-containing high-energy materials. Graphical abstract The structural characteristics, thermodynamic stabilities, and exothermic properties of nitrogen-rich N 4 B 2 isomers were investigated by means of density functional theory.

Reactivity of amino acid anions with nitrogen and oxygen atoms.

PubMed

Wang, Zhe-Chen; Li, Ya-Ke; He, Sheng-Gui; Bierbaum, Veronica M

2018-02-14

For many decades, astronomers have searched for biological molecules, including amino acids, in the interstellar medium; this endeavor is important for investigating the hypothesis of the origin of life from space. The space environment is complex and atomic species, such as nitrogen and oxygen atoms, are widely distributed. In this work, the reactions of eight typical deprotonated amino acids (glycine, alanine, cysteine, proline, aspartic acid, histidine, tyrosine, and tryptophan) with ground state nitrogen and oxygen atoms are studied by experiment and theory. These amino acid anions do not react with nitrogen atoms. However, the reactions of these ions with oxygen atoms show an intriguing variety of ionic products and the reaction rate constants are of the order of 10 -10 cm 3 s -1 . Density functional calculations provide detailed mechanisms of the reactions, and demonstrate that spin conversion is essential for some processes. Our study provides important data and insights for understanding the kinetic and dynamic behavior of amino acids in space environments.

Single-electron quantization at room temperature in a-few-donor quantum dot in silicon nano-transistors

NASA Astrophysics Data System (ADS)

Samanta, Arup; Muruganathan, Manoharan; Hori, Masahiro; Ono, Yukinori; Mizuta, Hiroshi; Tabe, Michiharu; Moraru, Daniel

2017-02-01

Quantum dots formed by donor-atoms in Si nanodevices can provide a breakthrough for functionality at the atomic level with one-by-one control of electrons. However, single-electron effects in donor-atom devices have only been observed at low temperatures mainly due to the low tunnel barriers. If a few donor-atoms are closely coupled as a molecule to form a quantum dot, the ground-state energy level is significantly deepened, leading to higher tunnel barriers. Here, we demonstrate that such an a-few-donor quantum dot, formed by selective conventional doping of phosphorus (P) donors in a Si nano-channel, sustains Coulomb blockade behavior even at room temperature. In this work, such a quantum dot is formed by 3 P-donors located near the center of the selectively-doped area, which is consistent with a statistical analysis. This finding demonstrates practical conditions for atomic- and molecular-level electronics based on donor-atoms in silicon nanodevices.

Potential energy distribution function and its application to the problem of evaporation

NASA Astrophysics Data System (ADS)

Gerasimov, D. N.; Yurin, E. I.

2017-10-01

Distribution function on potential energy in a strong correlated system can be calculated analytically. In an equilibrium system (for instance, in the bulk of the liquid) this distribution function depends only on temperature and mean potential energy, which can be found through the specific heat of vaporization. At the surface of the liquid this distribution function differs significantly, but its shape still satisfies analytical correlation. Distribution function on potential energy nearby the evaporation surface can be used instead of the work function of the atom of the liquid.

Crater function moments: Role of implanted noble gas atoms

NASA Astrophysics Data System (ADS)

Hobler, Gerhard; Maciążek, Dawid; Postawa, Zbigniew

2018-04-01

Spontaneous pattern formation by energetic ion beams is usually explained in terms of surface-curvature dependent sputtering and atom redistribution in the target. Recently, the effect of ion implantation on surface stability has been studied for nonvolatile ion species, but for the case of noble gas ion beams it has always been assumed that the implanted atoms can be neglected. In this work, we show by molecular dynamics (MD) and Monte Carlo (MC) simulations that this assumption is not valid in a wide range of implant conditions. Sequential-impact MD simulations are performed for 1-keV Ar, 2-keV Kr, and 2-keV Xe bombardments of Si, starting with a pure single-crystalline Si target and running impacts until sputtering equilibrium has been reached. The simulations demonstrate the importance of the implanted ions for crater-function estimates. The atomic volumes of Ar, Kr, and Xe in Si are found to be a factor of two larger than in the solid state. To extend the study to a wider range of energies, MC simulations are performed. We find that the role of the implanted ions increases with the ion energy although the increase is attenuated for the heavier ions. The analysis uses the crater function formalism specialized to the case of sputtering equilibrium.

Length-dependent transport in molecular junctions based on SAMs of alkanethiols and alkanedithiols: effect of metal work function and applied bias on tunneling efficiency and contact resistance.

PubMed

Engelkes, Vincent B; Beebe, Jeremy M; Frisbie, C Daniel

2004-11-03

Nanoscopic tunnel junctions were formed by contacting Au-, Pt-, or Ag-coated atomic force microscopy (AFM) tips to self-assembled monolayers (SAMs) of alkanethiol or alkanedithiol molecules on polycrystalline Au, Pt, or Ag substrates. Current-voltage traces exhibited sigmoidal behavior and an exponential attenuation with molecular length, characteristic of nonresonant tunneling. The length-dependent decay parameter, beta, was found to be approximately 1.1 per carbon atom (C(-1)) or 0.88 A(-)(1) and was independent of applied bias (over a voltage range of +/-1.5 V) and electrode work function. In contrast, the contact resistance, R(0), extrapolated from resistance versus molecular length plots showed a notable decrease with both applied bias and increasing electrode work function. The doubly bound alkanedithiol junctions were observed to have a contact resistance approximately 1 to 2 orders of magnitude lower than the singly bound alkanethiol junctions. However, both alkanethiol and dithiol junctions exhibited the same length dependence (beta value). The resistance versus length data were also used to calculate transmission values for each type of contact (e.g., Au-S-C, Au/CH(3), etc.) and the transmission per C-C bond (T(C)(-)()(C)).

Watching Silica's Dance: Imaging the Structure and Dynamics of the Atomic (Re-) Arrangements in 2D Glass

NASA Astrophysics Data System (ADS)

Muller, David

2014-03-01

Even though glasses are almost ubiquitous--in our windows, on our iPhones, even on our faces--they are also mysterious. Because glasses are notoriously difficult to study, basic questions like: ``How are the atoms arranged? Where and how do glasses break?'' are still under contention. We use aberration corrected transmission electron microscopy (TEM) to image the atoms in a new two-dimensional phase of silica glass - freestanding it becomes the world's thinnest pane of glass at only 3-atoms thick, and take a unique look into these questions. Using atom-by-atom imaging and spectroscopy, we are able to reconstruct the full structure and bonding of this 2D glass and identify it as a bi-tetrahedral layer of SiO2. Our images also strikingly resemble Zachariasen's original cartoon models of glasses, drawn in 1932. As such, our work realizes an 80-year-old vision for easily understandable glassy systems and introduces promising methods to test theoretical predictions against experimental data. We image atoms in the disordered solid and track their motions in response to local strain. We directly obtain ring statistics and pair distribution functions that span short-, medium-, and long-range order, and test these against long-standing theoretical predictions of glass structure and dynamics. We use the electron beam to excite atomic rearrangements, producing surprisingly rich and beautiful videos of how a glass bends and breaks, as well as the exchange of atoms at a solid/liquid interface. Detailed analyses of these videos reveal a complex dance of elastic and plastic deformations, phase transitions, and their interplay. These examples illustrate the wide-ranging and fundamental materials physics that can now be studied at atomic-resolution via transmission electron microscopy of two-dimensional glasses. Work in collaboration with: S. Kurasch, U. Kaiser, R. Hovden, Q. Mao, J. Kotakoski, J. S. Alden, A. Shekhawat, A. A. Alemi, J. P. Sethna, P. L. McEuen, A.V. Krasheninnikov, A. Srivastava, V. Skakalova, J. C. Meyer, and J.H. Smet. This work was supported by the NSF through the Cornell Center for Materials Research (NSF DMR-1120296).

The interaction of excited atoms and few-cycle laser pulses

PubMed Central

Calvert, J. E.; Xu, Han; Palmer, A. J.; Glover, R. D.; Laban, D. E.; Tong, X. M.; Kheifets, A. S.; Bartschat, K.; Litvinyuk, I. V.; Kielpinski, D.; Sang, R. T.

2016-01-01

This work describes the first observations of the ionisation of neon in a metastable atomic state utilising a strong-field, few-cycle light pulse. We compare the observations to theoretical predictions based on the Ammosov-Delone-Krainov (ADK) theory and a solution to the time-dependent Schrödinger equation (TDSE). The TDSE provides better agreement with the experimental data than the ADK theory. We optically pump the target atomic species and measure the ionisation rate as the a function of different steady-state populations in the fine structure of the target state which shows significant ionisation rate dependence on populations of spin-polarised states. The physical mechanism for this effect is unknown. PMID:27666403

The interaction of excited atoms and few-cycle laser pulses.

PubMed

Calvert, J E; Xu, Han; Palmer, A J; Glover, R D; Laban, D E; Tong, X M; Kheifets, A S; Bartschat, K; Litvinyuk, I V; Kielpinski, D; Sang, R T

2016-09-26

This work describes the first observations of the ionisation of neon in a metastable atomic state utilising a strong-field, few-cycle light pulse. We compare the observations to theoretical predictions based on the Ammosov-Delone-Krainov (ADK) theory and a solution to the time-dependent Schrödinger equation (TDSE). The TDSE provides better agreement with the experimental data than the ADK theory. We optically pump the target atomic species and measure the ionisation rate as the a function of different steady-state populations in the fine structure of the target state which shows significant ionisation rate dependence on populations of spin-polarised states. The physical mechanism for this effect is unknown.

Theoretical study for heterojunction surface of NEA GaN photocathode dispensed with Cs activation

NASA Astrophysics Data System (ADS)

Xia, Sihao; Liu, Lei; Wang, Honggang; Wang, Meishan; Kong, Yike

2016-09-01

For the disadvantages of conventional negative electron affinity (NEA) GaN photocathodes activated by Cs or Cs/O, new-type NEA GaN photocathodes with heterojunction surface dispensed with Cs activation are investigated based on first-principle study with density functional theory. Through the growth of an ultrathin n-type GaN cap layer on p-type GaN emission layer, a p-n heterojunction is formed on the surface. According to the calculation results, it is found that Si atoms tend to replace Ga atoms to result in an n-type doped cap layer which contributes to the decreasing of work function. After the growth of n-type GaN cap layer, the atom structure near the p-type emission layer is changed while that away from the surface has no obvious variations. By analyzing the E-Mulliken charge distribution of emission surface with and without cap layer, it is found that the positive charge of Ga and Mg atoms in the emission layer decrease caused by the cap layer, while the negative charge of N atom increases. The conduction band moves downwards after the growth of cap layer. Si atom produces donor levels around the valence band maximum. The absorption coefficient of GaN emission layer decreases and the reflectivity increases caused by n-type GaN cap layer.

Quantum nuclear effects in water using centroid molecular dynamics

NASA Astrophysics Data System (ADS)

Kondratyuk, N. D.; Norman, G. E.; Stegailov, V. V.

2018-01-01

The quantum nuclear effects are studied in water using the method of centroid molecular dynamics (CMD). The aim is the calibration of CMD implementation in LAMMPS. The calculated intramolecular energy, atoms gyration radii and radial distribution functions are shown in comparison with previous works. The work is assumed to be the step toward to solution of the discrepancy between the simulation results and the experimental data of liquid n-alkane properties in our previous works.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yongsoo; Chen, Chien-Chun; Scott, M. C.

Perfect crystals are rare in nature. Real materials often contain crystal defects and chemical order/disorder such as grain boundaries, dislocations, interfaces, surface reconstructions and point defects. Such disruption in periodicity strongly affects material properties and functionality. Despite rapid development of quantitative material characterization methods, correlating three-dimensional (3D) atomic arrangements of chemical order/disorder and crystal defects with material properties remains a challenge. On a parallel front, quantum mechanics calculations such as density functional theory (DFT) have progressed from the modelling of ideal bulk systems to modelling ‘real’ materials with dopants, dislocations, grain boundaries and interfaces; but these calculations rely heavily onmore » average atomic models extracted from crystallography. To improve the predictive power of first-principles calculations, there is a pressing need to use atomic coordinates of real systems beyond average crystallographic measurements. Here we determine the 3D coordinates of 6,569 iron and 16,627 platinum atoms in an iron-platinum nanoparticle, and correlate chemical order/disorder and crystal defects with material properties at the single-atom level. We identify rich structural variety with unprecedented 3D detail including atomic composition, grain boundaries, anti-phase boundaries, anti-site point defects and swap defects. We show that the experimentally measured coordinates and chemical species with 22 picometre precision can be used as direct input for DFT calculations of material properties such as atomic spin and orbital magnetic moments and local magnetocrystalline anisotropy. The work presented here combines 3D atomic structure determination of crystal defects with DFT calculations, which is expected to advance our understanding of structure–property relationships at the fundamental level.« less

Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites.

PubMed

Wu, Xiaoxi; Tan, Liang Z; Shen, Xiaozhe; Hu, Te; Miyata, Kiyoshi; Trinh, M Tuan; Li, Renkai; Coffee, Ryan; Liu, Shi; Egger, David A; Makasyuk, Igor; Zheng, Qiang; Fry, Alan; Robinson, Joseph S; Smith, Matthew D; Guzelturk, Burak; Karunadasa, Hemamala I; Wang, Xijie; Zhu, Xiaoyang; Kronik, Leeor; Rappe, Andrew M; Lindenberg, Aaron M

2017-07-01

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. This work shows the important role of light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role ofmore » light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.« less

Structure prediction of boron-doped graphene by machine learning

NASA Astrophysics Data System (ADS)

M. Dieb, Thaer; Hou, Zhufeng; Tsuda, Koji

2018-06-01

Heteroatom doping has endowed graphene with manifold aspects of material properties and boosted its applications. The atomic structure determination of doped graphene is vital to understand its material properties. Motivated by the recently synthesized boron-doped graphene with relatively high concentration, here we employ machine learning methods to search the most stable structures of doped boron atoms in graphene, in conjunction with the atomistic simulations. From the determined stable structures, we find that in the free-standing pristine graphene, the doped boron atoms energetically prefer to substitute for the carbon atoms at different sublattice sites and that the para configuration of boron-boron pair is dominant in the cases of high boron concentrations. The boron doping can increase the work function of graphene by 0.7 eV for a boron content higher than 3.1%.

Deciphering chemical order/disorder and material properties at the single-atom level

DOE PAGES

Yang, Yongsoo; Chen, Chien-Chun; Scott, M. C.; ...

2017-02-01

Perfect crystals are rare in nature. Real materials often contain crystal defects and chemical order/disorder such as grain boundaries, dislocations, interfaces, surface reconstructions and point defects. Such disruption in periodicity strongly affects material properties and functionality. Despite rapid development of quantitative material characterization methods, correlating three-dimensional (3D) atomic arrangements of chemical order/disorder and crystal defects with material properties remains a challenge. On a parallel front, quantum mechanics calculations such as density functional theory (DFT) have progressed from the modelling of ideal bulk systems to modelling ‘real’ materials with dopants, dislocations, grain boundaries and interfaces; but these calculations rely heavily onmore » average atomic models extracted from crystallography. To improve the predictive power of first-principles calculations, there is a pressing need to use atomic coordinates of real systems beyond average crystallographic measurements. Here we determine the 3D coordinates of 6,569 iron and 16,627 platinum atoms in an iron-platinum nanoparticle, and correlate chemical order/disorder and crystal defects with material properties at the single-atom level. We identify rich structural variety with unprecedented 3D detail including atomic composition, grain boundaries, anti-phase boundaries, anti-site point defects and swap defects. We show that the experimentally measured coordinates and chemical species with 22 picometre precision can be used as direct input for DFT calculations of material properties such as atomic spin and orbital magnetic moments and local magnetocrystalline anisotropy. The work presented here combines 3D atomic structure determination of crystal defects with DFT calculations, which is expected to advance our understanding of structure–property relationships at the fundamental level.« less

Control of Rydberg atom blockade by dc electric field orientation in a quasi-one-dimensional sample

NASA Astrophysics Data System (ADS)

Goncalves, Luís Felipe; Marcassa, Luis Gustavo

2017-04-01

Rydberg atoms posse a strong atom-atom interaction, which limits its density in an atomic sample. Such effect is known as Rydberg atom blockade. Here, we present a novel way to control such effect by direct orienting the induced atomic dipole moment using a dc external electrical field. To demonstrate it, we excite the 50S1 / 2 Rb atomic state in a quasi-one-dimensional sample held in a quasi-electrostatic trap. A pure nS state holds only van der Waals interaction at long range, but in the presence of an external electric field the state mixing leads to strong dipole-dipole interactions. We have measured the Rydberg atom population as a function of ground state atoms density for several angles between the electric field and the main axis of the unidimensional sample. The results indicate that the limit on the final Rydberg density can be controlled by electric field orientation. Besides, we have characterized the sample by using direct spatial ion imaging, demonstrating that it does behave as an unidimensional sample. This work was supported by Sao Paulo Research Foundation (FAPESP) Grants No. 2011/22309-8 and No. 2013/02816- 8, the U.S. Army Research Office Grant No. W911NF-15-1-0638 and CNPq.

Atom probe trajectory mapping using experimental tip shape measurements.

PubMed

Haley, D; Petersen, T; Ringer, S P; Smith, G D W

2011-11-01

Atom probe tomography is an accurate analytical and imaging technique which can reconstruct the complex structure and composition of a specimen in three dimensions. Despite providing locally high spatial resolution, atom probe tomography suffers from global distortions due to a complex projection function between the specimen and detector which is different for each experiment and can change during a single run. To aid characterization of this projection function, this work demonstrates a method for the reverse projection of ions from an arbitrary projection surface in 3D space back to an atom probe tomography specimen surface. Experimental data from transmission electron microscopy tilt tomography are combined with point cloud surface reconstruction algorithms and finite element modelling to generate a mapping back to the original tip surface in a physically and experimentally motivated manner. As a case study, aluminium tips are imaged using transmission electron microscopy before and after atom probe tomography, and the specimen profiles used as input in surface reconstruction methods. This reconstruction method is a general procedure that can be used to generate mappings between a selected surface and a known tip shape using numerical solutions to the electrostatic equation, with quantitative solutions to the projection problem readily achievable in tens of minutes on a contemporary workstation. © 2011 The Authors Journal of Microscopy © 2011 Royal Microscopical Society.

Atomic layer deposition-based functionalization of materials for medical and environmental health applications

PubMed Central

Narayan, Roger J.; Adiga, Shashishekar P.; Pellin, Michael J.; Curtiss, Larry A.; Hryn, Alexander J.; Stafslien, Shane; Chisholm, Bret; Shih, Chun-Che; Shih, Chun-Ming; Lin, Shing-Jong; Su, Yea-Yang; Jin, Chunming; Zhang, Junping; Monteiro-Riviere, Nancy A.; Elam, Jeffrey W.

2010-01-01

Nanoporous alumina membranes exhibit high pore densities, well-controlled and uniform pore sizes, as well as straight pores. Owing to these unusual properties, nanoporous alumina membranes are currently being considered for use in implantable sensor membranes and water purification membranes. Atomic layer deposition is a thin-film growth process that may be used to modify the pore size in a nanoporous alumina membrane while retaining a narrow pore distribution. In addition, films deposited by means of atomic layer deposition may impart improved biological functionality to nanoporous alumina membranes. In this study, zinc oxide coatings and platinum coatings were deposited on nanoporous alumina membranes by means of atomic layer deposition. PEGylated nanoporous alumina membranes were prepared by self-assembly of 1-mercaptoundec-11-yl hexa(ethylene glycol) on platinum-coated nanoporous alumina membranes. The pores of the PEGylated nanoporous alumina membranes remained free of fouling after exposure to human platelet-rich plasma; protein adsorption, fibrin networks and platelet aggregation were not observed on the coated membrane surface. Zinc oxide-coated nanoporous alumina membranes demonstrated activity against two waterborne pathogens, Escherichia coli and Staphylococcus aureus. The results of this work indicate that nanoporous alumina membranes may be modified using atomic layer deposition for use in a variety of medical and environmental health applications. PMID:20308114

Continuous measurement of an atomic current

NASA Astrophysics Data System (ADS)

Laflamme, C.; Yang, D.; Zoller, P.

2017-04-01

We are interested in dynamics of quantum many-body systems under continuous observation, and its physical realizations involving cold atoms in lattices. In the present work we focus on continuous measurement of atomic currents in lattice models, including the Hubbard model. We describe a Cavity QED setup, where measurement of a homodyne current provides a faithful representation of the atomic current as a function of time. We employ the quantum optical description in terms of a diffusive stochastic Schrödinger equation to follow the time evolution of the atomic system conditional to observing a given homodyne current trajectory, thus accounting for the competition between the Hamiltonian evolution and measurement back action. As an illustration, we discuss minimal models of atomic dynamics and continuous current measurement on rings with synthetic gauge fields, involving both real space and synthetic dimension lattices (represented by internal atomic states). Finally, by "not reading" the current measurements the time evolution of the atomic system is governed by a master equation, where—depending on the microscopic details of our CQED setups—we effectively engineer a current coupling of our system to a quantum reservoir. This provides interesting scenarios of dissipative dynamics generating "dark" pure quantum many-body states.

HAADF-STEM atom counting in atom probe tomography specimens: Towards quantitative correlative microscopy.

PubMed

Lefebvre, W; Hernandez-Maldonado, D; Moyon, F; Cuvilly, F; Vaudolon, C; Shinde, D; Vurpillot, F

2015-12-01

The geometry of atom probe tomography tips strongly differs from standard scanning transmission electron microscopy foils. Whereas the later are rather flat and thin (<20 nm), tips display a curved surface and a significantly larger thickness. As far as a correlative approach aims at analysing the same specimen by both techniques, it is mandatory to explore the limits and advantages imposed by the particular geometry of atom probe tomography specimens. Based on simulations (electron probe propagation and image simulations), the possibility to apply quantitative high angle annular dark field scanning transmission electron microscopy to of atom probe tomography specimens has been tested. The influence of electron probe convergence and the benefice of deconvolution of electron probe point spread function electron have been established. Atom counting in atom probe tomography specimens is for the first time reported in this present work. It is demonstrated that, based on single projections of high angle annular dark field imaging, significant quantitative information can be used as additional input for refining the data obtained by correlative analysis of the specimen in APT, therefore opening new perspectives in the field of atomic scale tomography. Copyright © 2015 Elsevier B.V. All rights reserved.

Theoretical studies of the work functions of Pd-based bimetallic surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Zhao-Bin; Wu, Feng; Wang, Yue-Chao

2015-06-07

Work functions of Pd-based bimetallic surfaces, including mainly M/Pd(111), Pd/M, and Pd/M/Pd(111) (M = 4d transition metals, Cu, Au, and Pt), are studied using density functional theory. We find that the work function of these bimetallic surfaces is significantly different from that of parent metals. Careful analysis based on Bader charges and electron density difference indicates that the variation of the work function in bimetallic surfaces can be mainly attributed to two factors: (1) charge transfer between the two different metals as a result of their different intrinsic electronegativity, and (2) the charge redistribution induced by chemical bonding between themore » top two layers. The first factor can be related to the contact potential, i.e., the work function difference between two metals in direct contact, and the second factor can be well characterized by the change in the charge spilling out into vacuum. We also find that the variation in the work functions of Pd/M/Pd(111) surfaces correlates very well with the variation of the d-band center of the surface Pd atom. The findings in this work can be used to provide general guidelines to design new bimetallic surfaces with desired electronic properties.« less

Atomic pair distribution function at the Brazilian Synchrotron Light Laboratory: application to the Pb 1–x La xZr 0.40Ti 0.60O 3 ferroelectric system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saleta, M. E.; Eleotério, M.; Mesquita, A.

2017-07-29

This work reports the setting up of the X-ray diffraction and spectroscopy beamline at the Brazilian Synchrotron Light Laboratory for performing total scattering experiments to be analyzed by atomic pair distribution function (PDF) studies. The results of a PDF refinement for Al 2O 3 standard are presented and compared with data acquired at a beamline of the Advanced Photon Source, where it is common to perform this type of experiment. A preliminary characterization of the Pb 1–xLa xZr 0.40Ti 0.60O 3 ferroelectric system, withx= 0.11, 0.12 and 0.15, is also shown.

Determination of effective atomic number of biomedical samples using Gamma ray back-scattering

NASA Astrophysics Data System (ADS)

Singh, Inderjeet; Singh, Bhajan; Sandhu, B. S.; Sabharwal, Arvind D.

2018-05-01

The study of effective atomic number of biomedical sample has been carried out by using a non-destructive multiple back-scattering technique. Also radiation characterization method is used to compare the tissue equivalent material as human tissue. Response function of 3″ × 3″ NaI(Tl) scintillation detector is implemented on recorded pulse-height distribution to boost the counts under the photo-peak and help to reduce the uncertainty in the experimental result. Monte Carlo calculation for multiple back-scattered events supports the reported experimental work.

Ultra-small rhenium clusters supported on graphene.

PubMed

Miramontes, Orlando; Bonafé, Franco; Santiago, Ulises; Larios-Rodriguez, Eduardo; Velázquez-Salazar, Jesús J; Mariscal, Marcelo M; Yacaman, Miguel José

2015-03-28

The adsorption of very small rhenium clusters (2-13 atoms) supported on graphene was studied by high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM). The atomic structure of the clusters was fully resolved with the aid of density functional theory calculations and STEM simulations. It was found that octahedral and tetrahedral structures work as seeds to obtain more complex morphologies. Finally, a detailed analysis of the electronic structure suggested that a higher catalytic effect can be expected in Re clusters when adsorbed on graphene than in isolated ones.

Ultra-small rhenium clusters supported on graphene

PubMed Central

Miramontes, Orlando; Bonafé, Franco; Santiago, Ulises; Larios-Rodriguez, Eduardo; Velázquez-Salazar, Jesús J.; Mariscal, Marcelo M.; Yacaman, Miguel José

2015-01-01

The adsorption of very small rhenium clusters (2 – 13 atoms) supported on graphene was studied with high annular dark field - scanning transmission electron microscopy (HAADF-STEM). The atomic structure of the clusters was fully resolved with the aid of density functional calculations and STEM simulations. It was found that octahedral and tetrahedral structures work as seeds to obtain more complex morphologies. Finally, a detailed analysis of the electronic structure suggested that a higher catalytic effect can be expected in Re clusters when adsorbed on graphene than in isolated ones. PMID:25721176

Introducing a new bond reactivity index: Philicities for natural bond orbitals.

PubMed

Sánchez-Márquez, Jesús; Zorrilla, David; García, Víctor; Fernández, Manuel

2017-12-22

In the present work, a new methodology defined for obtaining reactivity indices (philicities) is proposed. This is based on reactivity functions such as the Fukui function or the dual descriptor, and makes it possible to project the information from reactivity functions onto molecular orbitals, instead of onto the atoms of the molecule (atomic reactivity indices). The methodology focuses on the molecules' natural bond orbitals (bond reactivity indices) because these orbitals have the advantage of being localized, allowing the reaction site of an electrophile or nucleophile to be determined within a very precise molecular region. This methodology provides a "philicity" index for every NBO, and a representative set of molecules has been used to test the new definition. A new methodology has also been developed to compare the "finite difference" and the "frontier molecular orbital" approximations. To facilitate their use, the proposed methodology as well as the possibility of calculating the new indices have been implemented in a new version of UCA-FUKUI software. In addition, condensation schemes based on atomic populations of the "atoms in molecules" theory, the Hirshfeld population analysis, the approximation of Mulliken (with a minimal basis set) and electrostatic potential-derived charges have also been implemented, including the calculation of "bond reactivity indices" defined in previous studies. Graphical abstract A new methodology defined for obtaining bond reactivity indices (philicities) is proposed and makes it possible to project the information from reactivity functions onto molecular orbitals. The proposed methodology as well as the possibility of calculating the new indices have been implemented in a new version of UCA-FUKUI software. In addition, this version can use new atomic condensation schemes and new "utilities" have also been included in this second version.

Contribution to viscosity from the structural relaxation via the atomic scale Green-Kubo stress correlation function.

PubMed

Levashov, V A

2017-11-14

We studied the connection between the structural relaxation and viscosity for a binary model of repulsive particles in the supercooled liquid regime. The used approach is based on the decomposition of the macroscopic Green-Kubo stress correlation function into the correlation functions between the atomic level stresses. Previously we used the approach to study an iron-like single component system of particles. The role of vibrational motion has been addressed through the demonstration of the relationship between viscosity and the shear waves propagating over large distances. In our previous considerations, however, we did not discuss the role of the structural relaxation. Here we suggest that the contribution to viscosity from the structural relaxation can be taken into account through the consideration of the contribution from the atomic stress auto-correlation term only. This conclusion, however, does not mean that only the auto-correlation term represents the contribution to viscosity from the structural relaxation. Previously the role of the structural relaxation for viscosity has been addressed through the considerations of the transitions between inherent structures and within the mode-coupling theory by other authors. In the present work, we study the structural relaxation through the considerations of the parent liquid and the atomic level stress correlations in it. The comparison with the results obtained on the inherent structures also is made. Our current results suggest, as our previous observations, that in the supercooled liquid regime, the vibrational contribution to viscosity extends over the times that are much larger than the Einstein's vibrational period and much larger than the times that it takes for the shear waves to propagate over the model systems. Besides addressing the atomic level shear stress correlations, we also studied correlations between the atomic level pressure elements.

Contribution to viscosity from the structural relaxation via the atomic scale Green-Kubo stress correlation function

NASA Astrophysics Data System (ADS)

Levashov, V. A.

2017-11-01

We studied the connection between the structural relaxation and viscosity for a binary model of repulsive particles in the supercooled liquid regime. The used approach is based on the decomposition of the macroscopic Green-Kubo stress correlation function into the correlation functions between the atomic level stresses. Previously we used the approach to study an iron-like single component system of particles. The role of vibrational motion has been addressed through the demonstration of the relationship between viscosity and the shear waves propagating over large distances. In our previous considerations, however, we did not discuss the role of the structural relaxation. Here we suggest that the contribution to viscosity from the structural relaxation can be taken into account through the consideration of the contribution from the atomic stress auto-correlation term only. This conclusion, however, does not mean that only the auto-correlation term represents the contribution to viscosity from the structural relaxation. Previously the role of the structural relaxation for viscosity has been addressed through the considerations of the transitions between inherent structures and within the mode-coupling theory by other authors. In the present work, we study the structural relaxation through the considerations of the parent liquid and the atomic level stress correlations in it. The comparison with the results obtained on the inherent structures also is made. Our current results suggest, as our previous observations, that in the supercooled liquid regime, the vibrational contribution to viscosity extends over the times that are much larger than the Einstein's vibrational period and much larger than the times that it takes for the shear waves to propagate over the model systems. Besides addressing the atomic level shear stress correlations, we also studied correlations between the atomic level pressure elements.

Engineering the work function of buckled boron α-sheet by lithium adsorption: a first-principles investigation.

PubMed

Zheng, Bing; Yu, Hai-tao; Xie, Ying; Lian, Yong-fu

2014-11-26

First-principles density functional theory calculations were performed to study the effect of Li adsorption on the structural and electronic properties, particularly the work function, of boron α-sheet. The calculated binding energies indicated that boron α-sheet could be well stabilized by the adsorption of Li atoms. Furthermore, the work functions of Li-adsorbed boron α-sheets were observed to decrease drastically with increasing Li coverage. The work functions are lower than that of Mg and even, for some of them, lower than that of Ca, indicating a considerable potential application of Li-adsorbed boron α-sheets as field-emission and electrode materials. Based on the calculated geometric and electronic structures, we discuss in details some possible aspects affecting the work function. The Li coverage dependence of the work functions of Li-adsorbed boron α-sheets was further confirmed by electrostatic potential analyses. The relationship between the work function variation and the Fermi and vacuum energy level shifts was also discussed, and we observed that the variation of the work function is primarily associated with the shift of the Fermi energy level. It is the surface dipole formed by the interaction between adatoms and substrate that should be responsible for the observed variation of the work function, whereas the increasing negative charge and rumpling for boron α-sheet only play minor roles. Additionally, the effect of Li adatoms on the work function of boron α-sheet was confirmed to be much stronger than that of graphene or a graphene double layer.

Determination of atomic hydrogen in non-thermal hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry.

PubMed

Wang, Wei-Guo; Xu, Yong; Yang, Xue-Feng; Wang, Wen-Chun; Zhu, Ai-Min

2005-01-01

Atomic hydrogen plays important roles in chemical vapor deposition of functional materials, plasma etching and new approaches to chemical synthesis of hydrogen-containing compounds. The present work reports experimental determinations of atomic hydrogen near the grounded electrode in medium-pressure dielectric barrier discharge hydrogen plasmas by means of molecular beam threshold ionization mass spectrometry (MB-TIMS). At certain discharge conditions (a.c. frequency of 24 kHz, 28 kV of peak-to-peak voltage), the measured hydrogen dissociation fraction is decreased from approximately 0.83% to approximately 0.14% as the hydrogen pressure increases from 2.0 to 14.0 Torr. A simulation method for extraction of the approximate electron beam energy distribution function in the mass spectrometer ionizer and a semi-quantitative approach to calibrate the mass discrimination effect caused by the supersonic beam formation and the mass spectrometer measurement are reported. Copyright 2005 John Wiley & Sons, Ltd.

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

The structural and electronic properties of metal atoms adsorbed on graphene

NASA Astrophysics Data System (ADS)

Liu, Wenjiang; Zhang, Cheng; Deng, Mingsen; Cai, Shaohong

2017-09-01

Based on density functional theory (DFT), we studied the structural and electronic properties of seven different metal atoms adsorbed on graphene (M + graphene). The geometries, adsorption energies, density of states (DOS), band structures, electronic dipole moment, magnetic moment and work function (WF) of M + graphene were calculated. The adsorption energies ΔE indicated that Li, Na, K, Ca and Fe adsorbed on graphene were tending to form stable structures. However, diffusion would occur on Cu and Ag adsorbed on graphene. In addition, the electronic structure near the Fermi level of graphene was significantly affected by Fe (Cu and Ag), compared with Li (Na, K and Ca). The electronic dipole moment and magnetic moment of M + graphene were sensitive to the adsorbed metal atoms. Moreover, we found electropositive (electronegative) adsorption can decrease (increase) the WF of the surface. Specially, the WF of Ag + graphene and Fe + graphene would increase because surface dipole moment make a contribution to electron.

Quantum Monte Carlo for electronic structure: Recent developments and applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodriquez, Maria Milagos Soto

Quantum Monte Carlo (QMC) methods have been found to give excellent results when applied to chemical systems. The main goal of the present work is to use QMC to perform electronic structure calculations. In QMC, a Monte Carlo simulation is used to solve the Schroedinger equation, taking advantage of its analogy to a classical diffusion process with branching. In the present work the author focuses on how to extend the usefulness of QMC to more meaningful molecular systems. This study is aimed at questions concerning polyatomic and large atomic number systems. The accuracy of the solution obtained is determined bymore » the accuracy of the trial wave function`s nodal structure. Efforts in the group have given great emphasis to finding optimized wave functions for the QMC calculations. Little work had been done by systematically looking at a family of systems to see how the best wave functions evolve with system size. In this work the author presents a study of trial wave functions for C, CH, C 2H and C 2H 2. The goal is to study how to build wave functions for larger systems by accumulating knowledge from the wave functions of its fragments as well as gaining some knowledge on the usefulness of multi-reference wave functions. In a MC calculation of a heavy atom, for reasonable time steps most moves for core electrons are rejected. For this reason true equilibration is rarely achieved. A method proposed by Batrouni and Reynolds modifies the way the simulation is performed without altering the final steady-state solution. It introduces an acceleration matrix chosen so that all coordinates (i.e., of core and valence electrons) propagate at comparable speeds. A study of the results obtained using their proposed matrix suggests that it may not be the optimum choice. In this work the author has found that the desired mixing of coordinates between core and valence electrons is not achieved when using this matrix. A bibliography of 175 references is included.« less

Atomic layer deposited TaCy metal gates: Impact on microstructure, electrical properties, and work function on HfO2 high-k dielectrics

NASA Astrophysics Data System (ADS)

Triyoso, D. H.; Gregory, R.; Schaeffer, J. K.; Werho, D.; Li, D.; Marcus, S.; Wilk, G. D.

2007-11-01

TaCy has been reported to have the appropriate work function for negative metal-oxide semiconductor metal in high-k metal-oxide field-effect transistors. As device size continues to shrink, a conformal deposition for metal gate electrodes is needed. In this work, we report on the development and characterization of a novel TaCy process by atomic layer deposition (ALD). Detailed physical properties of TaCy films are studied using ellipsometry, a four-point probe, Rutherford backscattering spectrometry (RBS), x-ray photoelectron spectroscopy (XPS), and x-ray diffraction (XRD). RBS and XPS analysis indicate that TaCy films are near-stoichiometric, nitrogen free, and have low oxygen impurities. Powder XRD spectra showed that ALD films have a cubic microstructure. XPS carbon bonding studies revealed that little or no glassy carbon is present in the bulk of the film. Excellent electrical properties are obtained using ALD TaCy as a metal gate electrode. Well-behaved capacitance-voltage characteristics with ALD HfO2 gate dielectrics are demonstrated for TaCy thicknesses of 50, 100, and 250 Å. A low fixed charge (˜2-4×10-11 cm-2) is observed for all ALD HfO2/ALD TaCy devices. Increasing the thickness of ALD TaCy results in a decrease in work function (4.77 to 4.54 eV) and lower threshold voltages.

Partially Oxidized SnS2 Atomic Layers Achieving Efficient Visible-Light-Driven CO2 Reduction.

PubMed

Jiao, Xingchen; Li, Xiaodong; Jin, Xiuyu; Sun, Yongfu; Xu, Jiaqi; Liang, Liang; Ju, Huanxin; Zhu, Junfa; Pan, Yang; Yan, Wensheng; Lin, Yue; Xie, Yi

2017-12-13

Unraveling the role of surface oxide on affecting its native metal disulfide's CO 2 photoreduction remains a grand challenge. Herein, we initially construct metal disulfide atomic layers and hence deliberately create oxidized domains on their surfaces. As an example, SnS 2 atomic layers with different oxidation degrees are successfully synthesized. In situ Fourier transform infrared spectroscopy spectra disclose the COOH* radical is the main intermediate, whereas density-functional-theory calculations reveal the COOH* formation is the rate-limiting step. The locally oxidized domains could serve as the highly catalytically active sites, which not only benefit for charge-carrier separation kinetics, verified by surface photovoltage spectra, but also result in electron localization on Sn atoms near the O atoms, thus lowering the activation energy barrier through stabilizing the COOH* intermediates. As a result, the mildly oxidized SnS 2 atomic layers exhibit the carbon monoxide formation rate of 12.28 μmol g -1 h -1 , roughly 2.3 and 2.6 times higher than those of the poorly oxidized SnS 2 atomic layers and the SnS 2 atomic layers under visible-light illumination. This work uncovers atomic-level insights into the correlation between oxidized sulfides and CO 2 reduction property, paving a new way for obtaining high-efficiency CO 2 photoreduction performances.

Surface determination through atomically resolved secondary-electron imaging

PubMed Central

Ciston, J.; Brown, H. G.; D'Alfonso, A. J.; Koirala, P.; Ophus, C.; Lin, Y.; Suzuki, Y.; Inada, H.; Zhu, Y.; Allen, L. J.; Marks, L. D.

2015-01-01

Unique determination of the atomic structure of technologically relevant surfaces is often limited by both a need for homogeneous crystals and ambiguity of registration between the surface and bulk. Atomically resolved secondary-electron imaging is extremely sensitive to this registration and is compatible with faceted nanomaterials, but has not been previously utilized for surface structure determination. Here we report a detailed experimental atomic-resolution secondary-electron microscopy analysis of the c(6 × 2) reconstruction on strontium titanate (001) coupled with careful simulation of secondary-electron images, density functional theory calculations and surface monolayer-sensitive aberration-corrected plan-view high-resolution transmission electron microscopy. Our work reveals several unexpected findings, including an amended registry of the surface on the bulk and strontium atoms with unusual seven-fold coordination within a typically high surface coverage of square pyramidal TiO5 units. Dielectric screening is found to play a critical role in attenuating secondary-electron generation processes from valence orbitals. PMID:26082275

Molecular dynamics simulation investigations of atomic-scale wear

NASA Astrophysics Data System (ADS)

Shao, Yuchong; Falk, Michael

2013-03-01

Frictional running-in and material transfer in wear take place at the micro- and nano-scale but the fundamental physics remain poorly understood. Here we intend to investigate wear and running-in phenomena in silicon based materials, which are widely utilized in micro/nano electromechanical systems(MEMS/NEMS). We use an atomic force microscopy (AFM) model composed of a crystalline silicon tip and substrate coated with native oxide layers. Molecular dynamics simulation has been performed over a range of temperatures, external loads and slip rates. Results show that adhesive wear takes place across the interface in an atom-by-atom fashion which remodels the tip leading to a final steady state. We quantify the rate of material transfer as a function of the coverage of non-bridging oxygen (NBO) atoms, which has a pronounced change of the system's tribological and wear behaviors. A constitutive rate and state model is proposed to predict the evolution of frictional strength and wear. This work is supported by the National Science Foundation under Award No. 0926111.

Direct visualization of atomically precise nitrogen-doped graphene nanoribbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yi; Zhang, Yanfang; Li, Geng

2014-07-14

We have fabricated atomically precise nitrogen-doped chevron-type graphene nanoribbons by using the on-surface synthesis technique combined with the nitrogen substitution of the precursors. Scanning tunneling microscopy and spectroscopy indicate that the well-defined nanoribbons tend to align with the neighbors side-by-side with a band gap of 1.02 eV, which is in good agreement with the density functional theory calculation result. The influence of the high precursor coverage on the quality of the nanoribbons is also studied. We find that graphene nanoribbons with sufficient aspect ratios can only be fabricated at sub-monolayer precursor coverage. This work provides a way to construct atomically precisemore » nitrogen-doped graphene nanoribbons.« less

Electronic transport properties of graphene doped by gallium.

PubMed

Mach, J; Procházka, P; Bartošík, M; Nezval, D; Piastek, J; Hulva, J; Švarc, V; Konečný, M; Kormoš, L; Šikola, T

2017-10-13

In this work we present the effect of low dose gallium (Ga) deposition (<4 ML) performed in UHV (10 -7 Pa) on the electronic doping and charge carrier scattering in graphene grown by chemical vapor deposition. In situ graphene transport measurements performed with a graphene field-effect transistor structure show that at low Ga coverages a graphene layer tends to be strongly n-doped with an efficiency of 0.64 electrons per one Ga atom, while the further deposition and Ga cluster formation results in removing electrons from graphene (less n-doping). The experimental results are supported by the density functional theory calculations and explained as a consequence of distinct interaction between graphene and Ga atoms in case of individual atoms, layers, or clusters.

Electronic transport properties of graphene doped by gallium

NASA Astrophysics Data System (ADS)

Mach, J.; Procházka, P.; Bartošík, M.; Nezval, D.; Piastek, J.; Hulva, J.; Švarc, V.; Konečný, M.; Kormoš, L.; Šikola, T.

2017-10-01

In this work we present the effect of low dose gallium (Ga) deposition (<4 ML) performed in UHV (10-7 Pa) on the electronic doping and charge carrier scattering in graphene grown by chemical vapor deposition. In situ graphene transport measurements performed with a graphene field-effect transistor structure show that at low Ga coverages a graphene layer tends to be strongly n-doped with an efficiency of 0.64 electrons per one Ga atom, while the further deposition and Ga cluster formation results in removing electrons from graphene (less n-doping). The experimental results are supported by the density functional theory calculations and explained as a consequence of distinct interaction between graphene and Ga atoms in case of individual atoms, layers, or clusters.

Strong Fermi-Level Pinning at Metal/n-Si(001) Interface Ensured by Forming an Intact Schottky Contact with a Graphene Insertion Layer.

PubMed

Yoon, Hoon Hahn; Jung, Sungchul; Choi, Gahyun; Kim, Junhyung; Jeon, Youngeun; Kim, Yong Soo; Jeong, Hu Young; Kim, Kwanpyo; Kwon, Soon-Yong; Park, Kibog

2017-01-11

We report the systematic experimental studies demonstrating that a graphene layer inserted at metal/n-Si(001) interface is efficient to explore interface Fermi-level pinning effect. It is confirmed that an inserted graphene layer prevents atomic interdiffusion to form an atomically abrupt Schottky contact. The Schottky barriers of metal/graphene/n-Si(001) junctions show a very weak dependence on metal work-function, implying that the metal Fermi-level is almost completely pinned at charge neutrality level close to the valence band edge of Si. The atomically impermeable and electronically transparent properties of graphene can be used generally to form an intact Schottky contact for all semiconductors.

Relating electronic and geometric structure of atomic layer deposited BaTiO 3 to its electrical properties

DOE PAGES

Torgersen, Jan; Acharya, Shinjita; Dadlani, Anup Lal; ...

2016-03-24

Atomic layer deposition allows the fabrication of BaTiO 3 (BTO) ultrathin films with tunable dielectric properties, which is a promising material for electronic and optical technology. Industrial applicability necessitates a better understanding of their atomic structure and corresponding properties. Through the use of element-specific X-ray absorption near edge structure (XANES) analysis, O K-edge of BTO as a function of cation composition and underlying substrate (RuO 2 and SiO 2) is revealed. By employing density functional theory and multiple scattering simulations, we analyze the distortions in BTO’s bonding environment captured by the XANES spectra. The spectral weight shifts to lower energymore » with increasing Ti content and provides an atomic scale (microscopic) explanation for the increase in leakage current density. Differences in film morphologies in the first few layers near substrate–film interfaces reveal BTO’s homogeneous growth on RuO 2 and its distorted growth on SiO 2. As a result, this work links structural changes to BTO thin-film properties and provides insight necessary for optimizing future BTO and other ternary metal oxide-based thin-film devices.« less

Grassmann phase space theory and the Jaynes-Cummings model

NASA Astrophysics Data System (ADS)

Dalton, B. J.; Garraway, B. M.; Jeffers, J.; Barnett, S. M.

2013-07-01

The Jaynes-Cummings model of a two-level atom in a single mode cavity is of fundamental importance both in quantum optics and in quantum physics generally, involving the interaction of two simple quantum systems—one fermionic system (the TLA), the other bosonic (the cavity mode). Depending on the initial conditions a variety of interesting effects occur, ranging from ongoing oscillations of the atomic population difference at the Rabi frequency when the atom is excited and the cavity is in an n-photon Fock state, to collapses and revivals of these oscillations starting with the atom unexcited and the cavity mode in a coherent state. The observation of revivals for Rydberg atoms in a high-Q microwave cavity is key experimental evidence for quantisation of the EM field. Theoretical treatments of the Jaynes-Cummings model based on expanding the state vector in terms of products of atomic and n-photon states and deriving coupled equations for the amplitudes are a well-known and simple method for determining the effects. In quantum optics however, the behaviour of the bosonic quantum EM field is often treated using phase space methods, where the bosonic mode annihilation and creation operators are represented by c-number phase space variables, with the density operator represented by a distribution function of these variables. Fokker-Planck equations for the distribution function are obtained, and either used directly to determine quantities of experimental interest or used to develop c-number Langevin equations for stochastic versions of the phase space variables from which experimental quantities are obtained as stochastic averages. Phase space methods have also been developed to include atomic systems, with the atomic spin operators being represented by c-number phase space variables, and distribution functions involving these variables and those for any bosonic modes being shown to satisfy Fokker-Planck equations from which c-number Langevin equations are often developed. However, atomic spin operators satisfy the standard angular momentum commutation rules rather than the commutation rules for bosonic annihilation and creation operators, and are in fact second order combinations of fermionic annihilation and creation operators. Though phase space methods in which the fermionic operators are represented directly by c-number phase space variables have not been successful, the anti-commutation rules for these operators suggest the possibility of using Grassmann variables—which have similar anti-commutation properties. However, in spite of the seminal work by Cahill and Glauber and a few applications, the use of phase space methods in quantum optics to treat fermionic systems by representing fermionic annihilation and creation operators directly by Grassmann phase space variables is rather rare. This paper shows that phase space methods using a positive P type distribution function involving both c-number variables (for the cavity mode) and Grassmann variables (for the TLA) can be used to treat the Jaynes-Cummings model. Although it is a Grassmann function, the distribution function is equivalent to six c-number functions of the two bosonic variables. Experimental quantities are given as bosonic phase space integrals involving the six functions. A Fokker-Planck equation involving both left and right Grassmann differentiations can be obtained for the distribution function, and is equivalent to six coupled equations for the six c-number functions. The approach used involves choosing the canonical form of the (non-unique) positive P distribution function, in which the correspondence rules for the bosonic operators are non-standard and hence the Fokker-Planck equation is also unusual. Initial conditions, such as those above for initially uncorrelated states, are discussed and used to determine the initial distribution function. Transformations to new bosonic variables rotating at the cavity frequency enable the six coupled equations for the new c-number functions-that are also equivalent to the canonical Grassmann distribution function-to be solved analytically, based on an ansatz from an earlier paper by Stenholm. It is then shown that the distribution function is exactly the same as that determined from the well-known solution based on coupled amplitude equations. In quantum-atom optics theories for many atom bosonic and fermionic systems are needed. With large atom numbers, treatments must often take into account many quantum modes—especially for fermions. Generalisations of phase space distribution functions of phase space variables for a few modes to phase space distribution functionals of field functions (which represent the field operators, c-number fields for bosons, Grassmann fields for fermions) are now being developed for large systems. For the fermionic case, the treatment of the simple two mode problem represented by the Jaynes-Cummings model is a useful test case for the future development of phase space Grassmann distribution functional methods for fermionic applications in quantum-atom optics.

The ionic versus metallic nature of 2D electrides: a density-functional description.

PubMed

Dale, Stephen G; Johnson, Erin R

2017-10-18

The two-dimensional (2D) electrides are a highly unusual class of materials, possessing interstitial electron layers sandwiched between cationic atomic layers of the solid. In this work, density-functional theory, with the exchange-hole dipole moment dispersion correction, is used to investigate exfoliation and interlayer sliding of the only two experimentally known 2D electrides: [Ca 2 N] + e - and [Y 2 C] 2+ (2e - ). Examination of the valence states during exfoliation identifies intercalated electrons in the bulk and weakly-bound surface-states in the fully-expanded case. The calculated exfoliation energies for the 2D electrides are found to be much higher than for typical 2D materials, which is attributed to the ionic nature of the electrides and the strong Coulomb forces governing the interlayer interactions. Conversely, the calculated sliding barriers are found to be quite low, comparable to those for typical 2D materials, and are effectively unchanged by exclusion of dispersion. We conjecture that the metallic nature of the interstitial electrons allows the atomic layers to move relative to each other without significantly altering the interlayer binding. Finally, comparison with previous works reveals the importance of a system-dependent dispersion correction in the density-functional treatment.

Surface structure. Subatomic resolution force microscopy reveals internal structure and adsorption sites of small iron clusters.

PubMed

Emmrich, Matthias; Huber, Ferdinand; Pielmeier, Florian; Welker, Joachim; Hofmann, Thomas; Schneiderbauer, Maximilian; Meuer, Daniel; Polesya, Svitlana; Mankovsky, Sergiy; Ködderitzsch, Diemo; Ebert, Hubert; Giessibl, Franz J

2015-04-17

Clusters built from individual iron atoms adsorbed on surfaces (adatoms) were investigated by atomic force microscopy (AFM) with subatomic resolution. Single copper and iron adatoms appeared as toroidal structures and multiatom clusters as connected structures, showing each individual atom as a torus. For single adatoms, the toroidal shape of the AFM image depends on the bonding symmetry of the adatom to the underlying structure [twofold for copper on copper(110) and threefold for iron on copper(111)]. Density functional theory calculations support the experimental data. The findings correct our previous work, in which multiple minima in the AFM signal were interpreted as a reflection of the orientation of a single front atom, and suggest that dual and triple minima in the force signal are caused by dimer and trimer tips, respectively. Copyright © 2015, American Association for the Advancement of Science.

On the spray pulsations of the effervescent atomizers

NASA Astrophysics Data System (ADS)

Mlkvik, Marek; Knizat, Branislav

2018-06-01

The presented paper focuses on the comparison of the two effervescent atomizer configurations—the outside-in-gas (OIG) and the outside-in-liquid (OIL). The comparison was based on the spray pulsation assessment by different methods. The atomizers were tested under the same operating conditions given by the constant injection pressure (0.14 MPa) and the gas to the liquid mass ratio (GLR) varying from 2.5 to 5%. The aqueous maltodextrin solution was used as the working liquid (μ = 60 and 146 mPa·s). We found that the time-averaging method does not provide sufficient spray quality description. Based on the cumulative distribution function (CDF) we found that the OIG atomizer generated the spray with non-uniform droplet size distribution at all investigated GLRs. Exceptionally large droplets were present even in the spray which appeared stable when was analyzed by the time-averaging method.

A Density Functional Study of Atomic Hydrogen and Oxygen Chemisorptions on the (0001) Surface of Double Hexagonal Close Packed Americium

NASA Astrophysics Data System (ADS)

Dholabhai, Pratik; Atta-Fynn, Raymond; Ray, Asok

2008-03-01

Ab initio total energy calculations within the framework of density functional theory have been performed for atomic hydrogen and oxygen chemisorptions on the (0001) surface of double hexagonal packed americium using a full-potential all-electron linearized augmented plane wave plus local orbitals (FLAPW+lo) method. The three-fold hollow hcp site was found to be the most stable site for H adsorption, while the two-fold bridge adsorption site was found to be the most stable site for O adsorption. Chemisorption energies and adsorption geometries for different adsorption sites will be discussed. The change in work functions, magnetic moments, partial charges inside muffin-tins, difference charge density distributions and density of states for the bare Am slab and the Am slab after adsorption of the adatom will be discussed. The implications of chemisorption on Am 5f electron localization-delocalization will also be discussed.

Atomic Gaussian type orbitals and their Fourier transforms via the Rayleigh expansion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yükçü, Niyazi

Gaussian type orbitals (GTOs), which are one of the types of exponential type orbitals (ETOs), are used usually as basis functions in the multi-center atomic and molecular integrals to better understand physical and chemical properties of matter. In the Fourier transform method (FTM), basis functions have not simplicity to make mathematical operations, but their Fourier transforms are easier to use. In this work, with the help of FTM, Rayleigh expansion and some properties of unnormalized GTOs, we present new mathematical results for the Fourier transform of GTOs in terms of Laguerre polynomials, hypergeometric and Whittaker functions. Physical and analytical propertiesmore » of GTOs are discussed and some numerical results have been given in a table. Finally, we compare our mathematical results with the other known literature results by using a computer program and details of evaluation are presented.« less

Light-induced picosecond rotational disordering of the inorganic sublattice in hybrid perovskites

DOE PAGES

Wu, Xiaoxi; Tan, Liang Z.; Shen, Xiaozhe; ...

2017-07-26

Femtosecond resolution electron scattering techniques are applied to resolve the first atomic-scale steps following absorption of a photon in the prototypical hybrid perovskite methylammonium lead iodide. Following above-gap photoexcitation, we directly resolve the transfer of energy from hot carriers to the lattice by recording changes in the mean square atomic displacements on 10-ps time scales. Measurements of the time-dependent pair distribution function show an unexpected broadening of the iodine-iodine correlation function while preserving the Pb-I distance. This indicates the formation of a rotationally disordered halide octahedral structure developing on picosecond time scales. Here, this work shows the important role ofmore » light-induced structural deformations within the inorganic sublattice in elucidating the unique optoelectronic functionality exhibited by hybrid perovskites and provides new understanding of hot carrier-lattice interactions, which fundamentally determine solar cell efficiencies.« less

Current-induced changes of migration energy barriers in graphene and carbon nanotubes

NASA Astrophysics Data System (ADS)

Obodo, J. T.; Rungger, I.; Sanvito, S.; Schwingenschlögl, U.

2016-05-01

An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative.An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative. Electronic supplementary information (ESI) available. See DOI: 10.1039/C6NR00534A

A discriminatory function for prediction of protein-DNA interactions based on alpha shape modeling.

PubMed

Zhou, Weiqiang; Yan, Hong

2010-10-15

Protein-DNA interaction has significant importance in many biological processes. However, the underlying principle of the molecular recognition process is still largely unknown. As more high-resolution 3D structures of protein-DNA complex are becoming available, the surface characteristics of the complex become an important research topic. In our work, we apply an alpha shape model to represent the surface structure of the protein-DNA complex and developed an interface-atom curvature-dependent conditional probability discriminatory function for the prediction of protein-DNA interaction. The interface-atom curvature-dependent formalism captures atomic interaction details better than the atomic distance-based method. The proposed method provides good performance in discriminating the native structures from the docking decoy sets, and outperforms the distance-dependent formalism in terms of the z-score. Computer experiment results show that the curvature-dependent formalism with the optimal parameters can achieve a native z-score of -8.17 in discriminating the native structure from the highest surface-complementarity scored decoy set and a native z-score of -7.38 in discriminating the native structure from the lowest RMSD decoy set. The interface-atom curvature-dependent formalism can also be used to predict apo version of DNA-binding proteins. These results suggest that the interface-atom curvature-dependent formalism has a good prediction capability for protein-DNA interactions. The code and data sets are available for download on http://www.hy8.com/bioinformatics.htm kenandzhou@hotmail.com.

Atomic Processes and Diagnostics of Low Pressure Krypton Plasma

NASA Astrophysics Data System (ADS)

Srivastava, Rajesh; Goyal, Dipti; Gangwar, Reetesh; Stafford, Luc

2015-03-01

Optical emission spectroscopy along with suitable collisional-radiative (CR) model is used in plasma diagnostics. Importance of reliable cross-sections for various atomic processes is shown for low pressure argon plasma. In the present work, radially-averaged Kr emission lines from the 2pi --> 1sj were recorded as a function of pressure from 1 to 50mTorr. We have developed a CR model using our fine-structure relativistic-distorted wave cross sections. The various processes considered are electron-impact excitation, ionization and their reverse processes. The required rate coefficients have been calculated from these cross-sections assuming Maxwellian energy distribution. Electron temperature obtained from the CR model is found to be in good agreement with the probe measurements. Work is supported by IAEA Vienna, DAE-BRNS Mumbai and CSIR, New Delhi.

Search for magnetism in transition metal atoms doped tetragonal graphene: A DFT approach

NASA Astrophysics Data System (ADS)

Chowdhury, Suman; Majumdar, Arnab; Jana, Debnarayan

2017-11-01

The discovery of different two-dimensional (2D) materials both theoretically and experimentally, can change the scenario of the current electronic industry because of their intriguing properties. Among the 2D materials, the first one which was discovered experimentally was graphene. In this work we have studied the electronic and magnetic properties of a new allotrope of disordered graphene, which is not hexagonal, rather possesses tetragonal symmetry known as T-graphene (TG). Density functional theory (DFT) has been thoroughly employed to study the relevant electronic properties. In previous works, it has been reported that pristine TG is non-magnetic. It is also known that, introducing transition metal (TM) atoms is a feasible way to control the electronic and magnetic properties. Here we have reported the relevant properties of four TM atoms i.e. Sc, V, Cr and Mn doped TG. From the defect formation energy study, it has been noticed that all the structures are endothermic in nature. For each case, we have found appreciable amount of magnetic moment. With increasing atomic weight of the dopant atom, the magnitude of the magnetic moment also increases. We have tried to explain this magnetic ordering with the help of spin-polarized partial density of states (PDOS). Controlling spin degrees of freedom is important for building spintronic devices. From that point of view, we hope this study will be useful to build TG based spintronic devices.

Surface functionalization of two-dimensional metal chalcogenides by Lewis acid-base chemistry

NASA Astrophysics Data System (ADS)

Lei, Sidong; Wang, Xifan; Li, Bo; Kang, Jiahao; He, Yongmin; George, Antony; Ge, Liehui; Gong, Yongji; Dong, Pei; Jin, Zehua; Brunetto, Gustavo; Chen, Weibing; Lin, Zuan-Tao; Baines, Robert; Galvão, Douglas S.; Lou, Jun; Barrera, Enrique; Banerjee, Kaustav; Vajtai, Robert; Ajayan, Pulickel

2016-05-01

Precise control of the electronic surface states of two-dimensional (2D) materials could improve their versatility and widen their applicability in electronics and sensing. To this end, chemical surface functionalization has been used to adjust the electronic properties of 2D materials. So far, however, chemical functionalization has relied on lattice defects and physisorption methods that inevitably modify the topological characteristics of the atomic layers. Here we make use of the lone pair electrons found in most of 2D metal chalcogenides and report a functionalization method via a Lewis acid-base reaction that does not alter the host structure. Atomic layers of n-type InSe react with Ti4+ to form planar p-type [Ti4+n(InSe)] coordination complexes. Using this strategy, we fabricate planar p-n junctions on 2D InSe with improved rectification and photovoltaic properties, without requiring heterostructure growth procedures or device fabrication processes. We also show that this functionalization approach works with other Lewis acids (such as B3+, Al3+ and Sn4+) and can be applied to other 2D materials (for example MoS2, MoSe2). Finally, we show that it is possible to use Lewis acid-base chemistry as a bridge to connect molecules to 2D atomic layers and fabricate a proof-of-principle dye-sensitized photosensing device.

Formation of Triboelectric Series via Atomic-Level Surface Functionalization for Triboelectric Energy Harvesting.

PubMed

Shin, Sung-Ho; Bae, Young Eun; Moon, Hyun Kyung; Kim, Jungkil; Choi, Suk-Ho; Kim, Yongho; Yoon, Hyo Jae; Lee, Min Hyung; Nah, Junghyo

2017-06-27

Triboelectric charging involves frictional contact of two different materials, and their contact electrification usually relies on polarity difference in the triboelectric series. This limits the choices of materials for triboelectric contact pairs, hindering research and development of energy harvest devices utilizing triboelectric effect. A progressive approach to resolve this issue involves modification of chemical structures of materials for effectively engineering their triboelectric properties. Here, we describe a facile method to change triboelectric property of a polymeric surface via atomic-level chemical functionalizations using a series of halogens and amines, which allows a wide spectrum of triboelectric series over single material. Using this method, tunable triboelectric output power density is demonstrated in triboelectric generators. Furthermore, molecular-scale calculation using density functional theory unveils that electrons transferred through electrification are occupying the PET group rather than the surface functional group. The work introduced here would open the ability to tune triboelectric property of materials by chemical modification of surface and facilitate the development of energy harvesting devices and sensors exploiting triboelectric effect.

All-atom molecular dynamics of the HBV capsid reveals insights into biological function and cryo-EM resolution limits

PubMed Central

Perilla, Juan R; Schlicksup, Christopher John; Venkatakrishnan, Balasubramanian; Zlotnick, Adam; Schulten, Klaus

2018-01-01

The hepatitis B virus capsid represents a promising therapeutic target. Experiments suggest the capsid must be flexible to function; however, capsid structure and dynamics have not been thoroughly characterized in the absence of icosahedral symmetry constraints. Here, all-atom molecular dynamics simulations are leveraged to investigate the capsid without symmetry bias, enabling study of capsid flexibility and its implications for biological function and cryo-EM resolution limits. Simulation results confirm flexibility and reveal a propensity for asymmetric distortion. The capsid’s influence on ionic species suggests a mechanism for modulating the display of cellular signals and implicates the capsid’s triangular pores as the location of signal exposure. A theoretical image reconstruction performed using simulated conformations indicates how capsid flexibility may limit the resolution of cryo-EM. Overall, the present work provides functional insight beyond what is accessible to experimental methods and raises important considerations regarding asymmetry in structural studies of icosahedral virus capsids. PMID:29708495

A Priori Calculations of Thermodynamic Functions

DTIC Science & Technology

1991-12-01

Ten closes this work with a brief summary and offers suggestions for improving the model and for future research. S CHAPTER TWO In this chapter, we...we must first define the theoretical model . The molecules studied in this work contain up to 10 non- hydrogen atoms and, in general, are not...is given by equation (2-31) for two different geometries or two different theoretical models . Equation (2-31) shows the error in the force constant has

Equilibrium properties of simple metal thin films in the self-compressed stabilized jellium model.

PubMed

Mahmoodi, T; Payami, M

2009-07-01

In this work, we have applied the self-compressed stabilized jellium model to predict the equilibrium properties of isolated thin Al, Na and Cs slabs. To make a direct correspondence to atomic slabs, we have considered only those L values that correspond to n-layered atomic slabs with 2≤n≤20, for surface indices (100), (110), and (111). The calculations are based on the density functional theory and self-consistent solution of the Kohn-Sham equations in the local density approximation. Our results show that firstly, the quantum size effects are significant for slabs with sizes smaller than or near to the Fermi wavelength of the valence electrons λ(F), and secondly, some slabs expand while others contract with respect to the bulk spacings. Based on the results, we propose a criterion for realization of significant quantum size effects that lead to expansion of some thin slabs. For more justification of the criterion, we have tested it on Li slabs for 2≤n≤6. We have compared our Al results with those obtained from using all-electron or pseudo-potential first-principles calculations. This comparison shows excellent agreements for Al(100) work functions, and qualitatively good agreements for the other work functions and surface energies. These agreements justify the way we have used the self-compressed stabilized jellium model for the correct description of the properties of simple metal slab systems. On the other hand, our results for the work functions and surface energies of large- n slabs are in good agreement with those obtained from applying the stabilized jellium model for semi-infinite systems. In addition, we have performed the slab calculations in the presence of surface corrugation for selected Al slabs and have shown that the results are worsened.

Highly reflective polymeric substrates functionalized utilizing atomic layer deposition

NASA Astrophysics Data System (ADS)

Zuzuarregui, Ana; Coto, Borja; Rodríguez, Jorge; Gregorczyk, Keith E.; Ruiz de Gopegui, Unai; Barriga, Javier; Knez, Mato

2015-08-01

Reflective surfaces are one of the key elements of solar plants to concentrate energy in the receivers of solar thermal electricity plants. Polymeric substrates are being considered as an alternative to the widely used glass mirrors due to their intrinsic and processing advantages, but optimizing both the reflectance and the physical stability of polymeric mirrors still poses technological difficulties. In this work, polymeric surfaces have been functionalized with ceramic thin-films by atomic layer deposition. The characterization and optimization of the parameters involved in the process resulted in surfaces with a reflection index of 97%, turning polymers into a real alternative to glass substrates. The solution we present here can be easily applied in further technological areas where seemingly incompatible combinations of polymeric substrates and ceramic coatings occur.

A density functional global optimisation study of neutral 8-atom Cu-Ag and Cu-Au clusters

NASA Astrophysics Data System (ADS)

Heard, Christopher J.; Johnston, Roy L.

2013-02-01

The effect of doping on the energetics and dimensionality of eight atom coinage metal subnanometre particles is fully resolved using a genetic algorithm in tandem with on the fly density functional theory calculations to determine the global minima (GM) for Cu n Ag(8- n) and Cu n Au(8- n) clusters. Comparisons are made to previous ab initio work on mono- and bimetallic clusters, with excellent agreement found. Charge transfer and geometric arguments are considered to rationalise the stability of the particular permutational isomers found. An interesting transition between three dimensional and two dimensional GM structures is observed for copper-gold clusters, which is sharper and appears earlier in the doping series than is known for gold-silver particles.

Multiscale multiphysics and multidomain models—Flexibility and rigidity

PubMed Central

Xia, Kelin; Opron, Kristopher; Wei, Guo-Wei

2013-01-01

The emerging complexity of large macromolecules has led to challenges in their full scale theoretical description and computer simulation. Multiscale multiphysics and multidomain models have been introduced to reduce the number of degrees of freedom while maintaining modeling accuracy and achieving computational efficiency. A total energy functional is constructed to put energies for polar and nonpolar solvation, chemical potential, fluid flow, molecular mechanics, and elastic dynamics on an equal footing. The variational principle is utilized to derive coupled governing equations for the above mentioned multiphysical descriptions. Among these governing equations is the Poisson-Boltzmann equation which describes continuum electrostatics with atomic charges. The present work introduces the theory of continuum elasticity with atomic rigidity (CEWAR). The essence of CEWAR is to formulate the shear modulus as a continuous function of atomic rigidity. As a result, the dynamics complexity of a macromolecular system is separated from its static complexity so that the more time-consuming dynamics is handled with continuum elasticity theory, while the less time-consuming static analysis is pursued with atomic approaches. We propose a simple method, flexibility-rigidity index (FRI), to analyze macromolecular flexibility and rigidity in atomic detail. The construction of FRI relies on the fundamental assumption that protein functions, such as flexibility, rigidity, and energy, are entirely determined by the structure of the protein and its environment, although the structure is in turn determined by all the interactions. As such, the FRI measures the topological connectivity of protein atoms or residues and characterizes the geometric compactness of the protein structure. As a consequence, the FRI does not resort to the interaction Hamiltonian and bypasses matrix diagonalization, which underpins most other flexibility analysis methods. FRI's computational complexity is of \\documentclass[12pt]{minimal}\\begin{document}${\\cal O}(N^2)$\\end{document}O(N2) at most, where N is the number of atoms or residues, in contrast to \\documentclass[12pt]{minimal}\\begin{document}${\\cal O}(N^3)$\\end{document}O(N3) for Hamiltonian based methods. We demonstrate that the proposed FRI gives rise to accurate prediction of protein B-Factor for a set of 263 proteins. We show that a parameter free FRI is able to achieve about 95% accuracy of the parameter optimized FRI. An interpolation algorithm is developed to construct continuous atomic flexibility functions for visualization and use with CEWAR. PMID:24320318

Structural paradox in submonolayer chlorine coverage on Au(111)

NASA Astrophysics Data System (ADS)

Zheltov, V. V.; Cherkez, V. V.; Andryushechkin, B. V.; Zhidomirov, G. M.; Kierren, B.; Fagot-Revurat, Y.; Malterre, D.; Eltsov, K. N.

2014-05-01

In this work, we present a combined low-temperature scanning tunneling microscopy (STM) and density functional theory (DFT) study of chlorine adsorption on Au(111) at low coverages. Our STM study of Cl/Au(111) system has shown that at submonolayer coverages (θ < 0.1 ML) chlorine atoms form chainlike structures with abnormally short distances of 3.8 Å between them. Our DFT calculations have shown that chlorine atoms can interact with each other through distortion of the substrate and this indirect elastic interaction is strong enough to affect their arrangement in the chainlike structures.

How to Connect Cardiac Excitation to the Atomic Interactions of Ion Channels.

PubMed

Silva, Jonathan R

2018-01-23

Many have worked to create cardiac action potential models that explicitly represent atomic-level details of ion channel structure. Such models have the potential to define new therapeutic directions and to show how nanoscale perturbations to channel function predispose patients to deadly cardiac arrhythmia. However, there have been significant experimental and theoretical barriers that have limited model usefulness. Recently, many of these barriers have come down, suggesting that considerable progress toward creating these long-sought models may be possible in the near term. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Atomic Forces for Geometry-Dependent Point Multipole and Gaussian Multipole Models

PubMed Central

Elking, Dennis M.; Perera, Lalith; Duke, Robert; Darden, Thomas; Pedersen, Lee G.

2010-01-01

In standard treatments of atomic multipole models, interaction energies, total molecular forces, and total molecular torques are given for multipolar interactions between rigid molecules. However, if the molecules are assumed to be flexible, two additional multipolar atomic forces arise due to 1) the transfer of torque between neighboring atoms, and 2) the dependence of multipole moment on internal geometry (bond lengths, bond angles, etc.) for geometry-dependent multipole models. In the current study, atomic force expressions for geometry-dependent multipoles are presented for use in simulations of flexible molecules. The atomic forces are derived by first proposing a new general expression for Wigner function derivatives ∂Dlm′m/∂Ω. The force equations can be applied to electrostatic models based on atomic point multipoles or Gaussian multipole charge density. Hydrogen bonded dimers are used to test the inter-molecular electrostatic energies and atomic forces calculated by geometry-dependent multipoles fit to the ab initio electrostatic potential (ESP). The electrostatic energies and forces are compared to their reference ab initio values. It is shown that both static and geometry-dependent multipole models are able to reproduce total molecular forces and torques with respect to ab initio, while geometry-dependent multipoles are needed to reproduce ab initio atomic forces. The expressions for atomic force can be used in simulations of flexible molecules with atomic multipoles. In addition, the results presented in this work should lead to further development of next generation force fields composed of geometry-dependent multipole models. PMID:20839297

Effect of atomic size on undercoolability of binary solid solution alloy liquids with Zr, Ti, and Hf using electrostatic levitation

NASA Astrophysics Data System (ADS)

Jeon, S.; Kang, D.-H.; Lee, Y. H.; Lee, S.; Lee, G. W.

2016-11-01

We investigate the relationship between the excess volume and undercoolability of Zr-Ti and Zr-Hf alloy liquids by using electrostatic levitation. Unlike in the case of Zr-Hf alloy liquids in which sizes of the constituent atoms are matched, a remarkable increase of undercoolability and negative excess volumes are observed in Zr-Ti alloy liquids as a function of their compositional ratios. In this work, size mismatch entropies for the liquids were obtained by calculating their hard sphere diameters, number densities, and packing fractions. We also show that the size mismatch entropy, which arises from the differences in atomic sizes of the constituent elements, plays an important role in determining the stabilities of metallic liquids.

First stages of oxide growth on Al(1 1 0) and core-level shifts from density functional theory calculations

NASA Astrophysics Data System (ADS)

Lousada, Cláudio M.; Korzhavyi, Pavel A.

2018-05-01

The formation of islands of O-atoms is the dominant mode of growth of the oxide in the first stages of oxidation of Al(1 1 1). It is however unknown if a similar mechanism exists for other low index surfaces of Al. We performed a density functional theory (DFT) and ab initio molecular dynamics investigation of the first stages of the oxidation of Al(1 1 0) using two distinct models: a homogeneous surface disposition of O-atoms; and a model where the O-atoms are close-spaced forming clusters or islands. We investigated the surface reactions with oxygen up to a coverage of 2 ML and found that for both models the adsorption energy per dissociating O2(g) becomes more negative with increasing coverage. Our results show that for coverages up to 1.25 ML the oxide forms clusters or islands while for coverages higher than 1.5 ML the oxide covers the surface homogeneously. This is because the O-atoms bind preferably to neighboring sites even at the minimum coverage. With increasing coverage, the clusters of O start to form stripes along the [1 1 bar 0] direction. The work function (ϕ) of the surface decreases when going from bare Al(1 1 0) to up to 1 ML coverage of O-atoms, but for coverages of 1.25 ML and higher, ϕ increases. The Al 2p surface core level shifts (SCLS) shift towards higher binding energies with increasing surface coverage of O-atoms and start to approach the values of Al 2p in Al2O3 already at a coverage of 2ML. A relation between the SCLS and the coordination number of Al to O-atoms was made. The Al 2p SCLS increases with increasing coordination to O-atoms, for single, twofold and three-fourfold coordinated cations. For the O-atoms that terminate the surface at the short-bridge sites, the SCLS of O 1s, is largely affected by the proximity to other O-atoms. These results demonstrate that the cooperative effects between surface bound O-atoms have important roles in the mechanism of growth of the oxide at Al(1 1 0), and similarly to what happens for Al(1 1 1), the initial oxidation of Al(1 1 0) proceeds via the formation of islands of O-atoms.

Friction and work function oscillatory behavior for an even and odd number of layers in polycrystalline MoS 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lavini, Francesco; Calò, Annalisa; Gao, Yang

We report on a new oscillatory behavior of nanoscopic friction in continuous polycrystalline MoS 2 films for an odd and even number of atomic layers, related to the different in-plane polarization of crystalline grains and different capability of absorbing charged molecules.

Friction and work function oscillatory behavior for an even and odd number of layers in polycrystalline MoS 2

DOE PAGES

Lavini, Francesco; Calò, Annalisa; Gao, Yang; ...

2018-01-01

We report on a new oscillatory behavior of nanoscopic friction in continuous polycrystalline MoS 2 films for an odd and even number of atomic layers, related to the different in-plane polarization of crystalline grains and different capability of absorbing charged molecules.

The Story of Nanomaterials in Modern Technology: An Advanced Course for Chemistry Teachers

ERIC Educational Resources Information Center

Blonder, Ron

2011-01-01

Nanoscience is an important new field in modern science. It deals with the ability to create materials, devices, and systems having fundamentally new properties and functions by working at the atomic, molecular, and macromolecular levels. Many teachers in the educational system have relatively limited knowledge related to nanochemistry and…

Analytically derived switching functions for exact H2+ eigenstates

NASA Astrophysics Data System (ADS)

Thorson, W. R.; Kimura, M.; Choi, J. H.; Knudson, S. K.

1981-10-01

Electron translation factors (ETF's) appropriate for slow atomic collisions may be constructed using switching functions. In this paper we derive a set of switching functions for the H2+ system by an analytical "two-center decomposition" of the exact molecular eigenstates. These switching functions are closely approximated by the simple form f=bη, where η is the "angle variable" of prolate spheroidal coordinates. For given united atom angular momentum quantum numbers (l,m), the characteristic parameter blm depends only on the quantity c2=-ɛR22, where ɛ is the electronic binding energy and R the internuclear distance in a.u. The resulting parameters are in excellent agreement with those found in our earlier work by a heuristic "optimization" scheme based on a study of coupling matrix-element behavior for a number of H2+ states. An approximate extension to asymmetric cases (HeH2+) has also been made. Nonadiabatic couplings based on these switching functions have been used in recent close-coupling calculations for H+-H(1s) collisions and He2+-H(1s) collisions at energies 1.0-20 keV.

Periodic boundary conditions for QM/MM calculations: Ewald summation for extended Gaussian basis sets

DOE Office of Scientific and Technical Information (OSTI.GOV)

Holden, Zachary C.; Richard, Ryan M.; Herbert, John M., E-mail: herbert@chemistry.ohio-state.edu

2013-12-28

An implementation of Ewald summation for use in mixed quantum mechanics/molecular mechanics (QM/MM) calculations is presented, which builds upon previous work by others that was limited to semi-empirical electronic structure for the QM region. Unlike previous work, our implementation describes the wave function's periodic images using “ChElPG” atomic charges, which are determined by fitting to the QM electrostatic potential evaluated on a real-space grid. This implementation is stable even for large Gaussian basis sets with diffuse exponents, and is thus appropriate when the QM region is described by a correlated wave function. Derivatives of the ChElPG charges with respect tomore » the QM density matrix are a potentially serious bottleneck in this approach, so we introduce a ChElPG algorithm based on atom-centered Lebedev grids. The ChElPG charges thus obtained exhibit good rotational invariance even for sparse grids, enabling significant cost savings. Detailed analysis of the optimal choice of user-selected Ewald parameters, as well as timing breakdowns, is presented.« less

Formic acid decomposition on Pt1/Cu (111) single platinum atom catalyst: Insights from DFT calculations and energetic span model analysis

NASA Astrophysics Data System (ADS)

Wang, Ying-Fan; Li, Kun; Wang, Gui-Chang

2018-04-01

Inspired by the recent surface experimental results that the monatomic Pt catalysts has more excellent hydrogen production that Cu(111) surface, the mechanism of decomposition of formic acid on Cu(111) and single atom Pt1/Cu(111) surface was studied by periodic density functional theory calculations in the present work. The results show that the formic acid tends to undergo dehydrogenation on both surfaces to obtain the hydrogen product of the target product, and the selectivity and catalytic activity of Pt1/Cu (111) surface for formic acid dehydrogenation are better. The reason is that the single atom Pt1/Cu(111) catalyst reduces the reaction energy barrier (i.e., HCOO → CO2 + H) of the critical step of the dehydrogenation reaction due to the fact that the single atom Pt1/Cu(111) catalyst binds formate weakly compared to that of Cu (111) one. Moreover, it was found that the Pt1/Cu (111) binds CO more strongly than that of Cu (111) one and thus leading to the difficult for the formation of CO. These two factors would make the single Pt atom catalyst had the high selectivity for the H2 production. It is hoped that the present work may help people to design the efficient H2 production from HCOOH decomposition by reduce the surface binding strength of HCOO species, for example, using the low coordination number active site like single atom or other related catalytic system.

Nanoscale electrical property studies of individual GeSi quantum rings by conductive scanning probe microscopy.

PubMed

Lv, Yi; Cui, Jian; Jiang, Zuimin M; Yang, Xinju

2012-11-29

The nanoscale electrical properties of individual self-assembled GeSi quantum rings (QRs) were studied by scanning probe microscopy-based techniques. The surface potential distributions of individual GeSi QRs are obtained by scanning Kelvin microscopy (SKM). Ring-shaped work function distributions are observed, presenting that the QRs' rim has a larger work function than the QRs' central hole. By combining the SKM results with those obtained by conductive atomic force microscopy and scanning capacitance microscopy, the correlations between the surface potential, conductance, and carrier density distributions are revealed, and a possible interpretation for the QRs' conductance distributions is suggested.

Defense Small Business Innovation Research Program (SBIR). Abstracts of Phase II Awards. 1985.

DTIC Science & Technology

1985-01-01

SILICIDES : NEW SILICON COMPATIBLE ELECTRO-OPTIC MATERIALS TOPIC: 3 OFFICE: DARPA THE GOAL OF THIS WORK IS TO OBTAIN SINGLE CRYSTAL FILMS OF SEMI...CONSTITUENTS. CON- STITUENTS WITH IONIZATION POTENTIALS COMPARABLE TO THE WORK FUNCTION A ARE EVOLVED AS POSITIVE IONS (USUALLY SODIUM ATOMIC IONS FROM... SODIUM COMPOUND IMPURITIES). ARRIVAL OF A PARTICLE AT THE SURFACE CAUSES A BURST OF MANY IONS WHICH ARE DRAWN TO A NEARBY ION COLLECTOR ELECT- RODE

Nanotechnology Presentation Agenda

NASA Technical Reports Server (NTRS)

2005-01-01

Working at the atomic, molecular and supra-molecular levels, in the length scale of approximately 1 - 100 nm range, in order to understand, create and use materials, devices and systems with fundamentally new properties and functions because of their small structure. NNI definition encourages new contributions that were not possible.before. Novel phenomena, properties and functions at nanoscale,which are non scalable outside of the nm domain. The ability to measure / control / manipulate matter at the nanoscale in order to change those properties and functions. Integration along length scales, and fields of application.

Evaluation of optical and electronic properties of silicon nano-agglomerates embedded in SRO: applying density functional theory

PubMed Central

2014-01-01

In systems in atomic scale and nanoscale such as clusters or agglomerates constituted by particles from a few to less than 100 atoms, quantum confinement effects are very important. Their optical and electronic properties are often dependent on the size of the systems and the way in which the atoms in these clusters are bonded. Generally, these nanostructures display optical and electronic properties significantly different to those found in corresponding bulk materials. Silicon agglomerates embedded in silicon rich oxide (SRO) films have optical properties, which have been reported to be directly dependent on silicon nanocrystal size. Furthermore, the room temperature photoluminescence (PL) of SRO has repeatedly generated a huge interest due to its possible applications in optoelectronic devices. However, a plausible emission mechanism has not been widely accepted in the scientific community. In this work, we present a short review about the experimental results on silicon nanoclusters in SRO considering different techniques of growth. We focus mainly on their size, Raman spectra, and photoluminescence spectra. With this as background, we employed the density functional theory with a functional B3LYP and a basis set 6-31G* to calculate the optical and electronic properties of clusters of silicon (constituted by 15 to 20 silicon atoms). With the theoretical calculation of the structural and optical properties of silicon clusters, it is possible to evaluate the contribution of silicon agglomerates in the luminescent emission mechanism, experimentally found in thin SRO films. PMID:25276105

Study of solid/liquid and solid/gas interfaces in Cu-isoleucine complex by surface X-ray diffraction

NASA Astrophysics Data System (ADS)

Ferrer, Pilar; Rubio-Zuazo, Juan; Castro, German R.

2013-02-01

The enzymes could be understood like structures formed by amino acids bonded with metals, which act as active sites. The research on the coordination of metal-amino acid complexes will bring light on the behavior of metal enzymes, due to the close relation existing between the atomic structure and the functionality. The Cu-isoleucine bond is considered as a good model system to attain a better insight into the characteristics of naturally occurring copper metalloproteins. The surface structure of metal-amino acid complex could be considered as a more realistic model for real systems under biologic working conditions, since the molecular packing is decreased. In the surface, the structural constrains are reduced, keeping the structural capability of surface complex to change as a function of the surrounding environment. In this work, we present a surface X-ray diffraction study on Cu-isoleucine complex under different ambient conditions. Cu(Ile)2 crystals of about 5 mm × 5 mm × 1 mm have been growth, by seeding method in a supersaturated solution, presenting a surface of high quality. The sample for the surface diffraction study was mounted on a cell specially designed for solid/liquid or solid/gas interface analysis. The Cu-isoleucine crystal was measured under a protective dry N2 gas flow and in contact with a saturated metal amino acid solution. The bulk and the surface signals were compared, showing different atomic structures. In both cases, from surface diffraction data, it is observed that the atomic structure of the top layer undergoes a clear structural deformation. A non-uniform surface relaxation is observed producing an inhomogeneous displacement of the surface atoms towards the surface normal.

Spatial transport of electron quantum states with strong attosecond pulses

NASA Astrophysics Data System (ADS)

Chovancova, M.; Agueny, H.; Førre, M.; Kocbach, L.; Hansen, J. P.

2017-11-01

This work follows up the work of Dimitrovsky, Briggs and co-workers on translated electron atomic states by a strong field of an atto-second laser pulse, also described as creation of atoms without a nucleus. Here, we propose a new approach by analyzing the electron states in the Kramers-Henneberger moving frame in the dipole approximation. The wave function follows the displacement vector α (t). This allows arbitrarily shaped pulses, including the model delta-function potentials in the Dimitrovsky and Briggs approach. In the case of final-length single-cycle pulses, we apply both the Kramers-Henneberger moving frame analysis and a full numerical treatment of our 1D model. When the laser pulse frequency exceeds the frequency associated by the energy difference between initial and final states, the entire wavefunction is translated in space nearly without loss of coherence, to a well defined distance from the original position where the ionized core is left behind. This statement is demonstrated on the excited Rydberg states (n = 10, n = 15), where almost no distortion in the transported wave functions has been observed. However, the ground state (n = 1) is visibly distorted during the removal by pulses of reasonable frequencies, as also predicted by Dimitrovsky and Briggs analysis. Our approach allows us to analyze general pulses as well as the model delta-function potentials on the same footing in the Kramers-Henneberger frame.

The interaction of hydrogen with the {010} surfaces of Mg and Fe olivine as models for interstellar dust grains: a density functional theory study

PubMed Central

Downing, C. A.; Ahmady, B.; Catlow, C. R. A.; de Leeuw, N. H.

2013-01-01

There is no consensus as yet to account for the significant presence of water on the terrestrial planets, but suggested sources include direct hydrogen adsorption from the parent molecular cloud after the planets’ formation, and delivery of hydrous material via comets or asteroids external to the zone of the terrestrial planets. Alternatively, a more recent idea is that water may have directly adsorbed onto the interstellar dust grains involved in planetary formation. In this work, we use electronic structure calculations based on the density functional theory to investigate and compare the bulk and {010} surface structures of the magnesium and iron end-members of the silicate mineral olivine, namely forsterite and fayalite, respectively. We also report our results on the adsorption of atomic hydrogen at the mineral surfaces, where our calculations show that there is no activation barrier to the adsorption of atomic hydrogen at these surfaces. Furthermore, different surface sites activate the atom to form either adsorbed hydride or proton species in the form of hydroxy groups on the same surface, which indicates that these mineral surfaces may have acted as catalytic sites in the immobilization and reaction of hydrogen atoms to form dihydrogen gas or water molecules. PMID:23734054

Atomic scale behavior of oxygen-based radicals in water

NASA Astrophysics Data System (ADS)

Verlackt, C. C. W.; Neyts, E. C.; Bogaerts, A.

2017-03-01

Cold atmospheric pressure plasmas in and in contact with liquids represent a growing field of research for various applications. Understanding the interactions between the plasma generated species and the liquid is crucial. In this work we perform molecular dynamics (MD) simulations based on a quantum mechanical method, i.e. density-functional based tight-binding (DFTB), to examine the interactions of OH radicals and O atoms in bulk water. Our calculations reveal that the transport of OH radicals through water is not only governed by diffusion, but also by an equilibrium reaction of H-abstraction with water molecules. Furthermore, when two OH radicals encounter each other, they either form a stable cluster, or react, resulting in the formation of a new water molecule and an O atom. In addition, the O atoms form either oxywater (when in singlet configuration) or they remain stable in solution (when in triplet configuration), stressing the important role that O atoms can play in aqueous solution, and in contact with biomolecules. Our observations are in line with both experimental and ab initio results from the literature.

Universality of maximum-work efficiency of a cyclic heat engine based on a finite system of ultracold atoms.

PubMed

Ye, Zhuolin; Hu, Yingying; He, Jizhou; Wang, Jianhui

2017-07-24

We study the performance of a cyclic heat engine which uses a small system with a finite number of ultracold atoms as its working substance and works between two heat reservoirs at constant temperatures T h and T c (

Charge injection in thin dielectric layers by atomic force microscopy: influence of geometry and material work function of the AFM tip on the injection process

NASA Astrophysics Data System (ADS)

Villeneuve-Faure, C.; Makasheva, K.; Boudou, L.; Teyssedre, G.

2016-06-01

Charge injection and retention in thin dielectric layers remain critical issues for the reliability of many electronic devices because of their association with a large number of failure mechanisms. To overcome this drawback, a deep understanding of the mechanisms leading to charge injection close to the injection area is needed. Even though the charge injection is extensively studied and reported in the literature to characterize the charge storage capability of dielectric materials, questions about charge injection mechanisms when using atomic force microscopy (AFM) remain open. In this paper, a thorough study of charge injection by using AFM in thin plasma-processed amorphous silicon oxynitride layers with properties close to that of thermal silica layers is presented. The study considers the impact of applied voltage polarity, work function of the AFM tip coating and tip curvature radius. A simple theoretical model was developed and used to analyze the obtained experimental results. The electric field distribution is computed as a function of tip geometry. The obtained experimental results highlight that after injection in the dielectric layer the charge lateral spreading is mainly controlled by the radial electric field component independently of the carrier polarity. The injected charge density is influenced by the nature of electrode metal coating (work function) and its geometry (tip curvature radius). The electron injection is mainly ruled by the Schottky injection barrier through the field electron emission mechanism enhanced by thermionic electron emission. The hole injection mechanism seems to differ from the electron one depending on the work function of the metal coating. Based on the performed analysis, it is suggested that for hole injection by AFM, pinning of the metal Fermi level with the metal-induced gap states in the studied silicon oxynitride layers starts playing a role in the injection mechanisms.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Strayer, M.R.

This talk surveys a thirteen-year collaboration with Chris Bottcher on various aspects of strong field electrodynamics. Most of the work centers on the atomic physics associated with the peripheral collisions of ultrarelativistic heavy atoms. The earliest, beginning in about 1979, dealt with the spontaneous emission of positrons from nuclear quasimolecules and touched briefly on the formation of axions as a possible explanation of the anomalous peaks in the spectrum. This work stimulated the extensive studies of particle production from coherent fields that laid the foundations for investigations of nuclear form factors, structure functions, and production mechanisms for the Higgs andmore » other exotic particles. Chris conjectured that the strong fields that are present in these collisions would give rise to nonperturbative effects. Thus, during this time, Chris also worked to develop basis-spline collocation methods for solving dynamical relativistic fermions in super strong fields. This was perhaps one of the best of times for Chris; on these problems alone, he co-authored fifty articles with more than twenty different collaborators.« less

On the work function and the charging of small ( r ≤ 5 nm) nanoparticles in plasmas

NASA Astrophysics Data System (ADS)

Kalered, E.; Brenning, N.; Pilch, I.; Caillault, L.; Minéa, T.; Ojamäe, L.

2017-01-01

The growth of nanoparticles (NPs) in plasmas is an attractive technique where improved theoretical understanding is needed for quantitative modeling. The variation of the work function W with size for small NPs, rN P≤ 5 nm, is a key quantity for modeling of three NP charging processes that become increasingly important at a smaller size: electron field emission, thermionic electron emission, and electron impact detachment. Here we report the theoretical values of the work function in this size range. Density functional theory is used to calculate the work functions for a set of NP charge numbers, sizes, and shapes, using copper for a case study. An analytical approximation is shown to give quite accurate work functions provided that rN P > 0.4 nm, i.e., consisting of about >20 atoms, and provided also that the NPs have relaxed close to spherical shape. For smaller sizes, W deviates from the approximation, and also depends on the charge number. Some consequences of these results for nanoparticle charging are outlined. In particular, a decrease in W for NP radius below about 1 nm has fundamental consequences for their charge in a plasma environment, and thereby on the important processes of NP nucleation, early growth, and agglomeration.

Lithium effects on the mechanical and electronic properties of germanium nanowires

NASA Astrophysics Data System (ADS)

González-Macías, A.; Salazar, F.; Miranda, A.; Trejo-Baños, A.; Pérez, L. A.; Carvajal, E.; Cruz-Irisson, M.

2018-04-01

Semiconductor nanowire arrays promise rapid development of a new generation of lithium (Li) batteries because they can store more Li atoms than conventional crystals due to their large surface areas. During the charge-discharge process, the electrodes experience internal stresses that fatigue the material and limit the useful life of the battery. The theoretical study of electronic and mechanical properties of lithiated nanowire arrays allows the designing of electrode materials that could improve battery performance. In this work, we present a density functional theory study of the electronic band structure, formation energy, binding energy, and Young’s modulus (Y) of hydrogen passivated germanium nanowires (H-GeNWs) grown along the [111] and [001] crystallographic directions with surface and interstitial Li atoms. The results show that the germanium nanowires (GeNWs) with surface Li atoms maintain their semiconducting behavior but their energy gap size decreases when the Li concentration grows. In contrast, the GeNWs can have semiconductor or metallic behavior depending on the concentration of the interstitial Li atoms. On the other hand, Y is an indicator of the structural changes that GeNWs suffer due to the concentration of Li atoms. For surface Li atoms, Y stays almost constant, whereas for interstitial Li atoms, the Y values indicate important structural changes in the GeNWs.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, W. R.; Nilsen, J.

Here, the influence of finite relaxation times on Thomson scattering from warm dense plasmas is examined within the framework of the average-atom approximation. Presently most calculations use the collision-free Lindhard dielectric function to evaluate the free-electron contribution to the Thomson cross section. In this work, we use the Mermin dielectric function, which includes relaxation time explicitly. The relaxation time is evaluated by treating the average atom as an impurity in a uniform electron gas and depends critically on the transport cross section. The calculated relaxation rates agree well with values inferred from the Ziman formula for the static conductivity andmore » also with rates inferred from a fit to the frequency-dependent conductivity. Transport cross sections determined by the phase-shift analysis in the average-atom potential are compared with those evaluated in the commonly used Born approximation. The Born approximation converges to the exact cross sections at high energies; however, differences that occur at low energies lead to corresponding differences in relaxation rates. The relative importance of including relaxation time when modeling x-ray Thomson scattering spectra is examined by comparing calculations of the free-electron dynamic structure function for Thomson scattering using Lindhard and Mermin dielectric functions. Applications are given to warm dense Be plasmas, with temperatures ranging from 2 to 32 eV and densities ranging from 2 to 64 g/cc.« less

Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

PubMed

Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

2016-12-28

Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

Parity oscillations and photon correlation functions in the Z2-U (1 ) Dicke model at a finite number of atoms or qubits

NASA Astrophysics Data System (ADS)

Yi-Xiang, Yu; Ye, Jinwu; Zhang, CunLin

2016-08-01

Four standard quantum optics models, that is, the Rabi, Dicke, Jaynes-Cummings, and Tavis-Cummings models, were proposed by physicists many decades ago. Despite their relative simple forms and many previous theoretical works, their physics at a finite N , especially inside the superradiant regime, remain unknown. In this work, by using the strong-coupling expansion and exact diagonalization (ED), we study the Z2-U(1 ) Dicke model with independent rotating-wave coupling g and counterrotating-wave coupling g' at a finite N . This model includes the four standard quantum optics models as its various special limits. We show that in the superradiant phase, the system's energy levels are grouped into doublets with even and odd parity. Any anisotropy β =g'/g ≠1 leads to the oscillation of parities in both the ground and excited doublets as the atom-photon coupling strength increases. The oscillations will be pushed to the infinite coupling strength in the isotropic Z2 limit β =1 . We find nearly perfect agreement between the strong-coupling expansion and the ED in the superradiant regime when β is not too small. We also compute the photon correlation functions, squeezing spectrum, and number correlation functions that can be measured by various standard optical techniques.

Geometrical comparison of two protein structures using Wigner-D functions.

PubMed

Saberi Fathi, S M; White, Diana T; Tuszynski, Jack A

2014-10-01

In this article, we develop a quantitative comparison method for two arbitrary protein structures. This method uses a root-mean-square deviation characterization and employs a series expansion of the protein's shape function in terms of the Wigner-D functions to define a new criterion, which is called a "similarity value." We further demonstrate that the expansion coefficients for the shape function obtained with the help of the Wigner-D functions correspond to structure factors. Our method addresses the common problem of comparing two proteins with different numbers of atoms. We illustrate it with a worked example. © 2014 Wiley Periodicals, Inc.

Early stages of epitaxial CoSi 2 formation on Si(111) surface as investigated by ARUPS, XPS, LEED and work function variation

NASA Astrophysics Data System (ADS)

Pirri, C.; Peruchetti, J. C.; Gewinner, G.; Derrien, J.

1985-04-01

We performed the CoSi 2 formation on a clean (7 × 7) Si(111) surface under UHV conditions. The used techniques were angle resolved UV photoemission, X-ray photoemission, work function change and low energy electron diffraction in order to study the electronic and structural properties of the interface during its formation. At room temperature, a small amount of Co reacts strongly with Si to form an interfacial and very thin cobalt suicide. The ultraviolet photoelectron spectrum displays already two features corresponding respectively to the Co 3d and Si 3p electron bonding states and the Co 3d non-bonding states. With increasing coverage ( θ ≳ 4 ML) it seems that the interfacial suicide prevents further Co-Si interdiffusion to achieve the suicide reaction and a metal rich film is found. At high temperature (˜ 600°C) and in the first monolayer range, several superstructures are found (√7 × √7, and 2 × 2). They are induced by a Co-Si bidimensional compound where the Co atoms are not yet completely surrounded by Si atoms as in their bulk CoSi 2 structure. With increasing coverage, a CoSi 2-like photoemission spectrum is observed reflecting the formation of the disilicide. The LEED pattern testifies an epitaxial growth displaying a (1 × 1) CoSi 2 diagram. The work function change technique also reflects faithfully this growth.

Theoretical analysis of the electronic properties of the sex pheromone and its analogue derivatives in the female processionary moth Thaumetopoea pytiocampa.

PubMed

Chamorro, Ester R; Sequeira, Alfredo F; Zalazar, M Fernanda; Peruchena, Nélida M

2008-09-15

In the present work, the distribution of the electronic charge density of the natural sex pheromone, the (Z)-13-hexadecen-11-ynyl acetate, in the female processionary moth, Thaumetopoea pytiocampa, and its nine analogue derivatives was studied within the framework of the Density Functional Theory and the Atoms in Molecules (AIM) Theory at B3LYP/6-31G *//B3LYP/6-31++G * * level. Additionally, molecular electrostatic potential (MEP) maps of the previously mentioned compounds were computed and compared. Furthermore, the substitution of hydrogen atoms from the methyl group in the acetate group by electron withdrawing substituents (i.e., halogen atoms) as well as the replacement effect of hydrogen by electron donor substituents (+I effect) as methyl group, were explored. The key feature of the topological distribution of the charge density in analogue compounds, such as the variations of the topological properties encountered in the region formed by neighbouring atoms from the substitution site were presented and discussed. Using topological parameters, such as electronic charge density, Laplacian, kinetic energy density, and potential energy density evaluated at bond critical points (BCP), we provide here a detailed analysis of the nature of the chemical bonding of these molecules. In addition, the atomic properties (population, charge, energy, volume, and dipole moment) were determined on selected atoms. These properties were analyzed at the substitution site (with respect to the natural sex pheromone) and related to the biological activity and to the possible binding site with the pheromone binding protein, (PBP). Moreover, the Laplacian function of the electronic density was used to locate electrophilic regions susceptible to be attacked (by deficient electron atoms or donor hydrogen). Our results indicate that the change in the atomic properties, such as electronic population and atomic volume, are sensitive indicators of the loss of the biological activity in the analogues studied here. The crucial interaction between the acetate group of the natural sex pheromone and the PBP is most likely to be a hydrogen bonding and the substitution of hydrogen atoms by electronegative atoms in the pheromone molecule reduces the hydrogen acceptor capacity. This situation is mirrored by the diminish of the electronic population on carbon and oxygen atoms at the carbonylic group in the halo-acetate group. Additionally, the modified acetate group (with electronegative atoms) shows new charge concentration critical points or regions of concentration of charge density in which an electrophilic attack can also occur. Finally, the use of the topological analysis based in the charge density distribution and its Laplacian function, in conjunction with MEP maps provides valuable information about the steric volume and electronic requirement of the sex pheromone for binding to the PBP.

Li-Ion Localization and Energetics as a Function of Anode Structure.

PubMed

McNutt, Nicholas W; McDonnell, Marshall; Rios, Orlando; Keffer, David J

2017-03-01

In this work, we study the effect of carbon composite anode structure on the localization and energetics of Li-ions. A computational molecular dynamics study is combined with experimental results from neutron scattering experiments to understand the effect of composite density, crystallite size, volume fraction of crystalline carbon, and ion loading on the nature of ion storage in novel, lignin-derived composite materials. In a recent work, we demonstrated that these carbon composites display a fundamentally different mechanism for Li-ion storage than traditional graphitic anodes. The edges of the crystalline and amorphous fragments of aromatic carbon that exist in these composites are terminated by hydrogen atoms, which play a crucial role in adsorption. In this work, we demonstrate how differences in composite structure due to changes in the processing conditions alter the type and extent of the interface between the amorphous and crystalline domains, thus impacting the nature of Li-ion storage. The effects of structural properties are evaluated using a suite of pair distribution functions as well as an original technique to extract archetypal structures, in the form of three-dimensional atomic density distributions, from highly disordered systems. The energetics of Li-ion binding are understood by relating changes in the energy and charge distributions to changes in structural properties. The distribution of Li-ion energies reveals that some structures lead to greater chemisorption, while others have greater physisorption. Carbon composites with a high volume fraction of small crystallites demonstrate the highest ion storage capacity because of the high interfacial area between the crystalline and amorphous domains. At these interfaces, stable H atoms, terminating the graphitic crystallites, provide favorable sites for reversible Li adsorption.

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

NASA Astrophysics Data System (ADS)

Parrish, Robert M.; Sherrill, C. David

2014-07-01

We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work through the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-π interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.

Spatial assignment of symmetry adapted perturbation theory interaction energy components: The atomic SAPT partition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parrish, Robert M.; Sherrill, C. David, E-mail: sherrill@gatech.edu

2014-07-28

We develop a physically-motivated assignment of symmetry adapted perturbation theory for intermolecular interactions (SAPT) into atom-pairwise contributions (the A-SAPT partition). The basic precept of A-SAPT is that the many-body interaction energy components are computed normally under the formalism of SAPT, following which a spatially-localized two-body quasiparticle interaction is extracted from the many-body interaction terms. For electrostatics and induction source terms, the relevant quasiparticles are atoms, which are obtained in this work through the iterative stockholder analysis (ISA) procedure. For the exchange, induction response, and dispersion terms, the relevant quasiparticles are local occupied orbitals, which are obtained in this work throughmore » the Pipek-Mezey procedure. The local orbital atomic charges obtained from ISA additionally allow the terms involving local orbitals to be assigned in an atom-pairwise manner. Further summation over the atoms of one or the other monomer allows for a chemically intuitive visualization of the contribution of each atom and interaction component to the overall noncovalent interaction strength. Herein, we present the intuitive development and mathematical form for A-SAPT applied in the SAPT0 approximation (the A-SAPT0 partition). We also provide an efficient series of algorithms for the computation of the A-SAPT0 partition with essentially the same computational cost as the corresponding SAPT0 decomposition. We probe the sensitivity of the A-SAPT0 partition to the ISA grid and convergence parameter, orbital localization metric, and induction coupling treatment, and recommend a set of practical choices which closes the definition of the A-SAPT0 partition. We demonstrate the utility and computational tractability of the A-SAPT0 partition in the context of side-on cation-π interactions and the intercalation of DNA by proflavine. A-SAPT0 clearly shows the key processes in these complicated noncovalent interactions, in systems with up to 220 atoms and 2845 basis functions.« less

Intrinsic retrieval efficiency for quantum memories: A three-dimensional theory of light interaction with an atomic ensemble

NASA Astrophysics Data System (ADS)

Gujarati, Tanvi P.; Wu, Yukai; Duan, Luming

2018-03-01

Duan-Lukin-Cirac-Zoller quantum repeater protocol, which was proposed to realize long distance quantum communication, requires usage of quantum memories. Atomic ensembles interacting with optical beams based on off-resonant Raman scattering serve as convenient on-demand quantum memories. Here, a complete free space, three-dimensional theory of the associated read and write process for this quantum memory is worked out with the aim of understanding intrinsic retrieval efficiency. We develop a formalism to calculate the transverse mode structure for the signal and the idler photons and use the formalism to study the intrinsic retrieval efficiency under various configurations. The effects of atomic density fluctuations and atomic motion are incorporated by numerically simulating this system for a range of realistic experimental parameters. We obtain results that describe the variation in the intrinsic retrieval efficiency as a function of the memory storage time for skewed beam configuration at a finite temperature, which provides valuable information for optimization of the retrieval efficiency in experiments.

Hierarchical atom type definitions and extensible all-atom force fields.

PubMed

Jin, Zhao; Yang, Chunwei; Cao, Fenglei; Li, Feng; Jing, Zhifeng; Chen, Long; Shen, Zhe; Xin, Liang; Tong, Sijia; Sun, Huai

2016-03-15

The extensibility of force field is a key to solve the missing parameter problem commonly found in force field applications. The extensibility of conventional force fields is traditionally managed in the parameterization procedure, which becomes impractical as the coverage of the force field increases above a threshold. A hierarchical atom-type definition (HAD) scheme is proposed to make extensible atom type definitions, which ensures that the force field developed based on the definitions are extensible. To demonstrate how HAD works and to prepare a foundation for future developments, two general force fields based on AMBER and DFF functional forms are parameterized for common organic molecules. The force field parameters are derived from the same set of quantum mechanical data and experimental liquid data using an automated parameterization tool, and validated by calculating molecular and liquid properties. The hydration free energies are calculated successfully by introducing a polarization scaling factor to the dispersion term between the solvent and solute molecules. © 2015 Wiley Periodicals, Inc. © 2015 Wiley Periodicals, Inc.

Double-walled silicon nanotubes: an ab initio investigation

NASA Astrophysics Data System (ADS)

Lima, Matheus P.

2018-02-01

The synthesis of silicon nanotubes realized in the last decade demonstrates multi-walled tubular structures consisting of Si atoms in {{sp}}2 and the {{sp}}3 hybridizations. However, most of the theoretical models were elaborated taking as the starting point {{sp}}2 structures analogous to carbon nanotubes. These structures are unfavorable due to the natural tendency of the Si atoms to undergo {{sp}}3. In this work, through ab initio simulations based on density functional theory, we investigated double-walled silicon nanotubes proposing layered tubes possessing most of the Si atoms in an {{sp}}3 hybridization, and with few {{sp}}2 atoms localized at the outer wall. The lowest-energy structures have metallic behavior. Furthermore, the possibility to tune the band structure with the application of a strain was demonstrated, inducing a metal-semiconductor transition. Thus, the behavior of silicon nanotubes differs significantly from carbon nanotubes, and the main source of the differences is the distortions in the lattice associated with the tendency of Si to make four chemical bonds.

How polarizabilities and C6 coefficients actually vary with atomic volume

NASA Astrophysics Data System (ADS)

Gould, Tim

2016-08-01

In this work, we investigate how atomic C6 coefficients and static dipole polarizabilities α scale with effective volume. We show, using confined atoms covering rows 1-5 of the periodic table, that C 6 / C6 R ≈ ( V / VR ) p Z and α / α R ≈ ( V / VR ) pZ ' (for volume V = ∫ d r /4 π 3 r 3 n ( r ) ), where C6 R , αR, and VR are the reference values and effective volume of the free atom. The scaling exponents pZ and pZ ' vary substantially as a function of element number Z = N, in contrast to the standard "rule of thumb" that pZ = 2 and pZ ' = 1 . Remarkably, we find that the polarizability and C6 exponents p' and p are related by p' ≈ p - 0.615 rather than the expected p' ≈ p/2. Results are largely independent of the form of the confining potential (harmonic, cubic, and quartic potentials are considered) and kernel approximation, justifying this analysis.

DFT investigations of the hydrogenation effect on silicene/graphene hybrids.

PubMed

Drissi, L B; Saidi, E H; Bousmina, M; Fassi-Fehri, O

2012-12-05

We report here a study on the effect of hydrogenation on a new one-atom thick material made of silicon and carbon atoms (silicene/graphene (SG) hybrid) within density functional theory. The structural, electronic and magnetic properties are investigated for non-, semi- and fully hydrogenated SG hybrids in a chair configuration and are compared with their parent materials. Calculations reveal that pure SG is a non-zero band gap semi-conductor with stable planar honeycomb structure. So mixing C and Si in an alternating manner gives another way to generate a finite band gap in one-atom thick materials. Fully hydrogenation makes the gap larger; however half chemical modification with H reduces the gap in favor of ferromagnetism order. The findings of this work open a wide spectrum of possibilities for designing SG-based nanodevices with controlled and tuned properties.

Wave-packet continuum-discretization approach to ion-atom collisions including rearrangement: Application to differential ionization in proton-hydrogen scattering

NASA Astrophysics Data System (ADS)

Abdurakhmanov, I. B.; Bailey, J. J.; Kadyrov, A. S.; Bray, I.

2018-03-01

In this work, we develop a wave-packet continuum-discretization approach to ion-atom collisions that includes rearrangement processes. The total scattering wave function is expanded using a two-center basis built from wave-packet pseudostates. The exact three-body Schrödinger equation is converted into coupled-channel differential equations for time-dependent expansion coefficients. In the asymptotic region these time-dependent coefficients represent transition amplitudes for all processes including elastic scattering, excitation, ionization, and electron capture. The wave-packet continuum-discretization approach is ideal for differential ionization studies as it allows one to generate pseudostates with arbitrary energies and distribution. The approach is used to calculate the double differential cross section for ionization in proton collisions with atomic hydrogen. Overall good agreement with experiment is obtained for all considered cases.

Atomic mean-square displacement of a solid: A Green's-function approach

NASA Astrophysics Data System (ADS)

Shukla, R. C.; Hübschle, Hermann

1989-07-01

We have presented a Green's-function method of calculating the atomic mean-square displacement (MSD) of a solid. The method effectively sums a class of all anharmonic contributions to the MSD. From the point of view of perturbation theory (PT) our expression for MSD includes the lowest-order (λ2) PT contributions (cubic and quartic) with correct numerical coefficients. The numerical results obtained by this method in the high-temperature limit for a fcc nearest-neighbor Lennard-Jones-solid model are in excellent agreement with the Monte Carlo (MC) method for the same model over the entire temperature range of the solid. Highly accurate results for the order-λ2 PT contributions to MSD are obtained by eliminating the uncertainty in the convergence of the cubic contributions in the earlier work of Heiser, Shukla, and Cowly and they are now in much better agreement with the MC results but still inferior to the Green's-function method at the highest temperature.

Shot noise in parallel atomic wires from first principles

NASA Astrophysics Data System (ADS)

Lagerqvist, Johan; Chen, Yu-Chang; di Ventra, Massimiliano

2003-03-01

We report first-principles calculations of shot noise in two parallel carbon atomic wires as a function of the wires separation and length. The calculations have been performed with a novel field-theoretic approach to calculate shot noise [1] in terms of the single-particle wavefunctions obtained with density-functional theory.[2] We find that current fluctuations are a non-linear function of the distance between the wires and can be suppressed at wires separations small compared to the independent-wire distance. We discuss these results in terms of the coherence effects between the wires and the interference effects at the contacts. Work supported in part by NSF, Carilion Biomedical Institute and ACS-Petroleum Research Fund. [1] Y.-C. Chen and M. Di Ventra, submitted. [2] N.D. Lang, Phys. Rev. B 52, 5335 (1995); M. Di Ventra and N.D. Lang, Phys. Rev. B 65, 045402 (2002); Z. Yang, A. Tackett and M. Di Ventra, Phys. Rev. B 66, 041405 (2002).

Extremely-efficient, miniaturized, long-lived alpha-voltaic power source using liquid gallium

NASA Technical Reports Server (NTRS)

Snyder, G. Jeffrey (Inventor); Patel, Jagdishbhai (Inventor); Fleurial, Jean-Pierre (Inventor)

2004-01-01

A power source converts .alpha.-particle energy to electricity for use in electrical systems. Liquid gallium or other liquid medium is subjected to .alpha.-particle emissions. Electrons are freed by collision from neutral gallium atoms to provide gallium ions. The electrons migrate to a cathode while the gallium ions migrate to an anode. A current and/or voltage difference then arises between the cathode and anode because of the work function difference of the cathode and anode. Gallium atoms are regenerated by the receiving of electrons from the anode enabling the generation of additional electrons from additional .alpha.-particle collisions.

a Point-Like Picture of the Hydrogen Atom

NASA Astrophysics Data System (ADS)

Faghihi, F.; Jangjoo, A.; Khani, M.

A point-like picture of the Schrödinger solution for hydrogen atom is worked to emphasize that "point-like particles" may describe as "probability wave function". In each case, the three-dimensional shape of the |Ψnlm(rn, cosθ)|2 is plotted and the paths of the point-like electron (it is better to say reduced mass of the pair particles) are described in each closed shell. Finally, the orbital shape of the molecules are given according to the present simple model. In our opinion, "interpretations of the Correspondence Principle", which is a basic principle in all elementary quantum text, seems to be reviewed again!

Grassmann phase space theory and the Jaynes–Cummings model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalton, B.J., E-mail: bdalton@swin.edu.au; Centre for Atom Optics and Ultrafast Spectroscopy, Swinburne University of Technology, Melbourne, Victoria 3122; Garraway, B.M.

2013-07-15

The Jaynes–Cummings model of a two-level atom in a single mode cavity is of fundamental importance both in quantum optics and in quantum physics generally, involving the interaction of two simple quantum systems—one fermionic system (the TLA), the other bosonic (the cavity mode). Depending on the initial conditions a variety of interesting effects occur, ranging from ongoing oscillations of the atomic population difference at the Rabi frequency when the atom is excited and the cavity is in an n-photon Fock state, to collapses and revivals of these oscillations starting with the atom unexcited and the cavity mode in a coherentmore » state. The observation of revivals for Rydberg atoms in a high-Q microwave cavity is key experimental evidence for quantisation of the EM field. Theoretical treatments of the Jaynes–Cummings model based on expanding the state vector in terms of products of atomic and n-photon states and deriving coupled equations for the amplitudes are a well-known and simple method for determining the effects. In quantum optics however, the behaviour of the bosonic quantum EM field is often treated using phase space methods, where the bosonic mode annihilation and creation operators are represented by c-number phase space variables, with the density operator represented by a distribution function of these variables. Fokker–Planck equations for the distribution function are obtained, and either used directly to determine quantities of experimental interest or used to develop c-number Langevin equations for stochastic versions of the phase space variables from which experimental quantities are obtained as stochastic averages. Phase space methods have also been developed to include atomic systems, with the atomic spin operators being represented by c-number phase space variables, and distribution functions involving these variables and those for any bosonic modes being shown to satisfy Fokker–Planck equations from which c-number Langevin equations are often developed. However, atomic spin operators satisfy the standard angular momentum commutation rules rather than the commutation rules for bosonic annihilation and creation operators, and are in fact second order combinations of fermionic annihilation and creation operators. Though phase space methods in which the fermionic operators are represented directly by c-number phase space variables have not been successful, the anti-commutation rules for these operators suggest the possibility of using Grassmann variables—which have similar anti-commutation properties. However, in spite of the seminal work by Cahill and Glauber and a few applications, the use of phase space methods in quantum optics to treat fermionic systems by representing fermionic annihilation and creation operators directly by Grassmann phase space variables is rather rare. This paper shows that phase space methods using a positive P type distribution function involving both c-number variables (for the cavity mode) and Grassmann variables (for the TLA) can be used to treat the Jaynes–Cummings model. Although it is a Grassmann function, the distribution function is equivalent to six c-number functions of the two bosonic variables. Experimental quantities are given as bosonic phase space integrals involving the six functions. A Fokker–Planck equation involving both left and right Grassmann differentiations can be obtained for the distribution function, and is equivalent to six coupled equations for the six c-number functions. The approach used involves choosing the canonical form of the (non-unique) positive P distribution function, in which the correspondence rules for the bosonic operators are non-standard and hence the Fokker–Planck equation is also unusual. Initial conditions, such as those above for initially uncorrelated states, are discussed and used to determine the initial distribution function. Transformations to new bosonic variables rotating at the cavity frequency enable the six coupled equations for the new c-number functions–that are also equivalent to the canonical Grassmann distribution function–to be solved analytically, based on an ansatz from an earlier paper by Stenholm. It is then shown that the distribution function is exactly the same as that determined from the well-known solution based on coupled amplitude equations. In quantum–atom optics theories for many atom bosonic and fermionic systems are needed. With large atom numbers, treatments must often take into account many quantum modes—especially for fermions. Generalisations of phase space distribution functions of phase space variables for a few modes to phase space distribution functionals of field functions (which represent the field operators, c-number fields for bosons, Grassmann fields for fermions) are now being developed for large systems. For the fermionic case, the treatment of the simple two mode problem represented by the Jaynes–Cummings model is a useful test case for the future development of phase space Grassmann distribution functional methods for fermionic applications in quantum–atom optics. -- Highlights: •Novel phase space theory of the Jaynes–Cummings model using Grassmann variables. •Fokker–Planck equations solved analytically. •Results agree with the standard quantum optics treatment. •Grassmann phase space theory applicable to fermion many-body problems.« less

Multiscale multiphysics and multidomain models—Flexibility and rigidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Kelin; Opron, Kristopher; Wei, Guo-Wei, E-mail: wei@math.msu.edu

The emerging complexity of large macromolecules has led to challenges in their full scale theoretical description and computer simulation. Multiscale multiphysics and multidomain models have been introduced to reduce the number of degrees of freedom while maintaining modeling accuracy and achieving computational efficiency. A total energy functional is constructed to put energies for polar and nonpolar solvation, chemical potential, fluid flow, molecular mechanics, and elastic dynamics on an equal footing. The variational principle is utilized to derive coupled governing equations for the above mentioned multiphysical descriptions. Among these governing equations is the Poisson-Boltzmann equation which describes continuum electrostatics with atomicmore » charges. The present work introduces the theory of continuum elasticity with atomic rigidity (CEWAR). The essence of CEWAR is to formulate the shear modulus as a continuous function of atomic rigidity. As a result, the dynamics complexity of a macromolecular system is separated from its static complexity so that the more time-consuming dynamics is handled with continuum elasticity theory, while the less time-consuming static analysis is pursued with atomic approaches. We propose a simple method, flexibility-rigidity index (FRI), to analyze macromolecular flexibility and rigidity in atomic detail. The construction of FRI relies on the fundamental assumption that protein functions, such as flexibility, rigidity, and energy, are entirely determined by the structure of the protein and its environment, although the structure is in turn determined by all the interactions. As such, the FRI measures the topological connectivity of protein atoms or residues and characterizes the geometric compactness of the protein structure. As a consequence, the FRI does not resort to the interaction Hamiltonian and bypasses matrix diagonalization, which underpins most other flexibility analysis methods. FRI's computational complexity is of O(N{sup 2}) at most, where N is the number of atoms or residues, in contrast to O(N{sup 3}) for Hamiltonian based methods. We demonstrate that the proposed FRI gives rise to accurate prediction of protein B-Factor for a set of 263 proteins. We show that a parameter free FRI is able to achieve about 95% accuracy of the parameter optimized FRI. An interpolation algorithm is developed to construct continuous atomic flexibility functions for visualization and use with CEWAR.« less

A poly(acrylonitrile)-functionalized porous aromatic framework synthesized by atom-transfer radical polymerization for the extraction of uranium from seawater

DOE PAGES

Yue, Yanfeng; Zhang, Chenxi; Tang, Qing; ...

2015-10-30

In order to ensure a sustainable reserve of fuel for nuclear power generation, tremendous research efforts have been devoted to developing advanced sorbent materials for extracting uranium from seawater. In this work, a porous aromatic framework (PAF) was surface-functionalized with poly(acrylonitrile) through atom-transfer radical polymerization (ATRP). Batches of this adsorbent were conditioned with potassium hydroxide (KOH) at room temperature or 80 °C prior to contact with a uranium-spiked seawater simulant, with minimal differences in uptake observed as a function of conditioning temperature. A maximum capacity of 4.81 g-U/kg-ads was obtained following 42 days contact with uranium-spiked filtered environmental seawater, whichmore » demonstrates a comparable adsorption rate. A kinetic investigation revealed extremely rapid uranyl uptake, with more than 80% saturation reached within 14 days. Furthermore, relying on the semiordered structure of the PAF adsorbent, density functional theory (DFT) calculations reveal cooperative interactions between multiple adsorbent groups yield a strong driving force for uranium binding.« less

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

NASA Astrophysics Data System (ADS)

Zhou, Si; Liu, Cheng-Cheng; Zhao, Jijun; Yao, Yugui

2018-03-01

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.

Seeking to Improve Low Energy Neutral Atom Detection in Space

NASA Technical Reports Server (NTRS)

Shappirio, M.; Coplan, M.; Chornay, D.; Collier, M.; Herrero, F.; Ogilvie, K.; Williams, E.

2007-01-01

The detection of energetic neutral atoms allows for the remote examination of the interactions between plasmas and neutral populations in space. Before these neutral atoms can be measured, they must first be converted to ions. For the low energy end of this spectrum, interaction with a conversion surface is often the most efficient method to convert neutrals into ions. It is generally thought that the most efficient surfaces are low work functions materials. However, by their very nature, these surfaces are highly reactive and unstable, and therefore are not suitable for space missions where conditions cannot be controlled as they are in a laboratory. We therefore are looking to optimize a stable surface for conversion efficiency. Conversion efficiency can be increased either by changing the incident angle of the neutral particles to be grazing incidence and using stable surfaces with high conversion efficiencies. We have examined how to increase the angle of incidence from -80 degrees to -89 degrees, while maintaining or improving the total active conversion surface area without increasing the overall volume of the instrument. We are developing a method to micro-machine silicon, which will reduce the volume to surface area ratio by a factor of 60. We have also examined the material properties that affect the conversion efficiency of the surface for stable surfaces. Some of the parameters we have examined are work function, smoothness, and bond structure. We find that for stable surfaces, the most important property is the smoothness of the surface.

Carbon Dioxide Electroreduction into Syngas Boosted by a Partially Delocalized Charge in Molybdenum Sulfide Selenide Alloy Monolayers.

PubMed

Xu, Jiaqi; Li, Xiaodong; Liu, Wei; Sun, Yongfu; Ju, Zhengyu; Yao, Tao; Wang, Chengming; Ju, Huanxin; Zhu, Junfa; Wei, Shiqiang; Xie, Yi

2017-07-24

Structural parameters of ternary transition-metal dichalcogenide (TMD) alloy usually obey Vegard law well, while interestingly it often exhibits boosted electrocatalytic performances relative to its two pristine binary TMDs. To unveil the underlying reasons, we propose an ideal model of ternary TMDs alloy monolayer. As a prototype, MoSeS alloy monolayers are successfully synthesized, in which X-ray absorption fine structure spectroscopy manifests their shortened Mo-S and lengthened Mo-Se bonds, helping to tailor the d-band electronic structure of Mo atoms. Density functional theory calculations illustrate an increased density of states near their conduction band edge, which ensures faster electron transfer confirmed by their lower work function and smaller charge-transfer resistance. Energy calculations show the off-center charge around Mo atoms not only benefits for stabilizing COOH* intermediate confirmed by its most negative formation energy, but also facilitates the rate-limiting CO desorption step verified by CO temperature programmed desorption and electro-stripping tests. As a result, MoSeS alloy monolayers attain the highest 45.2 % Faradaic efficiency for CO production, much larger than that of MoS 2 monolayers (16.6 %) and MoSe 2 monolayers (30.5 %) at -1.15 V vs. RHE. This work discloses how the partially delocalized charge in ternary TMDs alloys accelerates electrocatalytic performances at atomic level, opening new horizons for manipulating CO 2 electroreduction properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of argon sputtering and UV-ozone radiation on the physico-chemical surface properties of ITO

NASA Astrophysics Data System (ADS)

Che, Hui; El Bouanani, M.

2018-01-01

X-ray photoelectron spectroscopy (XPS) and Ultraviolet Photoelectron Spectroscopy (UPS) were used to evaluate and determine the effects of 1 KeV Ar+ irradiation (sputtering) on the surface chemical composition and work function of Indium Thin Oxide (ITO). While Ar+ sputtering removes carbon-based surface contaminants, it also modifies the Sn-rich surface of ITO and leads to a reduction of the oxidation state of Sn from Sn4+ to Sn2+. The decrease in the work function of ITO is directly correlated to the decrease of Sn atomic concentration in the Sn-rich top surface layer and the reduction of the oxidation state of surface Sn.

Asymmetric 3d Electronic Structure for Enhanced Oxygen Evolution Catalysis.

PubMed

Liu, Yang; Yin, Shibin; Shen, Pei Kang

2018-06-27

The oxygen evolution reaction (OER) is an essential process for renewable energy, and designing a bifunctional oxygen electrocatalyst with high catalytic performance plays a significant role. In this work, FeS, Ni 3 S 2 , Fe 5 Ni 4 S 8 , and N, O, S-doped meshy carbon base were successfully synthesized. The sample containing Fe 5 Ni 4 S 8 exhibited excellent OER performance. The density functional theory calculations indicate that the partial density of states for 3d electrons (3d-PDOS) of Fe and Ni atoms are changed from monometallic sulfide to bimetallic sulfide at the sulfur vacancy. The asymmetric 3d electronic structure optimizes the 3d-PDOS of Fe and Ni atoms, and leads to an enhanced OER activity. This work provides a new strategy to prepare a low-cost electrocatalyst for oxygen evolution with high-efficiency.

Design Principles for the Atomic and Electronic Structure of Halide Perovskite Photovoltaic Materials: Insights from Computation.

PubMed

Berger, Robert F

2018-02-09

In the current decade, perovskite solar cell research has emerged as a remarkably active, promising, and rapidly developing field. Alongside breakthroughs in synthesis and device engineering, halide perovskite photovoltaic materials have been the subject of predictive and explanatory computational work. In this Minireview, we focus on a subset of this computation: density functional theory (DFT)-based work highlighting the ways in which the electronic structure and band gap of this class of materials can be tuned via changes in atomic structure. We distill this body of computational literature into a set of underlying design principles for the band gap engineering of these materials, and rationalize these principles from the viewpoint of band-edge orbital character. We hope that this perspective provides guidance and insight toward the rational design and continued improvement of perovskite photovoltaics. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Singly and Doubly Excited States of the D-Dimensional Helium Atom(Supported by DOD-ONR N00014-94-1-0998)

NASA Astrophysics Data System (ADS)

Carzoli, J.; Dunn, M.; Watson, D. K.

1998-05-01

Large order dimensional perturbation theory (DPT) has been used to study the ground and a number of excited states of two-electron atoms for the case L=0. Here we present the first application of recent work generalizing DPT to higher angular momentum.(M. Dunn, D.K. Watson, Ann. Phys. 251 (1996) 266)^,(M. Dunn, D.K. Watson, The Large Dimension Limit of Higher Angular Momentum States. Phys. Rev. A. (accepted for publication)) In this work we begin the investigation of P^o states, presenting results for the energies of some of the lowest lying states and discuss the analytic structure of these energies as functions of 1/D. We also obtain energies of corresponding D^o states with almost no additional effort by making use of interdimensional degeneracies with the P^o states.

Noncontact Atomic Force Microscopy: An Emerging Tool for Fundamental Catalysis Research.

PubMed

Altman, Eric I; Baykara, Mehmet Z; Schwarz, Udo D

2015-09-15

Although atomic force microscopy (AFM) was rapidly adopted as a routine surface imaging apparatus after its introduction in 1986, it has not been widely used in catalysis research. The reason is that common AFM operating modes do not provide the atomic resolution required to follow catalytic processes; rather the more complex noncontact (NC) mode is needed. Thus, scanning tunneling microscopy has been the principal tool for atomic scale catalysis research. In this Account, recent developments in NC-AFM will be presented that offer significant advantages for gaining a complete atomic level view of catalysis. The main advantage of NC-AFM is that the image contrast is due to the very short-range chemical forces that are of interest in catalysis. This motivated our development of 3D-AFM, a method that yields quantitative atomic resolution images of the potential energy surfaces that govern how molecules approach, stick, diffuse, and rebound from surfaces. A variation of 3D-AFM allows the determination of forces required to push atoms and molecules on surfaces, from which diffusion barriers and variations in adsorption strength may be obtained. Pushing molecules towards each other provides access to intermolecular interaction between reaction partners. Following reaction, NC-AFM with CO-terminated tips yields textbook images of intramolecular structure that can be used to identify reaction intermediates and products. Because NC-AFM and STM contrast mechanisms are distinct, combining the two methods can produce unique insight. It is demonstrated for surface-oxidized Cu(100) that simultaneous 3D-AFM/STM yields resolution of both the Cu and O atoms. Moreover, atomic defects in the Cu sublattice lead to variations in the reactivity of the neighboring O atoms. It is shown that NC-AFM also allows a straightforward imaging of work function variations which has been used to identify defect charge states on catalytic surfaces and to map charge transfer within an individual molecule. These advances highlight the potential for NC-AFM-based methods to become the cornerstone upon which a quantitative atomic scale view of each step of a catalytic process may be gained. Realizing this potential will rely on two breakthroughs: (1) development of robust methods for tip functionalization and (2) simplification of NC-AFM instrumentation and control schemes. Quartz force sensors may offer paths forward in both cases. They allow any material with an atomic asperity to be used as a tip, opening the door to a wide range of surface functionalization chemistry. In addition, they do not suffer from the instabilities that motivated the initial adoption of complex control strategies that are still used today.

Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

PubMed

Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

2014-01-25

To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution. Copyright © 2013 Elsevier B.V. All rights reserved.

Influence of bending of monoatomic copper chains with 10 and 22 atoms on their absorbance spectra: TD-DFT calculations

NASA Astrophysics Data System (ADS)

Markin, Alexey V.; Skaptsov, Alexander A.; Markina, Natalia E.

2018-04-01

The aim of the work is the investigation of bending on the properties of hypothetical one-atom-thick copper clusters (CC) (with 10 and 22 atoms). Time-dependent density functional theory with PBE0 functional and lanl2dz basis set were used for all calculations. The bending was performed by changing angle between copper atoms from 180° to 144° and 163.7° (2° step size) for CC with 10 and 22 atoms, correspondingly. The dependences of absorbance spectra in UVvisible-NIR range (400-2000 nm range) and various energetic characteristics (final energy, chemical potential, and binding energy) on bending angle were investigated. Non-bended (linear) clusters were assigned as references. First, absorbance spectra of all CC contain interband transitions (3d->4sp) in UV-visible range (below 600 nm). Linear configuration of CC also contain intensive absorbance band in NIR region (at 900 and 1700 nm for CC with 10 and 22 atoms) which is associated with 4s electron oscillations along clusters (longitudinal transitions). Significant dumping of low energy 4s transitions (HOMO->LUMO) and interband transitions in the range 600‒500 nm was observed during the bending of CC. Obtained results are in agreement with experimental results for 2D copper nanostructures from literature. We explain such influence of bending by formation merging 4s orbitals which form new 4s oscillations in-plane of bending (in the case of ring-like CC - diametral oscillations). An influence of bending on energy, stability, and chemical potential (Fermi level) of CC was also investigated and discussed.

Beta Atomic Contacts: Identifying Critical Specific Contacts in Protein Binding Interfaces

PubMed Central

Liu, Qian; Kwoh, Chee Keong; Hoi, Steven C. H.

2013-01-01

Specific binding between proteins plays a crucial role in molecular functions and biological processes. Protein binding interfaces and their atomic contacts are typically defined by simple criteria, such as distance-based definitions that only use some threshold of spatial distance in previous studies. These definitions neglect the nearby atomic organization of contact atoms, and thus detect predominant contacts which are interrupted by other atoms. It is questionable whether such kinds of interrupted contacts are as important as other contacts in protein binding. To tackle this challenge, we propose a new definition called beta (β) atomic contacts. Our definition, founded on the β-skeletons in computational geometry, requires that there is no other atom in the contact spheres defined by two contact atoms; this sphere is similar to the van der Waals spheres of atoms. The statistical analysis on a large dataset shows that β contacts are only a small fraction of conventional distance-based contacts. To empirically quantify the importance of β contacts, we design βACV, an SVM classifier with β contacts as input, to classify homodimers from crystal packing. We found that our βACV is able to achieve the state-of-the-art classification performance superior to SVM classifiers with distance-based contacts as input. Our βACV also outperforms several existing methods when being evaluated on several datasets in previous works. The promising empirical performance suggests that β contacts can truly identify critical specific contacts in protein binding interfaces. β contacts thus provide a new model for more precise description of atomic organization in protein quaternary structures than distance-based contacts. PMID:23630569

Atomic and electronic structure of Mo6S9-xIx nanowires

NASA Astrophysics Data System (ADS)

Meden, A.; Kodre, A.; Padeznik Gomilsek, J.; Arcon, I.; Vilfan, I.; Vrbanic, D.; Mrzel, A.; Mihailovic, D.

2005-09-01

Moybdenum-based subnanometre diameter nanowires are easy to synthesize and disperse, and they exhibit a variety of functional properties in which they are superior to other one-dimensional materials. However, further progress in the understanding of physical properties and the development of new and specific applications have so far been impeded by the fact that their structure was not accurately known. Here we report on a combination of systematic x-ray diffraction and extended x-ray absorption fine structure experiments, and first-principles theoretical structure calculations, which are used to determine the atomic skeletal structure of individual Mo6S9-xIx (MoSIx) nanowires, their packing arrangement within bundles and their electronic band structure. From this work we conclude that the variations in functional properties appear to arise from different stoichiometry, not skeletal structure. A supplementary data file is available from http://stacks.iop.org/0957-4484/16/1578

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rossi, Tuomas P., E-mail: tuomas.rossi@alumni.aalto.fi; Sakko, Arto; Puska, Martti J.

We present an approach for generating local numerical basis sets of improving accuracy for first-principles nanoplasmonics simulations within time-dependent density functional theory. The method is demonstrated for copper, silver, and gold nanoparticles that are of experimental interest but computationally demanding due to the semi-core d-electrons that affect their plasmonic response. The basis sets are constructed by augmenting numerical atomic orbital basis sets by truncated Gaussian-type orbitals generated by the completeness-optimization scheme, which is applied to the photoabsorption spectra of homoatomic metal atom dimers. We obtain basis sets of improving accuracy up to the complete basis set limit and demonstrate thatmore » the performance of the basis sets transfers to simulations of larger nanoparticles and nanoalloys as well as to calculations with various exchange-correlation functionals. This work promotes the use of the local basis set approach of controllable accuracy in first-principles nanoplasmonics simulations and beyond.« less

Continuous Wave Ring-Down Spectroscopy Diagnostic for Measuring Argon Ion and Neutral Velocity Distribution Functions in a Helicon Plasma

NASA Astrophysics Data System (ADS)

McCarren, Dustin; Vandervort, Robert; Soderholm, Mark; Carr, Jerry, Jr.; Galante, Matthew; Magee, Richard; Scime, Earl

2013-10-01

Cavity Ring-Down Spectroscopy CRDS is a proven, ultra-sensitive, cavity enhanced absorption spectroscopy technique. When combined with a continuous wavelength (CW) diode laser that has a sufficiently narrow line width, the Doppler broadened absorption line, i.e., the velocity distribution functions (IVDFs), can be measured. Measurements of IVDFS can be made using established techniques, such as laser induced fluorescence (LIF). However, LIF suffers from the requirement that the initial state of the LIF sequence have a substantial density. This usually limits LIF to ions and atoms with large metastable state densities for the given plasma conditions. CW-CRDS is considerably more sensitive than LIF and can potentially be applied to much lower density populations of ion and atom states. In this work we present ongoing measurements of the CW-CRDS diagnostic and discuss the technical challenges of using CW-CRDS to make measurements in a helicon plasma.

Investigation of static and dynamic behavior of functionally graded piezoelectric actuated Poly-Si micro cantilever probe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pandey, Vibhuti Bhushan; Parashar, Sandeep Kumar, E-mail: skparashar@rtu.ac.in

In the present paper a novel functionally graded piezoelectric (FGP) actuated Poly-Si micro cantilever probe is proposed for atomic force microscope. The shear piezoelectric coefficient d{sub 15} has much higher value than coupling coefficients d{sub 31} and d{sub 33}, hence in the present work the micro cantilever beam actuated by d{sub 15} effect is utilized. The material properties are graded in the thickness direction of actuator by a simple power law. A three dimensional finite element analysis has been performed using COMSOL Multiphysics® (version 4.2) software. Tip deflection and free vibration analysis for the micro cantilever probe has been done.more » The results presented in the paper shall be useful in the design of micro cantilever probe and their subsequent utilization in atomic force microscopes.« less

Dynamic Optical Tuning of Interlayer Interactions in the Transition Metal Dichalcogenides

DOE PAGES

Mannebach, Ehren M.; Nyby, Clara; Ernst, Friederike; ...

2017-11-09

Modulation of weak interlayer interactions between quasi-two-dimensional atomic planes in the transition metal dichalcogenides (TMDCs) provides avenues for tuning their functional properties. Here we show that above-gap optical excitation in the TMDCs leads to an unexpected large-amplitude, ultrafast compressive force between the two-dimensional layers, as probed by in situ measurements of the atomic layer spacing at femtosecond time resolution. We show that this compressive response arises from a dynamic modulation of the interlayer van der Waals interaction and that this represents the dominant light-induced stress at low excitation densities. A simple analytic model predicts the magnitude and carrier density dependencemore » of the measured strains. Furthermore, this work establishes a new method for dynamic, nonequilibrium tuning of correlation-driven dispersive interactions and of the optomechanical functionality of TMDC quasi-two-dimensional materials.« less

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

DOE PAGES

Lindsay, L.; Kuang, Y.

2017-03-13

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. We present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first principles calculations. We also use graphane, a buckled graphene backbone with covalently bonded Hydrogen atoms on both sides, as the base material and vary the mass of the Hydrogen atoms to simulate the effect of mass variance from other functional groups. We find non-monotonic behavior of κ with increasing mass of the functional group and an unusual cross-over from acoustic-dominated tomore » optic-dominated thermal transport behavior. We connect this cross-over to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection symmetry based scattering selection rule responsible for their large contributions in graphene. Our work demonstrates the potential for manipulation and engineering of thermal transport properties in two dimensional materials toward targeted applications.« less

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

NASA Astrophysics Data System (ADS)

Lindsay, L.; Kuang, Y.

2017-03-01

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. Here we present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first-principles calculations. We use graphane, a buckled graphene backbone with covalently bonded hydrogen atoms on both sides, as the base material and vary the mass of the hydrogen atoms to simulate the effect of mass variance from other functional groups. We find nonmonotonic behavior of κ with increasing mass of the functional group and an unusual crossover from acoustic-dominated to optic-dominated thermal transport behavior. We connect this crossover to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection-symmetry-based scattering selection rule responsible for their large contributions in graphene. This work demonstrates the potential for manipulation and engineering of thermal transport properties in two-dimensional materials toward targeted applications.

Effects of functional group mass variance on vibrational properties and thermal transport in graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lindsay, L.; Kuang, Y.

Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. We present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first principles calculations. We also use graphane, a buckled graphene backbone with covalently bonded Hydrogen atoms on both sides, as the base material and vary the mass of the Hydrogen atoms to simulate the effect of mass variance from other functional groups. We find non-monotonic behavior of κ with increasing mass of the functional group and an unusual cross-over from acoustic-dominated tomore » optic-dominated thermal transport behavior. We connect this cross-over to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection symmetry based scattering selection rule responsible for their large contributions in graphene. Our work demonstrates the potential for manipulation and engineering of thermal transport properties in two dimensional materials toward targeted applications.« less

Molecular Dynamics Simulations Provide Atomistic Insight into Hydrogen Exchange Mass Spectrometry Experiments.

PubMed

Petruk, Ariel A; Defelipe, Lucas A; Rodríguez Limardo, Ramiro G; Bucci, Hernán; Marti, Marcelo A; Turjanski, Adrian G

2013-01-08

It is now clear that proteins are flexible entities that in solution switch between conformations to achieve their function. Hydrogen/Deuterium Exchange Mass Spectrometry (HX/MS) is an invaluable tool to understand dynamic changes in proteins modulated by cofactor binding, post-transductional modifications, or protein-protein interactions. ERK2MAPK, a protein involved in highly conserved signal transduction pathways of paramount importance for normal cellular function, has been extensively studied by HX/MS. Experiments of the ERK2MAPK in the inactive and active states (in the presence or absence of bound ATP) have provided valuable information on the plasticity of the MAPK domain. However, interpretation of the HX/MS data is difficult, and changes are mostly explained in relation to available X-ray structures, precluding a complete atomic picture of protein dynamics. In the present work, we have used all atom Molecular Dynamics simulations (MD) to provide a theoretical framework for the interpretation of HX/MS data. Our results show that detailed analysis of protein-solvent interaction along the MD simulations allows (i) prediction of the number of protons exchanged for each peptide in the HX/MS experiments, (ii) rationalization of the experimentally observed changes in exchange rates in different protein conditions at the residue level, and (iii) that at least for ERK2MAPK, most of the functionally observed differences in protein dynamics are related to what can be considered the native state conformational ensemble. In summary, the combination of HX/MS experiments with all atom MD simulations emerges as a powerful approach to study protein native state dynamics with atomic resolution.

Accelerating large scale Kohn-Sham density functional theory calculations with semi-local functionals and hybrid functionals

NASA Astrophysics Data System (ADS)

Lin, Lin

The computational cost of standard Kohn-Sham density functional theory (KSDFT) calculations scale cubically with respect to the system size, which limits its use in large scale applications. In recent years, we have developed an alternative procedure called the pole expansion and selected inversion (PEXSI) method. The PEXSI method solves KSDFT without solving any eigenvalue and eigenvector, and directly evaluates physical quantities including electron density, energy, atomic force, density of states, and local density of states. The overall algorithm scales as at most quadratically for all materials including insulators, semiconductors and the difficult metallic systems. The PEXSI method can be efficiently parallelized over 10,000 - 100,000 processors on high performance machines. The PEXSI method has been integrated into a number of community electronic structure software packages such as ATK, BigDFT, CP2K, DGDFT, FHI-aims and SIESTA, and has been used in a number of applications with 2D materials beyond 10,000 atoms. The PEXSI method works for LDA, GGA and meta-GGA functionals. The mathematical structure for hybrid functional KSDFT calculations is significantly different. I will also discuss recent progress on using adaptive compressed exchange method for accelerating hybrid functional calculations. DOE SciDAC Program, DOE CAMERA Program, LBNL LDRD, Sloan Fellowship.

A Student Assembled Spectrograph with a CCD Detector to Assist with Students' Understanding of Spectrometry

ERIC Educational Resources Information Center

Grove, T. T.; Masters, M. F.

2007-01-01

To help students develop an understanding of the proper use and function of spectrographs and monochromators we describe a student-assembled spectrograph using a "webcam" detector. The apparatus also works well as a low-cost demonstration, helping students make connections between an atomic spectrum observed by eye and a plot of the relative…

Synthesis and Functionalization of Atomic Layer Boron Nitride Nanosheets for Advanced Material Applications

DTIC Science & Technology

2014-06-05

PAGES 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 5c. PROGRAM ELEMENT NUMBER 5b. GRANT NUMBER 5a. CONTRACT NUMBER Form Approved OMB...Phys., 89, (2001) 5243. [14] M. Depas, R. L. Van Meirhaegue, W. H. Laflère, F. Cardon , Solid- State Electron, 37, (1994) 433. [15] Muhammad Sajjad

Interactively Applying the Variational Method to the Dihydrogen Molecule: Exploring Bonding and Antibonding

ERIC Educational Resources Information Center

Cruzeiro, Vinícius Wilian D.; Roitberg, Adrian; Polfer, Nicolas C.

2016-01-01

In this work we are going to present how an interactive platform can be used as a powerful tool to allow students to better explore a foundational problem in quantum chemistry: the application of the variational method to the dihydrogen molecule using simple Gaussian trial functions. The theoretical approach for the hydrogen atom is quite…

Control over the branched structures of platinum nanocrystals for electrocatalytic applications.

PubMed

Ma, Liang; Wang, Chengming; Gong, Ming; Liao, Lingwen; Long, Ran; Wang, Jinguo; Wu, Di; Zhong, Wei; Kim, Moon J; Chen, Yanxia; Xie, Yi; Xiong, Yujie

2012-11-27

Structural control of branched nanocrystals allows tuning two parameters that are critical to their catalytic activity--the surface-to-volume ratio, and the number of atomic steps, ledges, and kinks on surface. In this work, we have developed a simple synthetic system that allows tailoring the numbers of branches in Pt nanocrystals by tuning the concentration of additional HCl. In the synthesis, HCl plays triple functions in tuning branched structures via oxidative etching: (i) the crystallinity of seeds and nanocrystals; (ii) the number of {111} or {100} faces provided for growth sites; (iii) the supply kinetics of freshly formed Pt atoms in solution. As a result, tunable Pt branched structures--tripods, tetrapods, hexapods, and octopods with identical chemical environment--can be rationally synthesized in a single system by simply altering the etching strength. The controllability in branched structures enables to reveal that their electrocatalytic performance can be optimized by constructing complex structures. Among various branched structures, Pt octopods exhibit particularly high activity in formic acid oxidation as compared with their counterparts and commercial Pt/C catalysts. It is anticipated that this work will open a door to design more complex nanostructures and to achieve specific functions for various applications.

Atom probe study of B2 order and A2 disorder of the FeCo matrix in an Fe-Co-Mo-alloy.

PubMed

Turk, C; Leitner, H; Schemmel, I; Clemens, H; Primig, S

2017-07-01

The physical and mechanical properties of intermetallic alloys can be tailored by controlling the degree of order of the solid solution by means of heat treatments. FeCo alloys with an appropriate composition exhibit an A2-disorder↔B2-order transition during continuous cooling from the disordered bcc region. The study of atomic order in intermetallic alloys by diffraction and its influence on the material properties is well established, however, investigating magnetic FeCo-based alloys by conventional methods such as X-ray diffraction is quite challenging. Thus, the imaging of ordered FeCo-nanostructures needs to be done with high resolution techniques. Transmission electron microscopy investigations of ordered FeCo domains are difficult, due to the chemical and physical similarity of Fe and Co atoms and the ferromagnetism of the samples. In this work it will be demonstrated, that the local atomic arrangement of ordered and disordered regions in an industrial Fe-Co-Mo alloy can be successfully imaged by atom probe measurements supported by field ion microscopy and transmission Kikuchi diffraction. Furthermore, a thorough atom probe parameter study will be presented and field evaporation artefacts as a function of crystallographic orientation in Fe-Co-samples will be discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Atomic-Level Co3O4 Layer Stabilized by Metallic Cobalt Nanoparticles: A Highly Active and Stable Electrocatalyst for Oxygen Reduction.

PubMed

Liu, Min; Liu, Jingjun; Li, Zhilin; Wang, Feng

2018-02-28

Developing atomic-level transition oxides may be one of the most promising ways for providing ultrahigh electrocatalytic performance for oxygen reduction reaction (ORR), compared with their bulk counterparts. In this article, we developed a set of atomically thick Co 3 O 4 layers covered on Co nanoparticles through partial reduction of Co 3 O 4 nanoparticles using melamine as a reductive additive at an elevated temperature. Compared with the original Co 3 O 4 nanoparticles, the synthesized Co 3 O 4 with a thickness of 1.1 nm exhibits remarkably enhanced ORR activity and durability, which are even higher than those obtained by a commercial Pt/C in an alkaline environment. The superior activity can be attributed to the unique physical and chemical structures of the atomic-level oxide featuring the narrowed band gap and decreased work function, caused by the escaped lattice oxygen and the enriched coordination-unsaturated Co 2+ in this atomic layer. Besides, the outstanding durability of the catalyst can result from the chemically epitaxial deposition of the Co 3 O 4 on the cobalt surface. Therefore, the proposed synthetic strategy may offer a smart way to develop other atomic-level transition metals with high electrocatalytic activity and stability for energy conversion and storage devices.

A knowledge-based potential with an accurate description of local interactions improves discrimination between native and near-native protein conformations.

PubMed

Ferrada, Evandro; Vergara, Ismael A; Melo, Francisco

2007-01-01

The correct discrimination between native and near-native protein conformations is essential for achieving accurate computer-based protein structure prediction. However, this has proven to be a difficult task, since currently available physical energy functions, empirical potentials and statistical scoring functions are still limited in achieving this goal consistently. In this work, we assess and compare the ability of different full atom knowledge-based potentials to discriminate between native protein structures and near-native protein conformations generated by comparative modeling. Using a benchmark of 152 near-native protein models and their corresponding native structures that encompass several different folds, we demonstrate that the incorporation of close non-bonded pairwise atom terms improves the discriminating power of the empirical potentials. Since the direct and unbiased derivation of close non-bonded terms from current experimental data is not possible, we obtained and used those terms from the corresponding pseudo-energy functions of a non-local knowledge-based potential. It is shown that this methodology significantly improves the discrimination between native and near-native protein conformations, suggesting that a proper description of close non-bonded terms is important to achieve a more complete and accurate description of native protein conformations. Some external knowledge-based energy functions that are widely used in model assessment performed poorly, indicating that the benchmark of models and the specific discrimination task tested in this work constitutes a difficult challenge.

Surface states and annihilation characteristics of positrons trapped at the oxidized Cu(100) surface

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Weiss, A. H.

2013-06-01

In this work we present the results of theoretical studies of positron surface and bulk states and annihilation probabilities of surface-trapped positrons with relevant core electrons at the oxidized Cu(100) surface under conditions of high oxygen coverage. Oxidation of the Cu(100) surface has been studied by performing an ab-initio investigation of the stability and electronic structure of the Cu(100) missing row reconstructed surface at various on-surface and subsurface oxygen coverages ranging from 0.5 to 1.5 monolayers using density functional theory (DFT). All studied structures have been found to be energetically more favorable as compared to structures formed by purely on-surface oxygen adsorption. The observed decrease in the positron work function when oxygen atoms occupy on-surface and subsurface sites has been attributed to a significant charge redistribution within the first two layers, buckling effects within each layer and an interlayer expansion. The computed positron binding energy, positron surface state wave function, and annihilation probabilities of the surface trapped positrons with relevant core electrons demonstrate their sensitivity to oxygen coverage, atomic structure of the topmost layers of surfaces, and charge transfer effects. Theoretical results are compared with experimental data obtained from studies of oxidation of the Cu(100) surface using positron annihilation induced Auger electron spectroscopy (PAES). The results presented provide an explanation for the changes observed in the probability of annihilation of surface trapped positrons with Cu 3p core-level electrons as a function of annealing temperature.

Localized spatially nonlinear matter waves in atomic-molecular Bose-Einstein condensates with space-modulated nonlinearity

PubMed Central

Yao, Yu-Qin; Li, Ji; Han, Wei; Wang, Deng-Shan; Liu, Wu-Ming

2016-01-01

The intrinsic nonlinearity is the most remarkable characteristic of the Bose-Einstein condensates (BECs) systems. Many studies have been done on atomic BECs with time- and space- modulated nonlinearities, while there is few work considering the atomic-molecular BECs with space-modulated nonlinearities. Here, we obtain two kinds of Jacobi elliptic solutions and a family of rational solutions of the atomic-molecular BECs with trapping potential and space-modulated nonlinearity and consider the effect of three-body interaction on the localized matter wave solutions. The topological properties of the localized nonlinear matter wave for no coupling are analysed: the parity of nonlinear matter wave functions depends only on the principal quantum number n, and the numbers of the density packets for each quantum state depend on both the principal quantum number n and the secondary quantum number l. When the coupling is not zero, the localized nonlinear matter waves given by the rational function, their topological properties are independent of the principal quantum number n, only depend on the secondary quantum number l. The Raman detuning and the chemical potential can change the number and the shape of the density packets. The stability of the Jacobi elliptic solutions depends on the principal quantum number n, while the stability of the rational solutions depends on the chemical potential and Raman detuning. PMID:27403634

Simultaneous measurements of work function and H‒ density including caesiation of a converter surface

NASA Astrophysics Data System (ADS)

Cristofaro, S.; Friedl, R.; Fantz, U.

2017-08-01

Negative hydrogen ion sources rely on the surface conversion of neutral atomic hydrogen and positive hydrogen ions to H-. The efficiency of this process depends on the actual work function of the converter surface. By introducing caesium into the source the work function decreases, enhancing the negative ion yield. In order to study the impact of the work function on the H- surface production at similar conditions to the ones in ion sources for fusion devices like ITER and DEMO, fundamental investigations are performed in a flexible laboratory experiment. The work function of the converter surface can be absolutely measured by photoelectric effect, while a newly installed cavity ring-down spectroscopy system (CRDS) measures the H- density. The CRDS is firstly tested and characterized by investigations on H- volume production. Caesiation of a stainless steel sample is then performed in vacuum and the plasma effect on the Cs layer is investigated also for long plasma-on times. A minimum work function of (1.9±0.1) eV is reached after some minutes of plasma treatment, resulting in a reduction by a value of 0.8 eV compared to vacuum measurements. The H- density above the surface is (2.1±0.5)×1015 m-3. With further plasma exposure of the caesiated surface, the work function increases up to 3.75 eV, due to the impinging plasma particles which gradually remove the Cs layer. As a result, the H- density decreases by a factor of at least 2.

Computational Study of Chemical Reactivity Using Information-Theoretic Quantities from Density Functional Reactivity Theory for Electrophilic Aromatic Substitution Reactions.

PubMed

Wu, Wenjie; Wu, Zemin; Rong, Chunying; Lu, Tian; Huang, Ying; Liu, Shubin

2015-07-23

The electrophilic aromatic substitution for nitration, halogenation, sulfonation, and acylation is a vastly important category of chemical transformation. Its reactivity and regioselectivity is predominantly determined by nucleophilicity of carbon atoms on the aromatic ring, which in return is immensely influenced by the group that is attached to the aromatic ring a priori. In this work, taking advantage of recent developments in quantifying nucleophilicity (electrophilicity) with descriptors from the information-theoretic approach in density functional reactivity theory, we examine the reactivity properties of this reaction system from three perspectives. These include scaling patterns of information-theoretic quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy and information gain at both molecular and atomic levels, quantitative predictions of the barrier height with both Hirshfeld charge and information gain, and energetic decomposition analyses of the barrier height for the reactions. To that end, we focused in this work on the identity reaction of the monosubstituted-benzene molecule reacting with hydrogen fluoride using boron trifluoride as the catalyst in the gas phase. We also considered 19 substituting groups, 9 of which are ortho/para directing and the other 9 meta directing, besides the case of R = -H. Similar scaling patterns for these information-theoretic quantities found for stable species elsewhere were disclosed for these reactions systems. We also unveiled novel scaling patterns for information gain at the atomic level. The barrier height of the reactions can reliably be predicted by using both the Hirshfeld charge and information gain at the regioselective carbon atom. The energy decomposition analysis ensued yields an unambiguous picture about the origin of the barrier height, where we showed that it is the electrostatic interaction that plays the dominant role, while the roles played by exchange-correlation and steric effects are minor but indispensable. Results obtained in this work should shed new light for better understanding of the factors governing the reactivity for this class of reactions and assisting ongoing efforts for the design of new and more efficient catalysts for such kind of transformations.

Optimal atomic structure of amorphous silicon obtained from density functional theory calculations

NASA Astrophysics Data System (ADS)

Pedersen, Andreas; Pizzagalli, Laurent; Jónsson, Hannes

2017-06-01

Atomic structure of amorphous silicon consistent with several reported experimental measurements has been obtained from annealing simulations using electron density functional theory calculations and a systematic removal of weakly bound atoms. The excess energy and density with respect to the crystal are well reproduced in addition to radial distribution function, angular distribution functions, and vibrational density of states. No atom in the optimal configuration is locally in a crystalline environment as deduced by ring analysis and common neighbor analysis, but coordination defects are present at a level of 1%-2%. The simulated samples provide structural models of this archetypal disordered covalent material without preconceived notion of the atomic ordering or fitting to experimental data.

Grassmann phase space methods for fermions. II. Field theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dalton, B.J., E-mail: bdalton@swin.edu.au; Jeffers, J.; Barnett, S.M.

In both quantum optics and cold atom physics, the behaviour of bosonic photons and atoms is often treated using phase space methods, where mode annihilation and creation operators are represented by c-number phase space variables, with the density operator equivalent to a distribution function of these variables. The anti-commutation rules for fermion annihilation, creation operators suggests the possibility of using anti-commuting Grassmann variables to represent these operators. However, in spite of the seminal work by Cahill and Glauber and a few applications, the use of Grassmann phase space methods in quantum-atom optics to treat fermionic systems is rather rare, thoughmore » fermion coherent states using Grassmann variables are widely used in particle physics. This paper presents a phase space theory for fermion systems based on distribution functionals, which replace the density operator and involve Grassmann fields representing anti-commuting fermion field annihilation, creation operators. It is an extension of a previous phase space theory paper for fermions (Paper I) based on separate modes, in which the density operator is replaced by a distribution function depending on Grassmann phase space variables which represent the mode annihilation and creation operators. This further development of the theory is important for the situation when large numbers of fermions are involved, resulting in too many modes to treat separately. Here Grassmann fields, distribution functionals, functional Fokker–Planck equations and Ito stochastic field equations are involved. Typical applications to a trapped Fermi gas of interacting spin 1/2 fermionic atoms and to multi-component Fermi gases with non-zero range interactions are presented, showing that the Ito stochastic field equations are local in these cases. For the spin 1/2 case we also show how simple solutions can be obtained both for the untrapped case and for an optical lattice trapping potential.« less

Rich interfacial chemistry and properties of carbon-doped hexagonal boron nitride nanosheets revealed by electronic structure calculations

NASA Astrophysics Data System (ADS)

Xie, Wei; Tamura, Takahiro; Yanase, Takashi; Nagahama, Taro; Shimada, Toshihiro

2018-04-01

The effect of C doping to hexagonal boron nitride (h-BN) to its electronic structure is examined by first principles calculations using the association from π-electron systems of organic molecules embedded in a two-dimensional insulator. In a monolayered carbon-doped structure, odd-number doping with carbon atoms confers metallic properties with different work functions. Various electronic interactions occur between two layers with odd-number carbon substitution. A direct sp3 covalent chemical bond is formed when C replaces adjacent B and N in different layers. A charge transfer complex between layers is found when C replaces B and N in the next-neighboring region, which results in narrower band gaps (e.g., 0.37 eV). Direct bonding between C and B atoms is found when two C atoms in different layers are at a certain distance.

Comparison of precursor infiltration into polymer thin films via atomic layer deposition and sequential vapor infiltration using in-situ quartz crystal microgravimetry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Padbury, Richard P.; Jur, Jesse S., E-mail: jsjur@ncsu.edu

Previous research exploring inorganic materials nucleation behavior on polymers via atomic layer deposition indicates the formation of hybrid organic–inorganic materials that form within the subsurface of the polymer. This has inspired adaptations to the process, such as sequential vapor infiltration, which enhances the diffusion of organometallic precursors into the subsurface of the polymer to promote the formation of a hybrid organic–inorganic coating. This work highlights the fundamental difference in mass uptake behavior between atomic layer deposition and sequential vapor infiltration using in-situ methods. In particular, in-situ quartz crystal microgravimetry is used to compare the mass uptake behavior of trimethyl aluminummore » in poly(butylene terephthalate) and polyamide-6 polymer thin films. The importance of trimethyl aluminum diffusion into the polymer subsurface and the subsequent chemical reactions with polymer functional groups are discussed.« less

Critical Landau Velocity in Helium Nanodroplets

NASA Astrophysics Data System (ADS)

Brauer, Nils B.; Smolarek, Szymon; Loginov, Evgeniy; Mateo, David; Hernando, Alberto; Pi, Marti; Barranco, Manuel; Buma, Wybren J.; Drabbels, Marcel

2013-10-01

The best-known property of superfluid helium is the vanishing viscosity that objects experience while moving through the liquid with speeds below the so-called critical Landau velocity. This critical velocity is generally considered a macroscopic property as it is related to the collective excitations of the helium atoms in the liquid. In the present work we determine to what extent this concept can still be applied to nanometer-scale, finite size helium systems. To this end, atoms and molecules embedded in helium nanodroplets of various sizes are accelerated out of the droplets by means of optical excitation, and the speed distributions of the ejected particles are determined. The measurements reveal the existence of a critical velocity in these systems, even for nanodroplets consisting of only a thousand helium atoms. Accompanying theoretical simulations based on a time-dependent density functional description of the helium confirm and further elucidate this experimental finding.

Thermodynamic properties of small aggregates of rare-gas atoms

NASA Technical Reports Server (NTRS)

Etters, R. D.; Kaelberer, J.

1975-01-01

The present work reports on the equilibrium thermodynamic properties of small clusters of xenon, krypton, and argon atoms, determined from a biased random-walk Monte Carlo procedure. Cluster sizes ranged from 3 to 13 atoms. Each cluster was found to have an abrupt liquid-gas phase transition at a temperature much less than for the bulk material. An abrupt solid-liquid transition is observed for thirteen- and eleven-particle clusters. For cluster sizes smaller than 11, a gradual transition from solid to liquid occurred over a fairly broad range of temperatures. Distribution of number of bond lengths as a function of bond length was calculated for several systems at various temperatures. The effects of box boundary conditions are discussed. Results show the importance of a correct description of boundary conditions. A surprising result is the slow rate at which system properties approach bulk behavior as cluster size is increased.

Non-uniformly functionalized titanium carbide-based MXenes as an anchoring material for Li-S batteries: A first-principles calculation

NASA Astrophysics Data System (ADS)

Sim, Eun Seob; Chung, Yong-Chae

2018-03-01

In this study, the influence of the non-uniform surface of F- and O-functionalized Ti2C on the anchoring behavior of lithium polysulfide (LiPS) is investigated using density functional theory. In order to consider the non-uniform surface, the substitutional, vacancy, and S-trapped sites of F- and O-functionalized Ti2C are designed. The anchoring behavior is investigated considering the adsorption energy of LiPS, reactivity between Li atoms and the substrate, and the reduction state of the S atoms. On the F-substitutional site of the O-functionalized surface, it is confirmed that the suppressing mechanism changes from the neutralization of S atoms to the anchoring of LiPS. However, too strong of an interaction between Ti atoms exposed at the vacancy site and S atoms induces trapping of the S atom at the vacancies of both F- and O-functionalized surfaces. As a result of the trapping of the S atom, the use of active material decreases. In addition, the S-trapped site originated from the vacancy site does not affect the suppressing mechanism. In conclusion, to optimize the Ti2C-based MXene as an anchoring material for Li-S batteries, the preparation process should be focused on eliminating the vacancy of functional groups.

Chemical Bonding: The Orthogonal Valence-Bond View

PubMed Central

Sax, Alexander F.

2015-01-01

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. PMID:25906476

Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom

ERIC Educational Resources Information Center

Baseden, Kyle A.; Tye, Jesse W.

2014-01-01

Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…

Molecular insight into the nanoconfined calcite–solution interface

PubMed Central

Diao, Yijue; Espinosa-Marzal, Rosa M.

2016-01-01

Little is known about the influence of nanoconfinement on calcium carbonate mineralization. Here, colloidal probe atomic force microscopy is used to confine the calcite–solution interface with a silica microsphere and to measure Derjaguin–Landau–Verwey–Overbeek (DLVO) and non-DLVO forces as a function of the calcium concentration, also after charge reversal of both surfaces occurs. Through the statistical analysis of the oscillatory component of a strong hydration force, the subnanometer interfacial structure of the confined atomically flat calcite is resolved in aqueous solution. By applying a mechanical work, both water and hydrated counterions are squeezed out from the nanoconfined solution, leaving the calcite surface more negatively charged than the analogous unconfined surfaces. Layer size and applied work allow a distinction between the hydration states of the counterions in the Stern layer; we propose counterions to be inner- and outer-sphere calcium ions, with a population of inner-sphere calcium ions larger than on unconfined calcite surfaces. It is also shown that the composition of the nanoconfined solution can be tuned by varying calcium concentration. This is a fundamental study of DLVO and hydration forces, and of their connection, on atomically flat calcite. More broadly, our work scrutinizes the greatly unexplored relation between surface science and confined mineralization, with implications for diverse areas of inquiry, such as nanoconfined biomineralization, CO2 sequestration in porous aquifers, and pressure solution and crystallization in confined hydrosystems. PMID:27790988

On the non-linear spectroscopy including saturated absorption and four-wave mixing in two and multi-level atoms: a computational study

NASA Astrophysics Data System (ADS)

Patel, M.; De Jager, G.; Nkosi, Z.; Wyngaard, A.; Govender, K.

2017-10-01

In this paper we report on the study of two and multi-level atoms interacting with multiple laser beams. The semi-classical approach is used to describe the system in which the atoms are treated quantum mechanically via the density matrix operator, while the laser beams are treated classically using Maxwells equations. We present results of a two level atom interacting with single and multiple laser beams and demonstrate Rabi oscillations between the levels. The effects of laser modulation on the dynamics of the atom (atomic populations and coherences) are examined by solving the optical Bloch equations. Plots of the density matrix elements as a function of time are presented for various parameters such as laser intensity, detuning, modulation etc. In addition, phase-space plots and Fourier analysis of the density matrix elements are provided. The atomic polarization, estimated from the coherence terms of the density matrix elements, is used in the numerical solution of Maxwells equations to determine the behaviour of the laser beams as they propagate through the atomic ensemble. The effects of saturation and hole-burning are demonstrated in the case of two counter propagating beams with one being a strong beam and the other being very weak. The above work is extended to include four-wave mixing in four level atoms in a diamond configuration. Two co-propagating beams of different wavelengths drive the atoms from a ground state |1〉 to an excited state |3〉 via an intermediate state |2〉. The atoms then move back to the ground state via another intermediate state |4〉, resulting in the generation of two additional correlated photon beams. The characteristics of these additional photons are studied.

Five- and six-electron harmonium atoms: Highly accurate electronic properties and their application to benchmarking of approximate 1-matrix functionals

NASA Astrophysics Data System (ADS)

Cioslowski, Jerzy; Strasburger, Krzysztof

2018-04-01

Electronic properties of several states of the five- and six-electron harmonium atoms are obtained from large-scale calculations employing explicitly correlated basis functions. The high accuracy of the computed energies (including their components), natural spinorbitals, and their occupation numbers makes them suitable for testing, calibration, and benchmarking of approximate formalisms of quantum chemistry and solid state physics. In the case of the five-electron species, the availability of the new data for a wide range of the confinement strengths ω allows for confirmation and generalization of the previously reached conclusions concerning the performance of the presently known approximations for the electron-electron repulsion energy in terms of the 1-matrix that are at heart of the density matrix functional theory (DMFT). On the other hand, the properties of the three low-lying states of the six-electron harmonium atom, computed at ω = 500 and ω = 1000, uncover deficiencies of the 1-matrix functionals not revealed by previous studies. In general, the previously published assessment of the present implementations of DMFT being of poor accuracy is found to hold. Extending the present work to harmonically confined systems with even more electrons is most likely counterproductive as the steep increase in computational cost required to maintain sufficient accuracy of the calculated properties is not expected to be matched by the benefits of additional information gathered from the resulting benchmarks.

The characterisation of atomic structure and glass-forming ability of the Zr-Cu-Co metallic glasses studied by molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Celtek, M.; Sengul, S.

2018-03-01

In the present work, the glass formation process and structural properties of Zr50Cu50-xCox (0 ≤ x ≤ 50) bulk metallic glasses were investigated by a molecular dynamics simulation with the many body tight-binding potentials. The evolution of structure and glass formation process with temperature were discussed using the coordination number, the radial distribution functions, the volume-temperature curve, icosahedral short-range order, glass transition temperature, Voronoi analysis, Honeycutt-Andersen pair analysis technique and the distribution of bond-angles. Results indicate that adding Co causes similar responses on the nature of the Zr50Cu50-xCox (0 ≤ x ≤ 50) alloys except for higher glass transition temperature and ideal icosahedral type ordered local atomic environment. Also, the differences of the atomic radii play the key role in influencing the atomic structure of these alloys. Both Cu and Co atoms play a significant role in deciding the chemical and topological short-range orders of the Zr50Cu50-xCox ternary liquids and amorphous alloys. The glass-forming ability of these alloys is supported by the experimental observations reported in the literature up to now.

Double-atomic layer of Tl on Si(111): Atomic arrangement and electronic properties

NASA Astrophysics Data System (ADS)

Mihalyuk, Alexey N.; Bondarenko, Leonid V.; Tupchaya, Alexandra Y.; Gruznev, Dimitry V.; Chou, Jyh-Pin; Hsing, Cheng-Rong; Wei, Ching-Ming; Zotov, Andrey V.; Saranin, Alexander A.

2018-02-01

Metastable double-atomic layer of Tl on Si(111) has recently been found to display interesting electric properties, namely superconductivity below 0.96 K and magnetic-field-induced transition into an insulating phase intermediated by a quantum metal state. In the present work, using a set of experimental techniques, including low-energy electron diffraction, scanning tunneling microscopy, angle-resolved photoelectron spectroscopy, in a combination with density-functional-theory calculations, we have characterized atomic and electronic properties of the Tl double layer on Si(111). The double Tl layer has been concluded to contain ∼ 2.4 monolayer of Tl. A top Tl layer has a '1 × 1' basic structure and displays 6 × 6 moiré pattern which originates from various residence sites of Tl atoms. Upon cooling below ∼ 140 K, the 6 × 6 moiré pattern changes to that having a 6√{ 3} × 6√{ 3} periodicity. However, the experimentally determined electron band dispersions show a 1 × 1 periodicity. The calculated band structure unfolded into the 1 × 1 surface Brillouin zone reproduces well the main features of the photoelectron spectra.

Transition metal decorated graphene-like zinc oxide monolayer: A first-principles investigation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lei, Jie; School of Science, Qilu University of Technology, Jinan, Shandong 250353; Xu, Ming-Chun

Transition metal (TM) atoms have been extensively employed to decorate the two-dimensional materials, endowing them with promising physical properties. Here, we have studied the adsorption of TM atoms (V, Cr, Mn, Fe, and Co) on graphene-like zinc oxide monolayer (g-ZnO) and the substitution of Zn by TM using first-principles calculations to search for the most likely configurations when TM atoms are deposited on g-ZnO. We found that when a V atom is initially placed on the top of Zn atom, V will squeeze out Zn from the two-dimensional plane then substitute it, which is a no barrier substitution process. Formore » heavier elements (Cr to Co), although the substitution configurations are more stable than the adsorption ones, there is an energy barrier for the adsorption-substitution transition with the height of tens to hundreds meV. Therefore, Cr to Co prefers to be adsorbed on the hollow site or the top of oxygen, which is further verified by the molecular dynamics simulations. The decoration of TM is revealed to be a promising approach in terms of tuning the work function of g-ZnO in a large energy range.« less

Transition metal decorated graphene-like zinc oxide monolayer: A first-principles investigation

NASA Astrophysics Data System (ADS)

Lei, Jie; Xu, Ming-Chun; Hu, Shu-Jun

2015-09-01

Transition metal (TM) atoms have been extensively employed to decorate the two-dimensional materials, endowing them with promising physical properties. Here, we have studied the adsorption of TM atoms (V, Cr, Mn, Fe, and Co) on graphene-like zinc oxide monolayer (g-ZnO) and the substitution of Zn by TM using first-principles calculations to search for the most likely configurations when TM atoms are deposited on g-ZnO. We found that when a V atom is initially placed on the top of Zn atom, V will squeeze out Zn from the two-dimensional plane then substitute it, which is a no barrier substitution process. For heavier elements (Cr to Co), although the substitution configurations are more stable than the adsorption ones, there is an energy barrier for the adsorption-substitution transition with the height of tens to hundreds meV. Therefore, Cr to Co prefers to be adsorbed on the hollow site or the top of oxygen, which is further verified by the molecular dynamics simulations. The decoration of TM is revealed to be a promising approach in terms of tuning the work function of g-ZnO in a large energy range.

First principles study of hydrogen adsorption on carbon nanowires.

NASA Astrophysics Data System (ADS)

Tapia, Alejandro; Aguilera, Luis; Murrieta, Gabriel; de Coss, Romeo

2007-03-01

Recently has been reported a new type of one-dimensional carbon structures. Carbon nanowires formed by a linear carbon-atom chain inside an armchair (5,5) carbon nanotube has been observed using high-resolution transmission electron microscopy. In the present work we have studied the changes in the electronic structure of a carbon nanowires and (5,5) single-walled carbon nanotubes (SWCN) when a hydrogen atom is adsorbed. We used the Density Functional Theory and the calculations where performed by the pseudopotentials LCAO method (SIESTA code) and the Generalized Gradient Approximation (GGA) for the exchange-correlation potential. We have analyzed the changes in the atomic structure, density of states (LDOS), and the local orbital population. We found charge transfer from the nanotube to the linear chain and the hydrogen atom, the electronic character of the chain and nanotube sub-systems in chain@SWCN is the same that in the corresponding isolated systems, chain or SWCN. But the hydrogen adsorption produced changes in the atomic estructure and the electronic properties. This research was supported by PRIORI-UADY under Grant No. FING-05-004 and Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grants No. 43830-F and 49985-J.

Ab initio theory of noble gas atoms in bcc transition metals.

PubMed

Jiang, Chao; Zhang, Yongfeng; Gao, Yipeng; Gan, Jian

2018-06-18

Systematic ab initio calculations based on density functional theory have been performed to gain fundamental understanding of the interactions between noble gas atoms (He, Ne, Ar and Kr) and bcc transition metals in groups 5B (V, Nb and Ta), 6B (Cr, Mo and W) and 8B (Fe). Our charge density analysis indicates that the strong polarization of nearest-neighbor metal atoms by noble gas interstitials is the electronic origin of their high formation energies. Such polarization becomes more significant with an increasing gas atom size and interstitial charge density in the host bcc metal, which explains the similar trend followed by the unrelaxed formation energies of noble gas interstitials. Upon allowing for local relaxation, nearby metal atoms move farther away from gas interstitials in order to decrease polarization, albeit at the expense of increasing the elastic strain energy. Such atomic relaxation is found to play an important role in governing both the energetics and site preference of noble gas atoms in bcc metals. Our most notable finding is that the fully relaxed formation energies of noble gas interstitials are strongly correlated with the elastic shear modulus of the bcc metal, and the physical origin of this unexpected correlation has been elucidated by our theoretical analysis based on the effective-medium theory. The kinetic behavior of noble gas atoms and their interaction with pre-existing vacancies in bcc transition metals have also been discussed in this work.

Determination of trace heavy metals in soil and sediments by atomic spectrometry following preconcentration with Schiff bases on Amberlite XAD-4.

PubMed

Kara, Derya; Fisher, Andrew; Hill, Steve J

2009-06-15

A matrix separation and analyte preconcentration system using Amberlite XAD copolymer resins functionalized by Schiff base reactions coupled with atomic spectrometry has been developed. Three different functionalized Amberlite XAD resins were synthesized using 4-phenylthiosemicarbazide, 2,3-dihydroxybenzaldehyde and 2-thiophenecarboxaldehyde as reagents. These resins could be used to preconcentrate transition and other trace heavy metal analytes from nitric acid digests of soil and sediment samples. Analyte retention was shown to work well at pH 6.0. After treatment of the digests with sodium fluoride and buffering to pH 6, samples that contain extremely large concentrations of iron were analysed for trace analytes without the excess iron overloading the capacity of the resin. The analytes Cd, Co, Cu, Ni and Pb were preconcentrated from acid extracts of certified soil/sediment samples and then eluted with 0.1M HNO(3) directly to the detection system. Flame atomic absorption spectrometry was used as a means of detection during the studies. The efficiency of the chelating resin and the accuracy of the proposed method were evaluated by the analysis of soil (SO-2) and sediment (LGC 6157 and MESS-3) certified reference materials.

Molecular dynamics simulation of coarse-grained poly(L-lysine) dendrimers.

PubMed

Rahimi, Ali; Amjad-Iranagh, Sepideh; Modarress, Hamid

2016-03-01

Poly(L-lysine) (PLL) dendrimer are amino acid based macromolecules and can be used as drug delivery agents. Their branched structure allows them to be functionalized by various groups to encapsulate drug agents into their structure. In this work, at first, an attempt was made on all-atom simulation of PLL dendrimer of different generations. Based on all-atom results, a course-grained model of this dendrimer was designed and its parameters were determined, to be used for simulation of three generations of PLL dendrimer, at two pHs. Similar to the all-atom, the coarse-grained results indicated that by increasing the generation, the dendrimer becomes more spherical. At pH 7, the dendrimer had larger size, whereas at pH 12, due to back folding of branching chains, they had the tendency to penetrate into the inner layers. The calculated radial probability and radial distribution functions confirm that at pH 7, the PLL dendrimer has more cavities and as a result it can encapsulate more water molecules into its inner structure. By calculating the moment of inertia and the aspect ratio, the formation of spherical structure for PLL dendrimer was confirmed.

Transient Absorption of Attosecond Pulses by He Atoms in Presence of Near-Infrared Laser Fields: A TDDFT Analysis of Sub-Cycle Temporal Structures

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2013-05-01

We study transient absorption of extreme ultraviolet (XUV) attosecond pulses in presence of near-infrared (NIR) laser fields by analyzing the population and photon emission of excited atomic energy levels. We consider He atoms and apply a self-interaction-free fully ab initio time-dependent density functional theory (TDDFT). Our method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential and incorporates explicitly the self-interaction correction. We focus on the sub-cycle (with respect to NIR field) temporal behavior of the population of the excited energy levels and related dynamics of photon emission. We observe and identify sub-cycle shifts in the photon emission spectrum as a function of the time delay between the XUV and NIR pulses. In the region where the two pulses overlap, the photon emission peaks have an oscillatory structure with a period of 1.3 fs, which is half of the NIR laser optical cycle. Such a structure was also observed in recent experiments on transient absorption. This work was partially supported by DOE and by MOE-NSC-NTU-Taiwan.

Development of Low Cost Gas Atomization of Precursor Powders for Simplified ODS Alloy Production

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anderson, Iver

2014-08-05

A novel gas atomization reaction synthesis (GARS) method was developed in this project to enable production (at our partner’s facility) a precursor Ni-Cr-Y-Ti powder with a surface oxide and an internal rare earth (RE) containing intermetallic compound (IMC) phase. Consolidation and heat-treatment experiments were performed at Ames Lab to promote the exchange of oxygen from the surface oxide to the RE intermetallic to form nano-metric oxide dispersoids. Alloy selection was aided by an internal oxidation and serial grinding experiments at Ames Lab and found that Hf-containing alloys may form more stable dispersoids than Ti-containing alloy, i.e., the Hf-containing system exhibitedmore » five different oxide phases and two different intermetallics compared to the two oxide phases and one intermetallic in the Ti-containing alloys. Since the simpler Ti-containing system was less complex to characterize, and make observations on the effects of processing parameters, the Ti-containing system was selected by Ames Lab for experimental atomization trials at our partner. An internal oxidation model was developed at Ames Lab and used to predict the heat treatment times necessary for dispersoid formation as a function of powder size and temperature. A new high-pressure gas atomization (HPGA) nozzle was developed at Ames Lab with the aim of promoting fine powder production at scales similar to that of the high gas-flow and melt-flow of industrial atomizers. The atomization nozzle was characterized using schlieren imaging and aspiration pressure testing at Ames Lab to determine the optimum melt delivery tip geometry and atomization pressure to promote enhanced secondary atomization mechanisms. Six atomization trials were performed at our partner to investigate the effects of: gas atomization pressure and reactive gas concentration on the particle size distribution (PSD) and the oxygen content of the resulting powder. Also, the effect on the rapidly solidified microstructure (as a function of powder size) was investigated at Ames Lab as a function of reactive gas composition and bulk alloy composition. The results indicated that the pulsatile gas atomization mechanism and a significantly enhanced yield of fine powders reported in the literature for this type of process were not observed. Also it was determined that reactive gas may marginally improve the fine powder yield but further experiments are required. The oxygen content in the gas also did not have any detrimental effect on the microstructure (i.e. did not significantly reduce undercooling). On the contrary, the oxygen addition to the atomization gas may have mitigated some potent catalytic nucleation sites, but not enough to significantly alter the microstructure vs. particle size relationship. Overall the downstream injection of oxygen was not found to significantly affect either the particle size distribution or undercooling (as inferred from microstructure and XRD observations) but injection further upstream, including in the gas atomization nozzle, remains to be investigated in later work.« less

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores.

PubMed

Pardon, Gaspard; Gatty, Hithesh K; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-11

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al(2)O(3)) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al(2)O(3) layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al(2)O(3) using ALD.

Pt-Al2O3 dual layer atomic layer deposition coating in high aspect ratio nanopores

NASA Astrophysics Data System (ADS)

Pardon, Gaspard; Gatty, Hithesh K.; Stemme, Göran; van der Wijngaart, Wouter; Roxhed, Niclas

2013-01-01

Functional nanoporous materials are promising for a number of applications ranging from selective biofiltration to fuel cell electrodes. This work reports the functionalization of nanoporous membranes using atomic layer deposition (ALD). ALD is used to conformally deposit platinum (Pt) and aluminum oxide (Al2O3) on Pt in nanopores to form a metal-insulator stack inside the nanopore. Deposition of these materials inside nanopores allows the addition of extra functionalities to nanoporous materials such as anodic aluminum oxide (AAO) membranes. Conformal deposition of Pt on such materials enables increased performances for electrochemical sensing applications or fuel cell electrodes. An additional conformal Al2O3 layer on such a Pt film forms a metal-insulator-electrolyte system, enabling field effect control of the nanofluidic properties of the membrane. This opens novel possibilities in electrically controlled biofiltration. In this work, the deposition of these two materials on AAO membranes is investigated theoretically and experimentally. Successful process parameters are proposed for a reliable and cost-effective conformal deposition on high aspect ratio three-dimensional nanostructures. A device consisting of a silicon chip supporting an AAO membrane of 6 mm diameter and 1.3 μm thickness with 80 nm diameter pores is fabricated. The pore diameter is reduced to 40 nm by a conformal deposition of 11 nm Pt and 9 nm Al2O3 using ALD.

Assessment of ten density functionals through the use of local hyper-softness to get insights about the catalytic activity : Iron-based organometallic compounds for ethylene polymerization as testing molecules.

PubMed

Martínez-Araya, Jorge I; Glossman-Mitnik, Daniel

2018-01-18

Ten functionals were used to assess their capability to compute a local reactivity descriptor coming from the Conceptual Density Functional Theory on a group of iron-based organometallic compounds that have been synthesized by Zohuri, G.H. et al. in 2010; these compounds bear the following substituent groups: H-, O 2 N- and CH 3 O- at the para position of the pyridine ring and their catalytic activities were experimentally measured by these authors. The present work involved a theoretical analysis applied on the aforementioned iron-based compounds thus leading to suggest a new 2,6-bis(imino)pyridine catalyst based on iron(II) bearing a fluorine atom whose possible catalytic activity is suggested to be near the catalytic activity of the complex bearing a hydrogen atom as a substituent group by means of the so called local hyper-softness (LHS) thus opening a chance to estimate a possible value of catalytic activity for a new catalyst that has not been synthesized yet without simulating the entire process of ethylene polymerization. Since Conceptual DFT is not a predictive theory, but rather interpretative, an analysis of the used reactivity descriptor and its dependence upon the level of theory was carried in the present work, thus revealing that care should be taken when DFT calculations are used for these purposes.

The baryonic mass function of galaxies.

PubMed

Read, J I; Trentham, Neil

2005-12-15

In the Big Bang about 5% of the mass that was created was in the form of normal baryonic matter (neutrons and protons). Of this about 10% ended up in galaxies in the form of stars or of gas (that can be in molecules, can be atomic, or can be ionized). In this work, we measure the baryonic mass function of galaxies, which describes how the baryonic mass is distributed within galaxies of different types (e.g. spiral or elliptical) and of different sizes. This can provide useful constraints on our current cosmology, convolved with our understanding of how galaxies form. This work relies on various large astronomical surveys, e.g. the optical Sloan Digital Sky Survey (to observe stars) and the HIPASS radio survey (to observe atomic gas). We then perform an integral over our mass function to determine the cosmological density of baryons in galaxies: Omega(b,gal)=0.0035. Most of these baryons are in stars: Omega(*)=0.0028. Only about 20% are in gas. The error on the quantities, as determined from the range obtained between different methods, is ca 10%; systematic errors may be much larger. Most (ca 90%) of the baryons in the Universe are not in galaxies. They probably exist in a warm/hot intergalactic medium. Searching for direct observational evidence and deeper theoretical understanding for this will form one of the major challenges for astronomy in the next decade.

Mechanism for transient migration of xenon in UO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, X.-Y.; Uberuaga, B. P.; Andersson, D. A.

2011-04-11

In this letter, we report recent work on atomistic modeling of diffusion migration events of the fission gas product xenon in UO{sub 2} nuclear fuel. Under nonequilibrium conditions, Xe atoms can occupy the octahedral interstitial site, in contrast to the thermodynamically most stable uranium substitutional site. A transient migration mechanism involving Xe and two oxygen atoms is identified using basin constrained molecular dynamics employing a Buckingham type interatomic potential. This mechanism is then validated using density functional theory calculations using the nudged elastic band method. An overall reduction in the migration barrier of 1.6-2.7 eV is obtained compared to vacancy-mediatedmore » diffusion on the uranium sublattice.« less

Simulating contrast inversion in atomic force microscopy imaging with real-space pseudopotentials

NASA Astrophysics Data System (ADS)

Lee, Alex; Sakai, Yuki; Chelikowsky, James

Atomic force microscopy measurements have reported contrast inversions for systems such as Cu2N and graphene that can hamper image interpretation and characterization. Here, we apply a simulation method based on ab initio real-space pseudopotentials to gain an understanding of the tip-sample interactions that influence the inversion. We find that chemically reactive tips induce an attractive binding force that results in the contrast inversion. The inversion is tip height dependent and not observed when using less reactive CO-functionalized tips. Work is supported by the DOE under DOE/DE-FG02-06ER46286 and by the Welch Foundation under Grant F-1837. Computational resources were provided by NERSC and XSEDE.

Atomistic simulations of TeO₂-based glasses: interatomic potentials and molecular dynamics.

PubMed

Gulenko, Anastasia; Masson, Olivier; Berghout, Abid; Hamani, David; Thomas, Philippe

2014-07-21

In this work we present for the first time empirical interatomic potentials that are able to reproduce TeO2-based systems. Using these potentials in classical molecular dynamics simulations, we obtained first results for the pure TeO2 glass structure model. The calculated pair distribution function is in good agreement with the experimental one, which indicates a realistic glass structure model. We investigated the short- and medium-range TeO2 glass structures. The local environment of the Te atom strongly varies, so that the glass structure model has a broad Q polyhedral distribution. The glass network is described as weakly connected with a large number of terminal oxygen atoms.

Configurational forces in electronic structure calculations using Kohn-Sham density functional theory

NASA Astrophysics Data System (ADS)

Motamarri, Phani; Gavini, Vikram

2018-04-01

We derive the expressions for configurational forces in Kohn-Sham density functional theory, which correspond to the generalized variational force computed as the derivative of the Kohn-Sham energy functional with respect to the position of a material point x . These configurational forces that result from the inner variations of the Kohn-Sham energy functional provide a unified framework to compute atomic forces as well as stress tensor for geometry optimization. Importantly, owing to the variational nature of the formulation, these configurational forces inherently account for the Pulay corrections. The formulation presented in this work treats both pseudopotential and all-electron calculations in a single framework, and employs a local variational real-space formulation of Kohn-Sham density functional theory (DFT) expressed in terms of the nonorthogonal wave functions that is amenable to reduced-order scaling techniques. We demonstrate the accuracy and performance of the proposed configurational force approach on benchmark all-electron and pseudopotential calculations conducted using higher-order finite-element discretization. To this end, we examine the rates of convergence of the finite-element discretization in the computed forces and stresses for various materials systems, and, further, verify the accuracy from finite differencing the energy. Wherever applicable, we also compare the forces and stresses with those obtained from Kohn-Sham DFT calculations employing plane-wave basis (pseudopotential calculations) and Gaussian basis (all-electron calculations). Finally, we verify the accuracy of the forces on large materials systems involving a metallic aluminum nanocluster containing 666 atoms and an alkane chain containing 902 atoms, where the Kohn-Sham electronic ground state is computed using a reduced-order scaling subspace projection technique [P. Motamarri and V. Gavini, Phys. Rev. B 90, 115127 (2014), 10.1103/PhysRevB.90.115127].

Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

PubMed

Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

2009-02-01

Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m

Correlated wave functions for three-particle systems with Coulomb interaction - The muonic helium atom

NASA Technical Reports Server (NTRS)

Huang, K.-N.

1977-01-01

A computational procedure for calculating correlated wave functions is proposed for three-particle systems interacting through Coulomb forces. Calculations are carried out for the muonic helium atom. Variational wave functions which explicitly contain interparticle coordinates are presented for the ground and excited states. General Hylleraas-type trial functions are used as the basis for the correlated wave functions. Excited-state energies of the muonic helium atom computed from 1- and 35-term wave functions are listed for four states.

Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

PubMed

Qi, Xuejun; Song, Wenwu; Shi, Jianwei

2017-01-01

Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

PubMed Central

Song, Wenwu; Shi, Jianwei

2017-01-01

Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

General method of solving the Schroedinger equation of atoms and molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakatsuji, Hiroshi

2005-12-15

We propose a general method of solving the Schroedinger equation of atoms and molecules. We first construct the wave function having the exact structure, using the ICI (iterative configuration or complement interaction) method and then optimize the variables involved by the variational principle. Based on the scaled Schroedinger equation and related principles, we can avoid the singularity problem of atoms and molecules and formulate a general method of calculating the exact wave functions in an analytical expansion form. We choose initial function {psi}{sub 0} and scaling g function, and then the ICI method automatically generates the wave function that hasmore » the exact structure by using the Hamiltonian of the system. The Hamiltonian contains all the information of the system. The free ICI method provides a flexible and variationally favorable procedure of constructing the exact wave function. We explain the computational procedure of the analytical ICI method routinely performed in our laboratory. Simple examples are given using hydrogen atom for the nuclear singularity case, the Hooke's atom for the electron singularity case, and the helium atom for both cases.« less

Atomic Force Microscopy Studies of Functional and Dysfunctional Pulmonary Surfactant Films. I. Micro- and Nanostructures of Functional Pulmonary Surfactant Films and the Effect of SP-A

PubMed Central

Zuo, Yi Y.; Keating, Eleonora; Zhao, Lin; Tadayyon, Seyed M.; Veldhuizen, Ruud A. W.; Petersen, Nils O.; Possmayer, Fred

2008-01-01

Monolayers of a functional pulmonary surfactant (PS) can reach very low surface tensions well below their equilibrium value. The mechanism by which PS monolayers reach such low surface tensions and maintain film stability remains unknown. As shown previously by fluorescence microscopy, phospholipid phase transition and separation seem to be important for the normal biophysical properties of PS. This work studied phospholipid phase transitions and separations in monolayers of bovine lipid extract surfactant using atomic force microscopy. Atomic force microscopy showed phospholipid phase separation on film compression and a monolayer-to-multilayer transition at surface pressure 40–50 mN/m. The tilted-condensed phase consisted of domains not only on the micrometer scale, as detected previously by fluorescence microscopy, but also on the nanometer scale, which is below the resolution limits of conventional optical methods. The nanodomains were embedded uniformly within the liquid-expanded phase. On compression, the microdomains broke up into nanodomains, thereby appearing to contribute to tilted-condensed and liquid-expanded phase remixing. Addition of surfactant protein A altered primarily the nanodomains and promoted the formation of multilayers. We conclude that the nanodomains play a predominant role in affecting the biophysical properties of PS monolayers and the monolayer-to-multilayer transition. PMID:18212010

Diffusion quantum Monte Carlo and density functional calculations of the structural stability of bilayer arsenene

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Santana, Juan A.; Özaydin, H. Duygu; Ersan, Fatih; Aktürk, O. Üzengi; Aktürk, Ethem; Reboredo, Fernando A.

2018-06-01

We have studied the structural stability of monolayer and bilayer arsenene (As) in the buckled (b) and washboard (w) phases with diffusion quantum Monte Carlo (DMC) and density functional theory (DFT) calculations. DMC yields cohesive energies of 2.826(2) eV/atom for monolayer b-As and 2.792(3) eV/atom for w-As. In the case of bilayer As, DMC and DFT predict that AA-stacking is the more stable form of b-As, while AB is the most stable form of w-As. The DMC layer-layer binding energies for b-As-AA and w-As-AB are 30(1) and 53(1) meV/atom, respectively. The interlayer separations were estimated with DMC at 3.521(1) Å for b-As-AA and 3.145(1) Å for w-As-AB. A comparison of DMC and DFT results shows that the van der Waals density functional method yields energetic properties of arsenene close to DMC, while the DFT + D3 method closely reproduced the geometric properties from DMC. The electronic properties of monolayer and bilayer arsenene were explored with various DFT methods. The bandgap values vary significantly with the DFT method, but the results are generally qualitatively consistent. We expect the present work to be useful for future experiments attempting to prepare multilayer arsenene and for further development of DFT methods for weakly bonded systems.

Apparatus for depositing a low work function material

DOEpatents

Balooch, Mehdi; Dinh, Long N.; Siekhaus, Wigbert J.

2006-10-10

Short-wavelength photons are used to ablate material from a low work function target onto a suitable substrate. The short-wavelength photons are at or below visible wavelength. The elemental composition of the deposit is controlled by the composition of the target and the gaseous environment in which the ablation process is performed. The process is carried out in a deposition chamber to which a short-wavelength laser is mounted and which includes a substrate holder which can be rotated, tilted, heated, or cooled. The target material is mounted onto a holder that spins the target during laser ablation. In addition, the deposition chamber is provided with a vacuum pump, an external gas supply with atomizer and radical generator, a gas generator for producing a flow of molecules on the substrate, and a substrate cleaning device, such as an ion gun. The substrate can be rotated and tilted, for example, whereby only the tip of an emitter can be coated with a low work function material.

Low work function surface layers produced by laser ablation using short-wavelength photons

DOEpatents

Balooch, Mehdi; Dinh, Long N.; Siekhaus, Wigbert J.

2000-01-01

Short-wavelength photons are used to ablate material from a low work function target onto a suitable substrate. The short-wavelength photons are at or below visible wavelength. The elemental composition of the deposit is controlled by the composition of the target and the gaseous environment in which the ablation process is performed. The process is carried out in a deposition chamber to which a short-wavelength laser is mounted and which includes a substrate holder which can be rotated, tilted, heated, or cooled. The target material is mounted onto a holder that spins the target during laser ablation. In addition, the deposition chamber is provided with a vacuum pump, an external gas supply with atomizer and radical generator, a gas generator for producing a flow of molecules on the substrate, and a substrate cleaning device, such as an ion gun. The substrate can be rotated and tilted, for example, whereby only the tip of an emitter can be coated with a low work function material.

Work function and surface stability of tungsten-based thermionic electron emission cathodes

NASA Astrophysics Data System (ADS)

Jacobs, Ryan; Morgan, Dane; Booske, John

2017-11-01

Materials that exhibit a low work function and therefore easily emit electrons into vacuum form the basis of electronic devices used in applications ranging from satellite communications to thermionic energy conversion. W-Ba-O is the canonical materials system that functions as the thermionic electron emitter commercially used in a range of high-power electron devices. However, the work functions, surface stability, and kinetic characteristics of a polycrystalline W emitter surface are still not well understood or characterized. In this study, we examined the work function and surface stability of the eight lowest index surfaces of the W-Ba-O system using density functional theory methods. We found that under the typical thermionic cathode operating conditions of high temperature and low oxygen partial pressure, the most stable surface adsorbates are Ba-O species with compositions in the range of Ba0.125O-Ba0.25O per surface W atom, with O passivating all dangling W bonds and Ba creating work function-lowering surface dipoles. Wulff construction analysis reveals that the presence of O and Ba significantly alters the surface energetics and changes the proportions of surface facets present under equilibrium conditions. Analysis of previously published data on W sintering kinetics suggests that fine W particles in the size range of 100-500 nm may be at or near equilibrium during cathode synthesis and thus may exhibit surface orientation fractions well described by the calculated Wulff construction.

Entanglement with negative Wigner function of three thousand atoms heralded by one photon

NASA Astrophysics Data System (ADS)

McConnell, Robert; Zhang, Hao; Hu, Jiazhong; Ćuk, Senka; Vuletić, Vladan

2016-06-01

Quantum-mechanically correlated (entangled) states of many particles are of interest in quantum information, quantum computing and quantum metrology. Metrologically useful entangled states of large atomic ensembles have been experimentally realized [1, 2, 3, 4, 5, 6, 7, 8, 9, 10], but these states display Gaussian spin distribution functions with a non-negative Wigner function. Non-Gaussian entangled states have been produced in small ensembles of ions [11, 12], and very recently in large atomic ensembles [13, 14, 15]. Here, we generate entanglement in a large atomic ensemble via the interaction with a very weak laser pulse; remarkably, the detection of a single photon prepares several thousand atoms in an entangled state. We reconstruct a negative-valued Wigner function, an important hallmark of nonclassicality, and verify an entanglement depth (minimum number of mutually entangled atoms) of 2910 ± 190 out of 3100 atoms. Attaining such a negative Wigner function and the mutual entanglement of virtually all atoms is unprecedented for an ensemble containing more than a few particles. While the achieved purity of the state is slightly below the threshold for entanglement-induced metrological gain, further technical improvement should allow the generation of states that surpass this threshold, and of more complex Schrödinger cat states for quantum metrology and information processing.

Measuring air core characteristics of a pressure-swirl atomizer via a transparent acrylic nozzle at various Reynolds numbers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Eun J.; Oh, Sang Youp; Kim, Ho Y.

2010-11-15

Because of thermal fluid-property dependence, atomization stability (or flow regime) can change even at fixed operating conditions when subject to temperature change. Particularly at low temperatures, fuel's high viscosity can prevent a pressure-swirl (or simplex) atomizer from sustaining a centrifugal-driven air core within the fuel injector. During disruption of the air core inside an injector, spray characteristics outside the nozzle reflect a highly unstable, nonlinear mode where air core length, Sauter mean diameter (SMD), cone angle, and discharge coefficient variability. To better understand injector performance, these characteristics of the pressure-swirl atomizer were experimentally investigated and data were correlated to Reynoldsmore » numbers (Re). Using a transparent acrylic nozzle, the air core length, SMD, cone angle, and discharge coefficient are observed as a function of Re. The critical Reynolds numbers that distinguish the transition from unstable mode to transitional mode and eventually to a stable mode are reported. The working fluids are diesel and a kerosene-based fuel, referred to as bunker-A. (author)« less

Joint Atomic Information Exchange Group information management project. Briefing outlining functions and specifications of JAIEG automated information management system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, M.G.

1983-07-20

The Joint Atomic Information Exchange Group (JAIEG) was formed in 1959. JAIEG's charter was to be the agent to determine the transmissibility of atomic information to foreign governments or regional defense organizations. JAIEG, operating from the joint policy direction of the Deputy Assistant Secretary for Military Application under the Department of Energy and of the Assistant to the Secretary of Defense for Atomic Energy under the Department of Defense, determines in a uniform and consistent manner the transmissibility of Restricted Data (RD) and Formerly Restricted Data (FRD). JAIEG also maintains records of all transmittal of such data, and maintains recordmore » copies of all information reviewed. This information exists only on paper and must be processed manually. JAIEG's work load has grown continuously with the size of its filing system. This has prompted an investigation of the potential benefits of automating JAIEG activities. Science Applications, Inc. (SAI) has studied JAIEG procedures and has identified several areas where JAIEG information processing activities can be automated to achieve greater system efficiency.« less

Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

2017-02-01

The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec-1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm-2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.

A theoretical and experimental study of neuromorphic atomic switch networks for reservoir computing.

PubMed

Sillin, Henry O; Aguilera, Renato; Shieh, Hsien-Hang; Avizienis, Audrius V; Aono, Masakazu; Stieg, Adam Z; Gimzewski, James K

2013-09-27

Atomic switch networks (ASNs) have been shown to generate network level dynamics that resemble those observed in biological neural networks. To facilitate understanding and control of these behaviors, we developed a numerical model based on the synapse-like properties of individual atomic switches and the random nature of the network wiring. We validated the model against various experimental results highlighting the possibility to functionalize the network plasticity and the differences between an atomic switch in isolation and its behaviors in a network. The effects of changing connectivity density on the nonlinear dynamics were examined as characterized by higher harmonic generation in response to AC inputs. To demonstrate their utility for computation, we subjected the simulated network to training within the framework of reservoir computing and showed initial evidence of the ASN acting as a reservoir which may be optimized for specific tasks by adjusting the input gain. The work presented represents steps in a unified approach to experimentation and theory of complex systems to make ASNs a uniquely scalable platform for neuromorphic computing.

Absence of single critical dose for the amorphization of quartz under ion irradiation

NASA Astrophysics Data System (ADS)

Zhang, S.; Pakarinen, O. H.; Backholm, M.; Djurabekova, F.; Nordlund, K.; Keinonen, J.; Wang, T. S.

2018-01-01

In this work, we first simulated the amorphization of crystalline quartz under 50 keV 23 Na ion irradiation with classical molecular dynamics (MD). We then used binary collision approximation algorithms to simulate the Rutherford backscattering spectrometry in channeling conditions (RBS-C) from these irradiated MD cells, and compared the RBS-C spectra with experiments. The simulated RBS-C results show an agreement with experiments in the evolution of amorphization as a function of dose, showing what appears to be (by this measure) full amorphization at about 2.2 eVṡatom-1 . We also applied other analysis methods, such as angular structure factor, Wigner-Seitz, coordination analysis and topological analysis, to analyze the structural evolution of the irradiated MD cells. The results show that the atomic-level structure of the sample keeps evolving after the RBS signal has saturated, until the dose of about 5 eVṡatom-1 . The continued evolution of the SiO2 structure makes the definition of what is, on the atomic level, an amorphized quartz ambiguous.

Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

PubMed

Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

2017-12-11

The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A theoretical and experimental study of neuromorphic atomic switch networks for reservoir computing

NASA Astrophysics Data System (ADS)

Sillin, Henry O.; Aguilera, Renato; Shieh, Hsien-Hang; Avizienis, Audrius V.; Aono, Masakazu; Stieg, Adam Z.; Gimzewski, James K.

2013-09-01

Atomic switch networks (ASNs) have been shown to generate network level dynamics that resemble those observed in biological neural networks. To facilitate understanding and control of these behaviors, we developed a numerical model based on the synapse-like properties of individual atomic switches and the random nature of the network wiring. We validated the model against various experimental results highlighting the possibility to functionalize the network plasticity and the differences between an atomic switch in isolation and its behaviors in a network. The effects of changing connectivity density on the nonlinear dynamics were examined as characterized by higher harmonic generation in response to AC inputs. To demonstrate their utility for computation, we subjected the simulated network to training within the framework of reservoir computing and showed initial evidence of the ASN acting as a reservoir which may be optimized for specific tasks by adjusting the input gain. The work presented represents steps in a unified approach to experimentation and theory of complex systems to make ASNs a uniquely scalable platform for neuromorphic computing.

Modeling protein structure at near atomic resolutions with Gorgon.

PubMed

Baker, Matthew L; Abeysinghe, Sasakthi S; Schuh, Stephen; Coleman, Ross A; Abrams, Austin; Marsh, Michael P; Hryc, Corey F; Ruths, Troy; Chiu, Wah; Ju, Tao

2011-05-01

Electron cryo-microscopy (cryo-EM) has played an increasingly important role in elucidating the structure and function of macromolecular assemblies in near native solution conditions. Typically, however, only non-atomic resolution reconstructions have been obtained for these large complexes, necessitating computational tools for integrating and extracting structural details. With recent advances in cryo-EM, maps at near-atomic resolutions have been achieved for several macromolecular assemblies from which models have been manually constructed. In this work, we describe a new interactive modeling toolkit called Gorgon targeted at intermediate to near-atomic resolution density maps (10-3.5 Å), particularly from cryo-EM. Gorgon's de novo modeling procedure couples sequence-based secondary structure prediction with feature detection and geometric modeling techniques to generate initial protein backbone models. Beyond model building, Gorgon is an extensible interactive visualization platform with a variety of computational tools for annotating a wide variety of 3D volumes. Examples from cryo-EM maps of Rotavirus and Rice Dwarf Virus are used to demonstrate its applicability to modeling protein structure. Copyright © 2011 Elsevier Inc. All rights reserved.

Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion

PubMed Central

Schmidt, Michael W.; Ivanic, Joseph; Ruedenberg, Klaus

2014-01-01

An analysis based on the variation principle shows that in the molecules H2+, H2, B2, C2, N2, O2, F2, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation. PMID:24880263

Covalent bonds are created by the drive of electron waves to lower their kinetic energy through expansion.

PubMed

Schmidt, Michael W; Ivanic, Joseph; Ruedenberg, Klaus

2014-05-28

An analysis based on the variation principle shows that in the molecules H2 (+), H2, B2, C2, N2, O2, F2, covalent bonding is driven by the attenuation of the kinetic energy that results from the delocalization of the electronic wave function. For molecular geometries around the equilibrium distance, two features of the wave function contribute to this delocalization: (i) Superposition of atomic orbitals extends the electronic wave function from one atom to two or more atoms; (ii) intra-atomic contraction of the atomic orbitals further increases the inter-atomic delocalization. The inter-atomic kinetic energy lowering that (perhaps counter-intuitively) is a consequence of the intra-atomic contractions drives these contractions (which per se would increase the energy). Since the contractions necessarily encompass both, the intra-atomic kinetic and potential energy changes (which add to a positive total), the fact that the intra-atomic potential energy change renders the total potential binding energy negative does not alter the fact that it is the kinetic delocalization energy that drives the bond formation.

Metal adsorption on monolayer blue phosphorene: A first principles study

NASA Astrophysics Data System (ADS)

Khan, Imran; Son, Jicheol; Hong, Jisang

2018-01-01

We investigated the electronic structure, adsorption energies, magnetic properties, dipole moment and work function of metal adatoms (Mg, Cr, Mo, Pd, Pt, and Au) adsorption on a blue phosphorene monolayer. For Mg, Pt and Au metals, the most stable state was found in hollow site while for Cr, Mo and Pd metals we found an adsorption in valley site. We suggest that the Pd and Pt atoms prefer 2D growth mode while the Mg, Cr, Mo and Au atoms prefer 3D island growth mode on monolayer phosphorene. The electronic band structures and magnetic properties were dependent on the doping site and dopant materials. For instance, the semiconducting features were preserved in Mg, Pd, Pt, and Au doped systems. However, the Cr and Mo doped systems displayed half-metallic band structures. The total magnetic moment of 4.05, 2.0 and 0.77 μB /impurity atom were obtained in Cr, Mo and Au doped systems whereas the Mg, Pd and Pt doped systems remained nonmagnetic. We also investigated the magnetic interaction between two transition metal impurities. We observed ferromagnetic coupling between two transition metal impurities in Cr and Mo doped systems while the Au doped system displayed almost degenerated magnetic state. For Mg, Cr, and Mo adsorptions, we found relatively large values of dipole moments compared to those in the Pd, Pt and Au adsorptions. This resulted in a significant suppression of the work function in Mg, Cr and Mo adsorptions. Overall, adsorption can tune the physical and magnetic properties of phosphorene monolayer.

3 CFR - Delegation of Certain Functions Under Section 104(g) of the United States-India Peaceful Atomic...

Code of Federal Regulations, 2011 CFR

2011-01-01

...) of the United States-India Peaceful Atomic Energy Cooperation Act of 2006, as Amended by Public Law... Certain Functions Under Section 104(g) of the United States-India Peaceful Atomic Energy Cooperation Act... President by section 104(g) of the United States-India Peaceful Atomic Energy Cooperation Act of 2006...

Zinc in Entamoeba invadens.

NASA Technical Reports Server (NTRS)

Morgan, R. S.; Sattilaro, R. F.

1972-01-01

Atomic absorption spectroscopy, electron microprobe analysis, and dithizone staining of trophozoites and cysts of Entamoeba invadens demonstrate that these cells have a high concentration of zinc (approximately one picogram per cell or 1% of their dry weight). In the cysts of this organism, the zinc is confined to the chromatoid bodies, which previous work has shown to contain crystals of ribosomes. The chemical state and function of this zinc are unknown.

Three Dimensional Positron Annihilation Momentum Measurement Technique Applied to Measure Oxygen-Atom Defects in 6H Silicon Carbide

DTIC Science & Technology

2010-03-01

Stormer et al [9] measured 6H SiC’s positron work function (Φ + ),-3.0 ± 0.2 eV, which is the same value for the most commonly used positron...Subjected to various Treatments‖, Materials Science Forum, Vols. 255-7, pp. 662-4. 9. Stormer J, Goodyear A, Anwand W, Brauer G, Coleman P, and

Adsorption of xenon on vicinal copper and platinum surfaces

NASA Astrophysics Data System (ADS)

Baker, Layton

The adsorption of xenon was studied on Cu(111), Cu(221), Cu(643) and on Pt(111), Pt(221), and Pt(531) using low energy electron diffraction (LEED), temperature programmed desorption (TPD) of xenon, and ultraviolet photoemission of adsorbed xenon (PAX). These experiments were performed to study the atomic and electronic structure of stepped and step-kinked, chiral metal surfaces. Xenon TPD and PAX were performed on each surface in an attempt to titrate terrace, step edge, and kink adsorption sites by adsorption energetics (TPD) and local work function differences (PAX). Due to the complex behavior of xenon on the vicinal copper and platinum metal surfaces, adsorption sites on these surfaces could not be adequately titrated by xenon TPD. On Cu(221) and Cu(643), xenon desorption from step adsorption sites was not apparent leading to the conclusion that the energy difference between terrace and step adsorption is minuscule. On Pt(221) and Pt(531), xenon TPD indicated that xenon prefers to bond at step edges and that the xenon-xenon interaction at step edges in repulsive but no further indication of step-kink adsorption was observed. The Pt(221) and Pt(531) TPD spectra indicated that the xenon overlayer undergoes strong compression near monolayer coverage on these surfaces due to repulsion between step-edge adsorbed xenon and other encroaching xenon atoms. The PAX experiments on the copper and platinum surfaces demonstrated that the step adsorption sites have lower local work functions than terrace adsorption sites and that higher step density leads to a larger separation in the local work function of terrace and step adsorption sites. The PAX spectra also indicated that, for all surfaces studied at 50--70 K, step adsorption is favored at low coverage but the step sites are not saturated until monolayer coverage is reached; this observation is due to the large entropy difference between terrace and step adsorption states and to repulsive interactions between xenon atoms adsorbed at step edges (on the platinum surfaces). The results herein provide several novel observations regarding the adsorptive behavior of xenon on vicinal copper and platinum surfaces.

The cataphoretic emitter effect exhibited in high intensity discharge lamp electrodes

NASA Astrophysics Data System (ADS)

Mentel, Juergen

2018-01-01

A mono-layer of atoms, electropositive with respect to the substrate atoms, forms a dipole layer, reducing its work function. Such a layer is generated by diffusion of emitter material from the interior of the substrate, by vapour deposition or by deposition of emitter material onto arc electrodes by cataphoresis. This cataphoretic emitter effect is investigated within metal halide lamps with transparent YAG ceramic burners, and within model lamps. Within the YAG lamps, arcs are operated with switched-dc current between rod shaped tungsten electrodes in high pressure Hg vapour seeded with metal iodides. Within the model lamps, dc arcs are operated between rod-shaped tungsten electrodes—one doped—in atmospheric pressure Ar. Electrode temperatures are determined by 1λ -pyrometry, combined with simulation of the electrode heat balance. Plasma temperatures, atom and ion densities of emitter material are determined by emission and absorption spectroscopy. Phase resolved measurements in YAG lamps seeded with CeI3, CsI, DyI3, TmI3 and LaI3 show, within the cathodic half period, a reduction of the electrode temperature and an enhanced metal ion density in front of the electrode, and an opposite behavior after phase reversal. With increasing operating frequency, the state of the cathode overlaps onto the anodic phase—except for Cs, being low in adsorption energy. Generally, the phase averaged electrode tip temperature is reduced by seeding a lamp with emitter material; its height depends on admixtures. Measurements at tungsten electrodes doped with ThO2, La2O3 and Ce2O3 within the model lamp show that evaporated emitter material is redeposited by an emitter ion current onto the electrode surface. It reduces the work function of tungsten cathodes above the evaporation temperature of the emitter material, too; and also of cold anodes, indicating a field reversal in front of them. The formation of an emitter spot at low cathode temperature and high emitter material density is traced back to a locally reduced work function generated by a locally enhanced emitter ion current density.

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

PubMed

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

Work Function Engineering of Graphene

PubMed Central

Garg, Rajni; Dutta, Naba K.; Roy Choudhury, Namita

2014-01-01

Graphene is a two dimensional one atom thick allotrope of carbon that displays unusual crystal structure, electronic characteristics, charge transport behavior, optical clarity, physical & mechanical properties, thermal conductivity and much more that is yet to be discovered. Consequently, it has generated unprecedented excitement in the scientific community; and is of great interest to wide ranging industries including semiconductor, optoelectronics and printed electronics. Graphene is considered to be a next-generation conducting material with a remarkable band-gap structure, and has the potential to replace traditional electrode materials in optoelectronic devices. It has also been identified as one of the most promising materials for post-silicon electronics. For many such applications, modulation of the electrical and optical properties, together with tuning the band gap and the resulting work function of zero band gap graphene are critical in achieving the desired properties and outcome. In understanding the importance, a number of strategies including various functionalization, doping and hybridization have recently been identified and explored to successfully alter the work function of graphene. In this review we primarily highlight the different ways of surface modification, which have been used to specifically modify the band gap of graphene and its work function. This article focuses on the most recent perspectives, current trends and gives some indication of future challenges and possibilities. PMID:28344223

Work Function Engineering of Graphene.

PubMed

Garg, Rajni; Dutta, Naba K; Choudhury, Namita Roy

2014-04-03

Graphene is a two dimensional one atom thick allotrope of carbon that displays unusual crystal structure, electronic characteristics, charge transport behavior, optical clarity, physical & mechanical properties, thermal conductivity and much more that is yet to be discovered. Consequently, it has generated unprecedented excitement in the scientific community; and is of great interest to wide ranging industries including semiconductor, optoelectronics and printed electronics. Graphene is considered to be a next-generation conducting material with a remarkable band-gap structure, and has the potential to replace traditional electrode materials in optoelectronic devices. It has also been identified as one of the most promising materials for post-silicon electronics. For many such applications, modulation of the electrical and optical properties, together with tuning the band gap and the resulting work function of zero band gap graphene are critical in achieving the desired properties and outcome. In understanding the importance, a number of strategies including various functionalization, doping and hybridization have recently been identified and explored to successfully alter the work function of graphene. In this review we primarily highlight the different ways of surface modification, which have been used to specifically modify the band gap of graphene and its work function. This article focuses on the most recent perspectives, current trends and gives some indication of future challenges and possibilities.

Compact representation of continuous energy surfaces for more efficient protein design

PubMed Central

Hallen, Mark A.; Gainza, Pablo; Donald, Bruce R.

2015-01-01

In macromolecular design, conformational energies are sensitive to small changes in atom coordinates, so modeling the small, continuous motions of atoms around low-energy wells confers a substantial advantage in structural accuracy; however, modeling these motions comes at the cost of a very large number of energy function calls, which form the bottleneck in the design calculation. In this work, we remove this bottleneck by consolidating all conformational energy evaluations into the precomputation of a local polynomial expansion of the energy about the “ideal” conformation for each low-energy, “rotameric” state of each residue pair. This expansion is called Energy as Polynomials in Internal Coordinates (EPIC), where the internal coordinates can be sidechain dihedrals, backrub angles, and/or any other continuous degrees of freedom of a macromolecule, and any energy function can be used without adding any asymptotic complexity to the design. We demonstrate that EPIC efficiently represents the energy surface for both molecular-mechanics and quantum-mechanical energy functions, and apply it specifically to protein design to model both sidechain and backbone degrees of freedom. PMID:26089744

Quantum Monte Carlo for atoms and molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barnett, R.N.

1989-11-01

The diffusion quantum Monte Carlo with fixed nodes (QMC) approach has been employed in studying energy-eigenstates for 1--4 electron systems. Previous work employing the diffusion QMC technique yielded energies of high quality for H{sub 2}, LiH, Li{sub 2}, and H{sub 2}O. Here, the range of calculations with this new approach has been extended to include additional first-row atoms and molecules. In addition, improvements in the previously computed fixed-node energies of LiH, Li{sub 2}, and H{sub 2}O have been obtained using more accurate trial functions. All computations were performed within, but are not limited to, the Born-Oppenheimer approximation. In our computations,more » the effects of variation of Monte Carlo parameters on the QMC solution of the Schroedinger equation were studied extensively. These parameters include the time step, renormalization time and nodal structure. These studies have been very useful in determining which choices of such parameters will yield accurate QMC energies most efficiently. Generally, very accurate energies (90--100% of the correlation energy is obtained) have been computed with single-determinant trail functions multiplied by simple correlation functions. Improvements in accuracy should be readily obtained using more complex trial functions.« less

Measurements of neutral and ion velocity distribution functions in a Hall thruster

NASA Astrophysics Data System (ADS)

Svarnas, Panagiotis; Romadanov, Iavn; Diallo, Ahmed; Raitses, Yevgeny

2015-11-01

Hall thruster is a plasma device for space propulsion. It utilizes a cross-field discharge to generate a partially ionized weakly collisional plasma with magnetized electrons and non-magnetized ions. The ions are accelerated by the electric field to produce the thrust. There is a relatively large number of studies devoted to characterization of accelerated ions, including measurements of ion velocity distribution function using laser-induced fluorescence diagnostic. Interactions of these accelerated ions with neutral atoms in the thruster and the thruster plume is a subject of on-going studies, which require combined monitoring of ion and neutral velocity distributions. Herein, laser-induced fluorescence technique has been employed to study neutral and single-charged ion velocity distribution functions in a 200 W cylindrical Hall thruster operating with xenon propellant. An optical system is installed in the vacuum chamber enabling spatially resolved axial velocity measurements. The fluorescence signals are well separated from the plasma background emission by modulating the laser beam and using lock-in detectors. Measured velocity distribution functions of neutral atoms and ions at different operating parameters of the thruster are reported and analyzed. This work was supported by DOE contract DE-AC02-09CH11466.

Interconfigurational energies in transition-metal atoms using gradient-corrected density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kutzler, F.W.; Painter, G.S.

1991-03-15

The rapid variation of charge and spin densities in atoms and molecules provides a severe test for local-density-functional theory and for the use of gradient corrections. In the study reported in this paper, we use the Langreth, Mehl, and Hu (LMH) functional and the generalized gradient approximation (GGA) of Perdew and Yue to calculate {ital s}-{ital d} transition energies, 4{ital s} ionization energies, and 3{ital d} ionization energies for the 3{ital d} transition-metal atoms. These calculations are compared with results from the local-density functional of Vosko, Wilk, and Nusair. By comparison with experimental energies, we find that the gradient functionalsmore » are only marginally more successful than the local-density approximation in calculating energy differences between states in transition-metal atoms. The GGA approximation is somewhat better than the LMH functional for most of the atoms studied, although there are several exceptions.« less

Travel time tomography with local image regularization by sparsity constrained dictionary learning

NASA Astrophysics Data System (ADS)

Bianco, M.; Gerstoft, P.

2017-12-01

We propose a regularization approach for 2D seismic travel time tomography which models small rectangular groups of slowness pixels, within an overall or `global' slowness image, as sparse linear combinations of atoms from a dictionary. The groups of slowness pixels are referred to as patches and a dictionary corresponds to a collection of functions or `atoms' describing the slowness in each patch. These functions could for example be wavelets.The patch regularization is incorporated into the global slowness image. The global image models the broad features, while the local patch images incorporate prior information from the dictionary. Further, high resolution slowness within patches is permitted if the travel times from the global estimates support it. The proposed approach is formulated as an algorithm, which is repeated until convergence is achieved: 1) From travel times, find the global slowness image with a minimum energy constraint on the pixel variance relative to a reference. 2) Find the patch level solutions to fit the global estimate as a sparse linear combination of dictionary atoms.3) Update the reference as the weighted average of the patch level solutions.This approach relies on the redundancy of the patches in the seismic image. Redundancy means that the patches are repetitions of a finite number of patterns, which are described by the dictionary atoms. Redundancy in the earth's structure was demonstrated in previous works in seismics where dictionaries of wavelet functions regularized inversion. We further exploit redundancy of the patches by using dictionary learning algorithms, a form of unsupervised machine learning, to estimate optimal dictionaries from the data in parallel with the inversion. We demonstrate our approach on densely, but irregularly sampled synthetic seismic images.

Photoinduced charge-transfer electronic excitation of tetracyanoethylene/tetramethylethylene complex in dichloromethane

NASA Astrophysics Data System (ADS)

Xu, Long-Kun; Bi, Ting-Jun; Ming, Mei-Jun; Wang, Jing-Bo; Li, Xiang-Yuan

2017-07-01

Based on the previous work on nonequilibrium solvation model by the authors, Intermolecular charge-transfer electronic excitation of tetracyanoethylene (TCE)/tetramethylethylene (TME) π -stacked complex in dichloromethane (DCM) has been investigated. For weak interaction correction, dispersion corrected functional DFT-D3 is adopted for geometry optimization. In order to identify the excitation metric, dipole moment components of each Cartesian direction, atomic charge, charge separation and Δr index are analyzed for TCE/TME complex. Calculation shows that the calculated excitation energy is dependent on the functional choice, when conjuncted with suitable time-dependent density functional, the modified nonequilibrium expression gives satisfied results for intermolecular charge-transfer electronic excitation.

Analysis of spatial correlations in a model two-dimensional liquid through eigenvalues and eigenvectors of atomic-level stress matrices.

PubMed

Levashov, V A; Stepanov, M G

2016-01-01

Considerations of local atomic-level stresses associated with each atom represent a particular approach to address structures of disordered materials at the atomic level. We studied structural correlations in a two-dimensional model liquid using molecular dynamics simulations in the following way. We diagonalized the atomic-level stress tensor of every atom and investigated correlations between the eigenvalues and orientations of the eigenvectors of different atoms as a function of distance between them. It is demonstrated that the suggested approach can be used to characterize structural correlations in disordered materials. In particular, we found that changes in the stress correlation functions on decrease of temperature are the most pronounced for the pairs of atoms with separation distance that corresponds to the first minimum in the pair density function. We also show that the angular dependencies of the stress correlation functions previously reported by Wu et al. [Phys. Rev. E 91, 032301 (2015)10.1103/PhysRevE.91.032301] do not represent the anisotropic Eshelby's stress fields, as it is suggested, but originate in the rotational properties of the stress tensors.

Experiments with bosonic atoms for quantum gas assembly

NASA Astrophysics Data System (ADS)

Brown, Mark; Lin, Yiheng; Lester, Brian; Kaufman, Adam; Ball, Randall; Brossard, Ludovic; Isaev, Leonid; Thiele, Tobias; Lewis-Swan, Robert; Schymik, Kai-Niklas; Rey, Ana Maria; Regal, Cindy

2017-04-01

Quantum gas assembly is a promising platform for preparing and observing neutral atom systems on the single-atom level. We have developed a toolbox that includes ground-state laser cooling, high-fidelity loading techniques, addressable spin control, and dynamic spatial control and coupling of atoms. Already, this platform has enabled us to pursue a number of experiments studying entanglement and interference of pairs of bosonic atoms. We discuss our recent work in probabilistically entangling neutral atoms via interference, measurement, and post-selection as well as our future pursuits of interesting spin-motion dynamics of larger arrays of atoms. This work was supported by the David and Lucile Packard Foundation, National Science Foundation Physics Frontier Centers, and the National Defense Science and Engineering Graduate Fellowships program.

Probing physical properties at the nanoscale using atomic force microscopy

NASA Astrophysics Data System (ADS)

Ditzler, Lindsay Rachel

Techniques that measure physical properties at the nanoscale with high sensitivity are significantly limited considering the number of new nanomaterials being developed. The development of atomic force microscopy (AFM) has lead to significant advancements in the ability to characterize physical properties of materials in all areas of science: chemistry, physics, engineering, and biology have made great scientific strides do to the versatility of the AFM. AFM is used for quantification of many physical properties such as morphology, electrical, mechanical, magnetic, electrochemical, binding interactions, and protein folding. This work examines the electrical and mechanical properties of materials applicable to the field of nano-electronics. As electronic devices are miniaturized the demand for materials with unique electrical properties, which can be developed and exploited, has increased. For example, discussed in this work, a derivative of tetrathiafulvalene, which exhibits a unique loss of conductivity upon compression of the self-assembled monolayer could be developed into a molecular switch. This work also compares tunable organic (tetraphenylethylene tetracarboxylic acid and bis(pyridine)s assemblies) and metal-organic (Silver-stilbizole coordination compounds) crystals which show high electrical conductivity. The electrical properties of these materials vary depending on their composition allowing for the development of compositionally tunable functional materials. Additional work was done to investigate the effects of molecular environment on redox active 11-ferroceneyl-1 undecanethiol (Fc) molecules. The redox process of mixed monolayers of Fc and decanethiol was measured using conductive probe atomic force microscopy and force spectroscopy. As the concentration of Fc increased large, variations in the force were observed. Using these variations the number of oxidized molecules in the monolayer was determined. AFM is additionally capable of investigating interactions at the nanoscale, such as ligand-receptor interactions. This work examines the interactions between the enzyme dihydrofolate reductase (DHFR), a widely investigated enzyme targeted for cancer and antimicrobial pharmaceutical, and methotrexate (MTX), a strong competitive inhibitor of DHFR. The DHFR was immobilized on a gold substrate, bound through a single surface cysteine, and maintained catalytic activity. AFM probe was functionalized with MTX and the interaction strength was measured using AFM. This work highlights the versatility of AFM, specifically force spectroscopy for the quantification of electrical, mechanical, and ligand-receptor interactions at the nanoscale.

Entanglement of 3000 atoms by detecting one photon

NASA Astrophysics Data System (ADS)

Vuletic, Vladan

2016-05-01

Quantum-mechanically correlated (entangled) states of many particles are of interest in quantum information, quantum computing and quantum metrology. In particular, entangled states of many particles can be used to overcome limits on measurements performed with ensembles of independent atoms (standard quantum limit). Metrologically useful entangled states of large atomic ensembles (spin squeezed states) have been experimentally realized. These states display Gaussian spin distribution functions with a non-negative Wigner quasiprobability distribution function. We report the generation of entanglement in a large atomic ensemble via an interaction with a very weak laser pulse; remarkably, the detection of a single photon prepares several thousand atoms in an entangled state. We reconstruct a negative-valued Wigner function, and verify an entanglement depth (the minimum number of mutually entangled atoms) that comprises 90% of the atomic ensemble containing 3100 atoms. Further technical improvement should allow the generation of more complex Schrödinger cat states, and of states the overcome the standard quantum limit.

Smallest Nanoelectronic with Atomic Devices with Precise Structures

NASA Technical Reports Server (NTRS)

Yamada, Toshishige

2000-01-01

Since its invention in 1948, the transistor has revolutionized our everyday life - transistor radios and TV's appeared in the early 1960s, personal computers came into widespread use in the mid-1980s, and cellular phones, laptops, and palm-sized organizers dominated the 1990s. The electronics revolution is based upon transistor miniaturization; smaller transistors are faster, and denser circuitry has more functionality. Transistors in current generation chips are 0.25 micron or 250 nanometers in size, and the electronics industry has completed development of 0.18 micron transistors which will enter production within the next few years. Industry researchers are now working to reduce transistor size down to 0.13 micron - a thousandth of the width of a human hair. However, studies indicate that the miniaturization of silicon transistors will soon reach its limit. For further progress in microelectronics, scientists have turned to nanotechnology to advance the science. Rather than continuing to miniaturize transistors to a point where they become unreliable, nanotechnology offers the new approach of building devices on the atomic scale [see sidebar]. One vision for the next generation of miniature electronics is atomic chain electronics, where devices are composed of atoms aligned on top of a substrate surface in a regular pattern. The Atomic Chain Electronics Project (ACEP) - part of the Semiconductor Device Modeling and Nanotechnology group, Integrated Product Team at the NAS Facility has been developing the theory of understanding atomic chain devices, and the author's patent for atomic chain electronics is now pending.

Biological monitoring of glazers exposed to lead in the ceramics industry in Iran.

PubMed

Shouroki, Fatemeh Kargar; Shahtaheri, Seyed Jamaleddin; Golbabaei, Farideh; Barkhordari, Abolfazle; Rahimi-Froushani, Abbas

2015-01-01

Exposure to heavy metals, particularly lead, takes place in the ceramics industry. Lead is used in glaze to produce smooth and brilliant surfaces; thus, there is a likelihood of occupational adverse effects on humans. Urine samples were collected from 49 glazers at the start and end of the work shifts (98 samples). Solid phase extraction was used for separation and pre-concentration of the analyte. Samples were analysed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Lung function tests were performed on both control and lead exposed subjects. Statistical analysis of covariance (ANCOVA) was used to evaluate the data obtained. The concentration of lead in glazers was 6.37 times higher than in the control group. Lung functions were significantly lower in the glazers compared to the control group (p < 0.001). Results showed that poor ventilation systems, overtime work and work history are effective determinants of high exposure levels.

Sulfur Atoms Adsorbed on Cu(100) at Low Coverage: Characterization and Stability against Complexation

DOE PAGES

Walen, Holly; Liu, Da-Jiang; Oh, Junepyo; ...

2017-08-22

By using scanning tunneling microscopy, we characterize the size and bias-dependent shape of sulfur atoms on Cu(100) at low coverage (below 0.1 monolayers) and low temperature (quenched from 300 to 5 K). Sulfur atoms populate the Cu(100) terraces more heavily than steps at low coverage, but as coverage approaches 0.1 monolayers, close-packed step edges become fully populated, with sulfur atoms occupying sites on top of the step. Density functional theory (DFT) corroborates the preferential population of terraces at low coverage as well as the step adsorption site. In experiment, small regions with p(2 × 2)-like atomic arrangements emerge on themore » terraces as sulfur coverage approaches 0.1 monolayer. Using DFT, a lattice gas model has been developed, and Monte Carlo simulations based on this model have been compared with the observed terrace configurations. A model containing eight pairwise interaction energies, all repulsive, gives qualitative agreement. Experiment shows that atomic adsorbed sulfur is the only species on Cu(100) up to a coverage of 0.09 monolayers. There are no Cu–S complexes. Conversely, prior work has shown that a Cu 2S 3 complex forms on Cu(111) under comparable conditions. On the basis of DFT, this difference can be attributed mainly to stronger adsorption of sulfur on Cu(100) as compared with Cu(111).« less

Sulfur Atoms Adsorbed on Cu(100) at Low Coverage: Characterization and Stability against Complexation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walen, Holly; Liu, Da-Jiang; Oh, Junepyo

By using scanning tunneling microscopy, we characterize the size and bias-dependent shape of sulfur atoms on Cu(100) at low coverage (below 0.1 monolayers) and low temperature (quenched from 300 to 5 K). Sulfur atoms populate the Cu(100) terraces more heavily than steps at low coverage, but as coverage approaches 0.1 monolayers, close-packed step edges become fully populated, with sulfur atoms occupying sites on top of the step. Density functional theory (DFT) corroborates the preferential population of terraces at low coverage as well as the step adsorption site. In experiment, small regions with p(2 × 2)-like atomic arrangements emerge on themore » terraces as sulfur coverage approaches 0.1 monolayer. Using DFT, a lattice gas model has been developed, and Monte Carlo simulations based on this model have been compared with the observed terrace configurations. A model containing eight pairwise interaction energies, all repulsive, gives qualitative agreement. Experiment shows that atomic adsorbed sulfur is the only species on Cu(100) up to a coverage of 0.09 monolayers. There are no Cu–S complexes. Conversely, prior work has shown that a Cu 2S 3 complex forms on Cu(111) under comparable conditions. On the basis of DFT, this difference can be attributed mainly to stronger adsorption of sulfur on Cu(100) as compared with Cu(111).« less

75 FR 23563 - Delegation of Certain Functions Under Section 104(g) of the United States-India Peaceful Atomic...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-05-04

... Certain Functions Under Section 104(g) of the United States-India Peaceful Atomic Energy Cooperation Act... President by section 104(g) of the United States-India Peaceful Atomic Energy Cooperation Act of 2006...

PREFACE: Atomically controlled fabrication technology: new physics and functional device realization Atomically controlled fabrication technology: new physics and functional device realization

NASA Astrophysics Data System (ADS)

Kuwahara, Yuji; Kasai, Hideaki

2011-10-01

To realize next generation functional devices, atomic level controllability of the application and fabrication techniques is necessary. The conventional route to advance solid state devices, which involves improvement of 'instrumental accuracy', is now facing a major paradigm shift towards 'phenomenal accuracy'. Therefore, to keep up with this critical turn in the development of devices, pioneering research (both theoretical and experimental) on relevant materials, focusing on new physics at the atomic scale, is inevitable. This special section contains articles on the advancements in fabrication of functional devices with an emphasis on the exploration, clarification and understanding of atomistic phenomena. Research articles reporting theoretical and experimental findings on various materials such as semiconductors, metals, magnetic and organic systems, collectively present and 'capture' the appropriate processes and mechanisms of this rapidly developing field. The theoretical investigations employ first-principles quantum-mechanical simulations to clarify and bring about design principles and guidelines, or to develop more reliable computational methods. Experimental studies, on the other hand, introduce novel capabilities to build, view and manipulate materials at the atomic scale by employing pioneering techniques. Thus, the section pays significant attention to novel structures and properties and the accompanying fabrication techniques and design arising from the understanding of properties and structures at the atomic scale. We hope that researchers in the area of physics, materials science and engineering, interested in the development of functional devices via atomic level control, will find valuable information in this collaborative work. We are grateful to all of the authors for their contributions. Atomically controlled fabrication contents On the mechanism of carbon nanotube formation: the role of the catalyst G N Ayre, T Uchino, B Mazumder, A L Hector, J L Hutchison, D C Smith, P Ashburn and C H de Groot Mechanism of atomic-scale passivation and flattening of semiconductor surfaces by wet-chemical preparationsKenta Arima, Katsuyoshi Endo, Kazuto Yamauchi, Kikuji Hirose, Tomoya Ono and Yasuhisa Sano Real-space calculations for electron transport properties of nanostructuresTomoya Ono, Shigeru Tsukamoto, Yoshiyuki Egami and Yoshitaka Fujimoto Thermally activated magnetization reversal in monatomic magnetic chains on surfaces studied by classical atomistic spin-dynamics simulationsDavid S G Bauer, Phivos Mavropoulos, Samir Lounis and Stefan Blügel An atomically controlled Si film formation process at low temperatures using atmospheric-pressure VHF plasmaK Yasutake, H Kakiuchi, H Ohmi, K Inagaki, Y Oshikane and M Nakano Single-nanometer focusing of hard x-rays by Kirkpatrick-Baez mirrorsKazuto Yamauchi, Hidekazu Mimura, Takashi Kimura, Hirokatsu Yumoto, Soichiro Handa, Satoshi Matsuyama, Kenta Arima, Yasuhisa Sano, Kazuya Yamamura, Koji Inagaki, Hiroki Nakamori, Jangwoo Kim, Kenji Tamasaku, Yoshinori Nishino, Makina Yabashi and Tetsuya Ishikawa Surface magnetism in O2 dissociation—from basics to applicationY Kunisada, M C Escaño and H Kasai Real-space finite-difference approach for multi-body systems: path-integral renormalization group method and direct energy minimization methodAkira Sasaki, Masashi Kojo, Kikuji Hirose and Hidekazu Goto Electrical conduction of organic ultrathin films evaluated by an independently driven double-tip scanning tunneling microscopeK Takami, S Tsuruta, Y Miyake, M Akai-Kasaya, A Saito, M Aono and Y Kuwahara

Materials by Design—A Perspective From Atoms to Structures

PubMed Central

Buehler, Markus J.

2013-01-01

Biological materials are effectively synthesized, controlled, and used for a variety of purposes—in spite of limitations in energy, quality, and quantity of their building blocks. Whereas the chemical composition of materials in the living world plays a some role in achieving functional properties, the way components are connected at different length scales defines what material properties can be achieved, how they can be altered to meet functional requirements, and how they fail in disease states and other extreme conditions. Recent work has demonstrated this by using large-scale computer simulations to predict materials properties from fundamental molecular principles, combined with experimental work and new mathematical techniques to categorize complex structure-property relationships into a systematic framework. Enabled by such categorization, we discuss opportunities based on the exploitation of concepts from distinct hierarchical systems that share common principles in how function is created, linking music to materials science. PMID:24163499

Novel trends in pair distribution function approaches on bulk systems with nanoscale heterogeneities

DOE PAGES

Emil S. Bozin; Billinge, Simon J. L.

2016-07-29

Novel materials for high performance applications increasingly exhibit structural order on the nanometer length scale; a domain where crystallography, the basis of Rietveld refinement, fails [1]. In such instances the total scattering approach, which treats Bragg and diffuse scattering on an equal basis, is a powerful approach. In recent years, the analysis of the total scattering data became an invaluable tool and the gold standard for studying nanocrystalline, nanoporous, and disordered crystalline materials. The data may be analyzed in reciprocal space directly, or Fourier transformed to the real-space atomic pair distribution function (PDF) and this intuitive function examined for localmore » structural information. Here we give a number of illustrative examples, for convenience picked from our own work, of recent developments and applications of total scattering and PDF analysis to novel complex materials. There are many other wonderful examples from the work of others.« less

Ultra-fast computation of electronic spectra for large systems by tight-binding based simplified Tamm-Dancoff approximation (sTDA-xTB)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Grimme, Stefan, E-mail: grimme@thch.uni-bonn.de; Bannwarth, Christoph

2016-08-07

The computational bottleneck of the extremely fast simplified Tamm-Dancoff approximated (sTDA) time-dependent density functional theory procedure [S. Grimme, J. Chem. Phys. 138, 244104 (2013)] for the computation of electronic spectra for large systems is the determination of the ground state Kohn-Sham orbitals and eigenvalues. This limits such treatments to single structures with a few hundred atoms and hence, e.g., sampling along molecular dynamics trajectories for flexible systems or the calculation of chromophore aggregates is often not possible. The aim of this work is to solve this problem by a specifically designed semi-empirical tight binding (TB) procedure similar to the wellmore » established self-consistent-charge density functional TB scheme. The new special purpose method provides orbitals and orbital energies of hybrid density functional character for a subsequent and basically unmodified sTDA procedure. Compared to many previous semi-empirical excited state methods, an advantage of the ansatz is that a general eigenvalue problem in a non-orthogonal, extended atomic orbital basis is solved and therefore correct occupied/virtual orbital energy splittings as well as Rydberg levels are obtained. A key idea for the success of the new model is that the determination of atomic charges (describing an effective electron-electron interaction) and the one-particle spectrum is decoupled and treated by two differently parametrized Hamiltonians/basis sets. The three-diagonalization-step composite procedure can routinely compute broad range electronic spectra (0-8 eV) within minutes of computation time for systems composed of 500-1000 atoms with an accuracy typical of standard time-dependent density functional theory (0.3-0.5 eV average error). An easily extendable parametrization based on coupled-cluster and density functional computed reference data for the elements H–Zn including transition metals is described. The accuracy of the method termed sTDA-xTB is first benchmarked for vertical excitation energies of open- and closed-shell systems in comparison to other semi-empirical methods and applied to exemplary problems in electronic spectroscopy. As side products of the development, a robust and efficient valence electron TB method for the accurate determination of atomic charges as well as a more accurate calculation scheme of dipole rotatory strengths within the Tamm-Dancoff approximation is proposed.« less

Process model-based atomic service discovery and composition of composite semantic web services using web ontology language for services (OWL-S)

NASA Astrophysics Data System (ADS)

Paulraj, D.; Swamynathan, S.; Madhaiyan, M.

2012-11-01

Web Service composition has become indispensable as a single web service cannot satisfy complex functional requirements. Composition of services has received much interest to support business-to-business (B2B) or enterprise application integration. An important component of the service composition is the discovery of relevant services. In Semantic Web Services (SWS), service discovery is generally achieved by using service profile of Ontology Web Languages for Services (OWL-S). The profile of the service is a derived and concise description but not a functional part of the service. The information contained in the service profile is sufficient for atomic service discovery, but it is not sufficient for the discovery of composite semantic web services (CSWS). The purpose of this article is two-fold: first to prove that the process model is a better choice than the service profile for service discovery. Second, to facilitate the composition of inter-organisational CSWS by proposing a new composition method which uses process ontology. The proposed service composition approach uses an algorithm which performs a fine grained match at the level of atomic process rather than at the level of the entire service in a composite semantic web service. Many works carried out in this area have proposed solutions only for the composition of atomic services and this article proposes a solution for the composition of composite semantic web services.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions.

PubMed

Bedford, Nicholas M; Hughes, Zak E; Tang, Zhenghua; Li, Yue; Briggs, Beverly D; Ren, Yang; Swihart, Mark T; Petkov, Valeri G; Naik, Rajesh R; Knecht, Marc R; Walsh, Tiffany R

2016-01-20

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction data and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.

Fatigue-Induced Damage in Zr-Based Bulk Metallic Glasses

PubMed Central

Chuang, Chih-Pin; Yuan, Tao; Dmowski, Wojciech; Wang, Gong-Yao; Freels, Matt; Liaw, Peter K.; Li, Ran; Zhang, Tao

2013-01-01

In the present work, we investigate the effect of “fatigue” on the fatigue behavior and atomic structure of Zr-based BMGs. Fatigue experiments on the failed-by-fatigue samples indicate that the remnants generally have similar or longer fatigue life than the as-cast samples. Meanwhile, the pair-distribution-function (PDF) analysis of the as-cast and post-fatigue samples showed very small changes of local atomic structures. These observations suggest that the fatigue life of the 6-mm in-diameter Zr-based BMG is dominated by the number of pre-existing crack-initiation sites in the sample. Once the crack initiates in the specimen, the fatigue-induced damage is accumulated locally on these initiated sites, while the rest of the region deforms elastically. The results suggest that the fatigue failure of BMGs under compression-compression fatigue experiments is a defect-controlled process. The present work indicates the significance of the improved fatigue resistance with decreasing the sample size. PMID:23999496

The general setting for the zero-flux condition: The lagrangian and zero-flux conditions that give the heisenberg equation of motion.

PubMed

Anderson, James S M; Ayers, Paul W

2018-06-30

Generalizing our recent work on relativistic generalizations of the quantum theory of atoms in molecules, we present the general setting under which the principle of stationary action for a region leads to open quantum subsystems. The approach presented here is general and works for any Hamiltonian, and when a reasonable Lagrangian is selected, it often leads to the integral of the Laplacian of the electron density on the region vanishing as a necessary condition for the zero-flux surface. Alternatively, with this method, one can design a Lagrangian that leads to a surface of interest (though this Lagrangian may not be, and indeed probably will not be, "reasonable"). For any reasonable Lagrangian for the electronic wave function and any two-component method (related by integration by parts to the Hamiltonian) considered, the Bader definition of an atom is recaptured. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Atomic Force Microscopy Based Cell Shape Index

NASA Astrophysics Data System (ADS)

Adia-Nimuwa, Usienemfon; Mujdat Tiryaki, Volkan; Hartz, Steven; Xie, Kan; Ayres, Virginia

2013-03-01

Stellation is a measure of cell physiology and pathology for several cell groups including neural, liver and pancreatic cells. In the present work, we compare the results of a conventional two-dimensional shape index study of both atomic force microscopy (AFM) and fluorescent microscopy images with the results obtained using a new three-dimensional AFM-based shape index similar to sphericity index. The stellation of astrocytes is investigated on nanofibrillar scaffolds composed of electrospun polyamide nanofibers that has demonstrated promise for central nervous system (CNS) repair. Recent work by our group has given us the ability to clearly segment the cells from nanofibrillar scaffolds in AFM images. The clear-featured AFM images indicated that the astrocyte processes were longer than previously identified at 24h. It was furthermore shown that cell spreading could vary significantly as a function of environmental parameters, and that AFM images could record these variations. The new three-dimensional AFM-based shape index incorporates the new information: longer stellate processes and cell spreading. The support of NSF PHY-095776 is acknowledged.

An all-atom structure-based potential for proteins: bridging minimal models with all-atom empirical forcefields.

PubMed

Whitford, Paul C; Noel, Jeffrey K; Gosavi, Shachi; Schug, Alexander; Sanbonmatsu, Kevin Y; Onuchic, José N

2009-05-01

Protein dynamics take place on many time and length scales. Coarse-grained structure-based (Go) models utilize the funneled energy landscape theory of protein folding to provide an understanding of both long time and long length scale dynamics. All-atom empirical forcefields with explicit solvent can elucidate our understanding of short time dynamics with high energetic and structural resolution. Thus, structure-based models with atomic details included can be used to bridge our understanding between these two approaches. We report on the robustness of folding mechanisms in one such all-atom model. Results for the B domain of Protein A, the SH3 domain of C-Src Kinase, and Chymotrypsin Inhibitor 2 are reported. The interplay between side chain packing and backbone folding is explored. We also compare this model to a C(alpha) structure-based model and an all-atom empirical forcefield. Key findings include: (1) backbone collapse is accompanied by partial side chain packing in a cooperative transition and residual side chain packing occurs gradually with decreasing temperature, (2) folding mechanisms are robust to variations of the energetic parameters, (3) protein folding free-energy barriers can be manipulated through parametric modifications, (4) the global folding mechanisms in a C(alpha) model and the all-atom model agree, although differences can be attributed to energetic heterogeneity in the all-atom model, and (5) proline residues have significant effects on folding mechanisms, independent of isomerization effects. Because this structure-based model has atomic resolution, this work lays the foundation for future studies to probe the contributions of specific energetic factors on protein folding and function.

An All-atom Structure-Based Potential for Proteins: Bridging Minimal Models with All-atom Empirical Forcefields

PubMed Central

Whitford, Paul C.; Noel, Jeffrey K.; Gosavi, Shachi; Schug, Alexander; Sanbonmatsu, Kevin Y.; Onuchic, José N.

2012-01-01

Protein dynamics take place on many time and length scales. Coarse-grained structure-based (Gō) models utilize the funneled energy landscape theory of protein folding to provide an understanding of both long time and long length scale dynamics. All-atom empirical forcefields with explicit solvent can elucidate our understanding of short time dynamics with high energetic and structural resolution. Thus, structure-based models with atomic details included can be used to bridge our understanding between these two approaches. We report on the robustness of folding mechanisms in one such all-atom model. Results for the B domain of Protein A, the SH3 domain of C-Src Kinase and Chymotrypsin Inhibitor 2 are reported. The interplay between side chain packing and backbone folding is explored. We also compare this model to a Cα structure-based model and an all-atom empirical forcefield. Key findings include 1) backbone collapse is accompanied by partial side chain packing in a cooperative transition and residual side chain packing occurs gradually with decreasing temperature 2) folding mechanisms are robust to variations of the energetic parameters 3) protein folding free energy barriers can be manipulated through parametric modifications 4) the global folding mechanisms in a Cα model and the all-atom model agree, although differences can be attributed to energetic heterogeneity in the all-atom model 5) proline residues have significant effects on folding mechanisms, independent of isomerization effects. Since this structure-based model has atomic resolution, this work lays the foundation for future studies to probe the contributions of specific energetic factors on protein folding and function. PMID:18837035

Formation of ultracold molecules induced by a high-power single frequency fiber laser

NASA Astrophysics Data System (ADS)

Fernandes Passagem, Henry; Colin-Rodriguez, Ricardo; Ventura da Silva, Paulo; Bouloufa-Maafa, Nadia; Dulieu, Olivier; Marcassa, Luis

2017-04-01

Photoassociation of a pair of ultracold atoms is a quite simple and rapid approach for cold molecule formation. The main limitation of PA is that the latter step is incoherent, so that the population of the created molecules is spread over many vibrational levels with weak or moderate binding energies. If the excited electronic molecular state exhibits a peculiar feature at short internuclear distance like a potential barrier or an avoided crossing, the population of deeply-bound ground state levels may be significantly enhanced. In this work, the influence of a high-power single frequency fiber laser on the formation of ultracold 85Rb2 molecules is investigated as a function of its frequency (in the 1062-1070 nm range) in a magneto optical trap. We found evidence for the formation of ground state 85Rb2 molecules in low vibrational levels (v <= 20) with a maximal rate of 104 s-1, induced by short-range photoassociation by the fiber laser followed by spontaneous emission. When this laser is used to set up a dipole trap, we measure an atomic loss rate at a wavelength far from the PA resonances only 4 times smaller than the one observed at a PA resonance wavelength. This work may have important consequences for atom trapping using lasers around 1060 nm. This work is supported by Grants 2013/02816-8 and 2014/24479-6, Sao Paulo Research Foundation (FAPESP).

Charge exchange cross sections in slow collisions of Si3+ with Hydrogen atom

NASA Astrophysics Data System (ADS)

Joseph, Dwayne; Quashie, Edwin; Saha, Bidhan

2011-05-01

In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. In recent years both the experimental and theoretical studies of electron transfer in ion-atom collisions have progressed considerably. Accurate determination of the cross sections and an understanding of the dynamics of the electron-capture process by multiply charged ions from atomic hydrogen over a wide range of projectile velocities are important in various field ranging from fusion plasma to astrophysics. The soft X-ray emission from comets has been explained by charge transfer of solar wind ions, among them Si3+, with neutrals in the cometary gas vapor. The cross sections are evaluated using the (a) full quantum and (b) semi-classical molecular orbital close coupling (MOCC) methods. Adiabatic potentials and wave functions for relavent singlet and triplet states are generated using the MRDCI structure codes. Details will be presented at the conference. Work supported by NSF CREST project (grant #0630370).

An electron of helium atom under a high-intensity laser field

NASA Astrophysics Data System (ADS)

Falaye, Babatunde James; Sun, Guo-Hua; Adepoju, Adenike Grace; Liman, Muhammed S.; Oyewumi, K. J.; Dong, Shi-Hai

2017-02-01

We scrutinize the behavior of eigenvalues of an electron in a helium (He) atom as it interacts with electric field directed along the z-axis and is exposed to linearly polarized intense laser field radiation. To achieve this, we freeze one electron of the He atom at its ionic ground state and the motion of the second electron in the ion core is treated via a more general case of screened Coulomb potential model. Using the Kramers-Henneberger (KH) unitary transformation, which is the semiclassical counterpart of the Block-Nordsieck transformation in the quantized field formalism, the squared vector potential that appears in the equation of motion is eliminated and the resultant equation is expressed in the KH frame. Within this frame, the resulting potential and the corresponding wave function are expanded in Fourier series and using Ehlotzky’s approximation, we obtain a laser-dressed potential to simulate intense laser field. By fitting the more general case of screened Coulomb potential model into the laser-dressed potential, and then expanding it in Taylor series up to O≤ft({{r}4},α 09\\right) , we obtain the solution (eigenvalues and wave function) of an electron in a He atom under the influence of external electric field and high-intensity laser field, within the framework of perturbation theory formalism. We found that the variation in frequency of laser radiation has no effect on the eigenvalues of a He electron for a particular electric field intensity directed along z-axis. Also, for a very strong external electric field and an infinitesimal screening parameter, the system is strongly bound. This work has potential application in the areas of atomic and molecular processes in external fields including interactions with strong fields and short pulses.

Solution of hydrogen in accident tolerant fuel candidate material: U3Si2

NASA Astrophysics Data System (ADS)

Middleburgh, S. C.; Claisse, A.; Andersson, D. A.; Grimes, R. W.; Olsson, P.; Mašková, S.

2018-04-01

Hydrogen uptake and accommodation into U3Si2, a candidate accident-tolerant fuel system, has been modelled on the atomic scale using the density functional theory. The solution energy of multiple H atoms is computed, reaching a stoichiometry of U3Si2H2 which has been experimentally observed in previous work (reported as U3Si2H1.8). The absorption of hydrogen is found to be favourable up to U3Si2H2 and the associated volume change is computed, closely matching experimental data. Entropic effects are considered to assess the dissociation temperature of H2, estimated to be at ∼800 K - again in good agreement with the experimentally observed transition temperature.

Spectroscopic determination of surface geometry: Ti(0001)-H(1×1)

NASA Astrophysics Data System (ADS)

Feibelman, Peter J.; Hamann, D. R.

1980-02-01

The electronic structure of a Ti(0001) film covered by a monolayer of H is shown to depend strongly on the location of the H atom in the surface unit cell. Best agreement with experiment is found with the H's in three-fold sites, 0.8 a.u. outside the outer Ti layer. In this geometry the H atoms "heal" the surface-the clean Ti(0001) surface state near the Fermi level is removed and the outer layer d-like local density of states (LDOS) is quite similar to that of the interior. Additionally, the calculated work function is 4.0 eV and an H-derived peak in the calculated LDOS appears 5 eV below EF, in agreement with photoemission measurements.

Electronic structure of lead pyrophosphate

NASA Astrophysics Data System (ADS)

Suewattana, Malliga; Singh, David

2007-03-01

Lead Pyrophosphate Pb2P2O7 is of interest for potential radiation detection applications and use in long term waste storage. It forms in triclinic P1 crystals and can also be grown as glasses. We performed electronic structure calculations using the crystal structure which determined by Mullica et. al (J. Solid State Chem (1986)) using x-ray diffraction and found large forces on atoms suggesting that the refined atomic positions were not fully correct. Here we report first principles structure relaxation and a revised crystal structure for this compound. We analyze the resulting structure using pair distribution functions and discuss the implications for the electronic properties. This work was supported by DOE NA22 and the Office of Naval Research.

Characterization of hot dense plasma with plasma parameters

NASA Astrophysics Data System (ADS)

Singh, Narendra; Goyal, Arun; Chaurasia, S.

2018-05-01

Characterization of hot dense plasma (HDP) with its parameters temperature, electron density, skin depth, plasma frequency is demonstrated in this work. The dependence of HDP parameters on temperature and electron density is discussed. The ratio of the intensities of spectral lines within HDP is calculated as a function of electron temperature. The condition of weakly coupled for HDP is verified by calculating coupling constant. Additionally, atomic data such as transition wavelength, excitation energies, line strength, etc. are obtained for Be-like ions on the basis of MCDHF method. In atomic data calculations configuration interaction and relativistic effects QED and Breit corrections are newly included for HDP characterization and this is first result of HDP parameters from extreme ultraviolet (EUV) radiations.

High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

NASA Astrophysics Data System (ADS)

Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

2012-08-01

Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

Superconducting Qubit (transmon) coupled to Surface Acoustic Waves (SAWs)

NASA Astrophysics Data System (ADS)

Guo, Lingzhen; Johansson, Göran

We work on a hybrid system, which couples the transmon in circuit QED to the propagating mechanical modes of Surface Acoustic Waves (SAWs). This is an analogue of circuit QED system but replacing the microwave photons by SAW phonons. We investigate the quantum dynamics of a single transmon qubit coupled to surface acoustic waves (SAWs) via two distant connection points. Since the acoustic speed is five orders of magnitude slower than the speed of light, the travelling time between the two connection points needs to be taken into account. Therefore, we treat the transmon qubit as a giant atom with a deterministic time delay. We find that the spontaneous emission of the system, formed by the giant atom and the SAWs between its connection points, initially follows a polynomial decay law instead of an exponential one, as would be the case for a small atom. We obtain exact analytical results for the scattering properties of the giant atom up to two-phonon processes by using a diagrammatic approach. The time delay gives rise to novel features in the reflection, transmission, power spectra, and second-order correlation functions of the system. We show that the giant atom can generate entangled phonon pairs, which may have applications in quantum communication. L.G. acknowledges financial support from Carl-Zeiss Stiftung (0563-2.8/508/2).

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

NASA Astrophysics Data System (ADS)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

2013-12-01

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

Parametric Time-Frequency Analysis and Its Applications in Music Classification

NASA Astrophysics Data System (ADS)

Shen, Ying; Li, Xiaoli; Ma, Ngok-Wah; Krishnan, Sridhar

2010-12-01

Analysis of nonstationary signals, such as music signals, is a challenging task. The purpose of this study is to explore an efficient and powerful technique to analyze and classify music signals in higher frequency range (44.1 kHz). The pursuit methods are good tools for this purpose, but they aimed at representing the signals rather than classifying them as in Y. Paragakin et al., 2009. Among the pursuit methods, matching pursuit (MP), an adaptive true nonstationary time-frequency signal analysis tool, is applied for music classification. First, MP decomposes the sample signals into time-frequency functions or atoms. Atom parameters are then analyzed and manipulated, and discriminant features are extracted from atom parameters. Besides the parameters obtained using MP, an additional feature, central energy, is also derived. Linear discriminant analysis and the leave-one-out method are used to evaluate the classification accuracy rate for different feature sets. The study is one of the very few works that analyze atoms statistically and extract discriminant features directly from the parameters. From our experiments, it is evident that the MP algorithm with the Gabor dictionary decomposes nonstationary signals, such as music signals, into atoms in which the parameters contain strong discriminant information sufficient for accurate and efficient signal classifications.

Vapor Grown Carbon Fiber/Hybrid Organic-Inorganic Matrix Composites. Nanometer-sized Silsesquiozane Phase Chemically Bound in a Matrix

DTIC Science & Technology

2006-04-28

for this work included: (1) Polyhedral oligomeric silsesquioxane chemicals (POSS macromers) of three types: those with no polymerizable group, those...Polyhedral oligomeric silsesquioxane chemicals (POSS macromers) of three types: those with no polymerizable group, those with one reactive function and...atoms and ions. Polyhedral Oligomeric Silsesquioxane/Organic Matrix Nanocomposites Major reviews of POSS polymer and copolymer chemistry. The first

Microgravity

NASA Image and Video Library

2000-04-19

Dr. Marc Pusey (seated) and Dr. Craig Kundrot use computers to analyze x-ray maps and generate three-dimensional models of protein structures. With this information, scientists at Marshall Space Flight Center can learn how proteins are made and how they work. The computer screen depicts a proten structure as a ball-and-stick model. Other models depict the actual volume occupied by the atoms, or the ribbon-like structures that are crucial to a protein's function.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. I. Adsorption on iron terminated α-Fe{sub 2}O{sub 3} (0001) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

This is the first of two papers dealing with the adsorption of Au and formation of Au{sub n} nanostructures (n = 1–4) on hematite (0001) surface and adsorption of CO thereon. The stoichiometric Fe-terminated (0001) surface of hematite was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties of the systems studied were examined for vertical and flattened configurations of Au{sub n} nanostructures adsorbed on the hematite surfaces. The flattened ones, which can be viewed as bilayer-like structures, weremore » found energetically more favored than vertical ones. For both classes of structures the adsorption binding energy increases with the number of Au atoms in a structure. The adsorption of Au{sub n} induces charge rearrangement at the Au{sub n}/oxide contact which is reflected in work function changes. In most considered cases Au{sub n} adsorption increases the work function. A detailed analysis of the bonding electron charge is presented and the corresponding electron charge rearrangements at the contacts were quantified by a Bader charge analyses. The interaction of a CO molecule with the Au{sub n} nanostructures supported on α-Fe{sub 2}O{sub 3} (0001) and the oxide support was studied. It is found that the CO adsorption binding to the hematite supported Au{sub n} structures is more than twice as strong as to the bare hematite surface. Analysis of the Bader charges on the atoms showed that in each case CO binds to the most positively charged (cationic) atom of the Au{sub n} structure. Changes in the electronic structure of the Au{sub n} species and of the oxide support, and their consequences for the interactions with CO, are discussed.« less

Calibration and validation of coarse-grained models of atomic systems: application to semiconductor manufacturing

NASA Astrophysics Data System (ADS)

Farrell, Kathryn; Oden, J. Tinsley

2014-07-01

Coarse-grained models of atomic systems, created by aggregating groups of atoms into molecules to reduce the number of degrees of freedom, have been used for decades in important scientific and technological applications. In recent years, interest in developing a more rigorous theory for coarse graining and in assessing the predictivity of coarse-grained models has arisen. In this work, Bayesian methods for the calibration and validation of coarse-grained models of atomistic systems in thermodynamic equilibrium are developed. For specificity, only configurational models of systems in canonical ensembles are considered. Among major challenges in validating coarse-grained models are (1) the development of validation processes that lead to information essential in establishing confidence in the model's ability predict key quantities of interest and (2), above all, the determination of the coarse-grained model itself; that is, the characterization of the molecular architecture, the choice of interaction potentials and thus parameters, which best fit available data. The all-atom model is treated as the "ground truth," and it provides the basis with respect to which properties of the coarse-grained model are compared. This base all-atom model is characterized by an appropriate statistical mechanics framework in this work by canonical ensembles involving only configurational energies. The all-atom model thus supplies data for Bayesian calibration and validation methods for the molecular model. To address the first challenge, we develop priors based on the maximum entropy principle and likelihood functions based on Gaussian approximations of the uncertainties in the parameter-to-observation error. To address challenge (2), we introduce the notion of model plausibilities as a means for model selection. This methodology provides a powerful approach toward constructing coarse-grained models which are most plausible for given all-atom data. We demonstrate the theory and methods through applications to representative atomic structures and we discuss extensions to the validation process for molecular models of polymer structures encountered in certain semiconductor nanomanufacturing processes. The powerful method of model plausibility as a means for selecting interaction potentials for coarse-grained models is discussed in connection with a coarse-grained hexane molecule. Discussions of how all-atom information is used to construct priors are contained in an appendix.

Silver clusters encapsulated in C{sub 60}: A density functional study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dhiman, Shobhna; Kumar, Ranjan; Dharamvir, Keya

2015-08-28

We explore the possibility of formation of endohedral complexes of Ag{sub n} atoms (n=1-9) inside C{sub 60} molecule using density functional theory and molecular dynamics. The obtained results reveal that Ag{sub n} (n=8) atoms can form stable complexes with the C{sub 60} molecule. Encapsulation of large number of Ag{sub n} atoms (n>8) make C{sub 60} cage instable, showing distortion of cage. Binding energy/atom increases with the number of Ag atoms up to n=4, after that it increases. Ionization potential decreases till n=4 and then increases, electron affinity increases till n=4 and then shows oscillatory nature as a function of Agmore » atoms inside the cage. Homo –Lumo gap shows no systematic pattern. Our results agreed well with the data available.« less

Atomically-thin molecular layers for electrode modification of organic transistors

NASA Astrophysics Data System (ADS)

Gim, Yuseong; Kang, Boseok; Kim, Bongsoo; Kim, Sun-Guk; Lee, Joong-Hee; Cho, Kilwon; Ku, Bon-Cheol; Cho, Jeong Ho

2015-08-01

Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs.Atomically-thin molecular layers of aryl-functionalized graphene oxides (GOs) were used to modify the surface characteristics of source-drain electrodes to improve the performances of organic field-effect transistor (OFET) devices. The GOs were functionalized with various aryl diazonium salts, including 4-nitroaniline, 4-fluoroaniline, or 4-methoxyaniline, to produce several types of GOs with different surface functional groups (NO2-Ph-GO, F-Ph-GO, or CH3O-Ph-GO, respectively). The deposition of aryl-functionalized GOs or their reduced derivatives onto metal electrode surfaces dramatically enhanced the electrical performances of both p-type and n-type OFETs relative to the performances of OFETs prepared without the GO modification layer. Among the functionalized rGOs, CH3O-Ph-rGO yielded the highest hole mobility of 0.55 cm2 V-1 s-1 and electron mobility of 0.17 cm2 V-1 s-1 in p-type and n-type FETs, respectively. Two governing factors: (1) the work function of the modified electrodes and (2) the crystalline microstructures of the benchmark semiconductors grown on the modified electrode surface were systematically investigated to reveal the origin of the performance improvements. Our simple, inexpensive, and scalable electrode modification technique provides a significant step toward optimizing the device performance by engineering the semiconductor-electrode interfaces in OFETs. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr03307a

Recent progress in density functional theory

NASA Astrophysics Data System (ADS)

Truhlar, Donald

2014-03-01

Ongoing work involves several areas of density functional theory: new methods for computing electronic excitation energies, including a new way to remove spin contamination in the spin-flip Tamm-Dancoff approximation and a configuration-interaction-corrected Tamm-Dancoff Approximation for treating conical intersections; new ways to treat open-shell states, including a reinterpreted broken-symmetry method and multi-configuration Kohn-Sham theory; a new exchange-correlation functional; new tests of density functional theory against databases for electronic transition energies and molecules and solids containing metal atoms; and applications. A selection of results will be presented. I am grateful to the following collaborators for contributions to the ongoing work: Boris Averkiev, Rebecca Carlson, Laura Fernandez, Laura Gagliardi, Chad Hoyer, Francesc Illas, Miho Isegawa, Shaohong Li, Giovanni Li Manni, Sijie Luo, Dongxia Ma, Remi Maurice, Rubén Means-Pañeda, Roberto Peverati, Nora Planas, Prasenjit Seal, Pragya Verma, Bo Wang, Xuefei Xu, Ke R. Yang, Haoyu Yu, Wenjing Zhang, and Jingjing Zheng. Supported in part by the AFOSR and U.S. DOE.

Directed Atom-by-Atom Assembly of Dopants in Silicon.

PubMed

Hudak, Bethany M; Song, Jiaming; Sims, Hunter; Troparevsky, M Claudia; Humble, Travis S; Pantelides, Sokrates T; Snijders, Paul C; Lupini, Andrew R

2018-05-17

The ability to controllably position single atoms inside materials is key for the ultimate fabrication of devices with functionalities governed by atomic-scale properties. Single bismuth dopant atoms in silicon provide an ideal case study in view of proposals for single-dopant quantum bits. However, bismuth is the least soluble pnictogen in silicon, meaning that the dopant atoms tend to migrate out of position during sample growth. Here, we demonstrate epitaxial growth of thin silicon films doped with bismuth. We use atomic-resolution aberration-corrected imaging to view the as-grown dopant distribution and then to controllably position single dopants inside the film. Atomic-scale quantum-mechanical calculations corroborate the experimental findings. These results indicate that the scanning transmission electron microscope is of particular interest for assembling functional materials atom-by-atom because it offers both real-time monitoring and atom manipulation. We envision electron-beam manipulation of atoms inside materials as an achievable route to controllable assembly of structures of individual dopants.

Structure-function mapping of BbCRASP-1, the key complement factor H and FHL-1 binding protein of Borrelia burgdorferi.

PubMed

Cordes, Frank S; Kraiczy, Peter; Roversi, Pietro; Simon, Markus M; Brade, Volker; Jahraus, Oliver; Wallis, Russell; Goodstadt, Leo; Ponting, Chris P; Skerka, Christine; Zipfel, Peter F; Wallich, Reinhard; Lea, Susan M

2006-05-01

Borrelia burgdorferi, a spirochaete transmitted to human hosts during feeding of infected Ixodes ticks, is the causative agent of Lyme disease, the most frequent vector-borne disease in Eurasia and North America. Sporadically Lyme disease develops into a chronic, multisystemic disorder. Serum-resistant B. burgdorferi strains bind complement factor H (FH) and FH-like protein 1 (FHL-1) on the spirochaete surface. This binding is dependent on the expression of proteins termed complement-regulator acquiring surface proteins (CRASPs). The atomic structure of BbCRASP-1, the key FHL-1/FH-binding protein of B. burgdorferi, has recently been determined. Our analysis indicates that its protein topology apparently evolved to provide a high affinity interaction site for FH/FHL-1 and leads to an atomic-level hypothesis for the functioning of BbCRASP-1. This work demonstrates that pathogens interact with complement regulators in ways that are distinct from the mechanisms used by the host and are thus obvious targets for drug design.

Theoretical aspects of studies of oxide and semiconductor surfaces using low energy positrons

NASA Astrophysics Data System (ADS)

Fazleev, N. G.; Maddox, W. B.; Weiss, A. H.

2011-01-01

This paper presents the results of a theoretical study of positron surface and bulk states and annihilation characteristics of surface trapped positrons at the oxidized Cu(100) single crystal and at both As- and Ga-rich reconstructed GaAs(100) surfaces. The variations in atomic structure and chemical composition of the topmost layers of the surfaces associated with oxidation and reconstructions and the charge redistribution at the surfaces are found to affect localization and spatial extent of the positron surface-state wave functions. The computed positron binding energy, work function, and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the surfaces. Theoretical positron annihilation probabilities with relevant core electrons computed for the oxidized Cu(100) surface and the As- and Ga-rich reconstructed GaAs(100) surfaces are compared with experimental ones estimated from the positron annihilation induced Auger peak intensities measured from these surfaces.

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Simulation of FRET dyes allows quantitative comparison against experimental data

NASA Astrophysics Data System (ADS)

Reinartz, Ines; Sinner, Claude; Nettels, Daniel; Stucki-Buchli, Brigitte; Stockmar, Florian; Panek, Pawel T.; Jacob, Christoph R.; Nienhaus, Gerd Ulrich; Schuler, Benjamin; Schug, Alexander

2018-03-01

Fully understanding biomolecular function requires detailed insight into the systems' structural dynamics. Powerful experimental techniques such as single molecule Förster Resonance Energy Transfer (FRET) provide access to such dynamic information yet have to be carefully interpreted. Molecular simulations can complement these experiments but typically face limits in accessing slow time scales and large or unstructured systems. Here, we introduce a coarse-grained simulation technique that tackles these challenges. While requiring only few parameters, we maintain full protein flexibility and include all heavy atoms of proteins, linkers, and dyes. We are able to sufficiently reduce computational demands to simulate large or heterogeneous structural dynamics and ensembles on slow time scales found in, e.g., protein folding. The simulations allow for calculating FRET efficiencies which quantitatively agree with experimentally determined values. By providing atomically resolved trajectories, this work supports the planning and microscopic interpretation of experiments. Overall, these results highlight how simulations and experiments can complement each other leading to new insights into biomolecular dynamics and function.

Atomic switch networks—nanoarchitectonic design of a complex system for natural computing

NASA Astrophysics Data System (ADS)

Demis, E. C.; Aguilera, R.; Sillin, H. O.; Scharnhorst, K.; Sandouk, E. J.; Aono, M.; Stieg, A. Z.; Gimzewski, J. K.

2015-05-01

Self-organized complex systems are ubiquitous in nature, and the structural complexity of these natural systems can be used as a model to design new classes of functional nanotechnology based on highly interconnected networks of interacting units. Conventional fabrication methods for electronic computing devices are subject to known scaling limits, confining the diversity of possible architectures. This work explores methods of fabricating a self-organized complex device known as an atomic switch network and discusses its potential utility in computing. Through a merger of top-down and bottom-up techniques guided by mathematical and nanoarchitectonic design principles, we have produced functional devices comprising nanoscale elements whose intrinsic nonlinear dynamics and memorization capabilities produce robust patterns of distributed activity and a capacity for nonlinear transformation of input signals when configured in the appropriate network architecture. Their operational characteristics represent a unique potential for hardware implementation of natural computation, specifically in the area of reservoir computing—a burgeoning field that investigates the computational aptitude of complex biologically inspired systems.

Tuning oxidation level, electrical conductance and band gap structure on graphene sheets by cyclic atomic layer reduction technique

DOE PAGES

Gu, Si-Yong; Hsieh, Chien-Te; Lin, Tzu-Wei; ...

2018-05-12

The present work develops an atomic layer reduction (ALR) method to accurately tune oxidation level, electrical conductance, band-gap structure, and photoluminescence (PL) response of graphene oxide (GO) sheets. The ALR route is carried out at 200 °C within ALR cycle number of 10–100. The ALR treatment is capable of striping surface functionalities (e.g., hydroxyl, carbonyl, and carboxylic groups), producing thermally-reduced GO sheets. The ALR cycle number serves as a controlling factor in adjusting the crystalline, surface chemistry, electrical, optical properties of GO sheets. With increasing the ALR cycle number, ALR-GO sheets display a high crystallinity, a low oxidation level, anmore » improved electrical conductivity, a narrow band gap, and a tunable PL response. Finally, on the basis of the results, the ALR technique offers a great potential for accurately tune electrical and optical properties of carbon materials through the cyclic removal of oxygen functionalities, without any complicated thermal and chemical desorption processes.« less

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

DOE Office of Scientific and Technical Information (OSTI.GOV)

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Investigation of atomic-layer-deposited TiO x as selective electron and hole contacts to crystalline silicon

DOE PAGES

Matsui, Takuya; Bivour, Martin; Ndione, Paul F.; ...

2017-09-21

Here, the applicability of atomic-layer-deposited titanium oxide (TiO x) thin films for the formation of carrier selective contacts to crystalline silicon (c-Si) is investigated. While relatively good electron selectivity was presented recently by other groups, we show that carrier selectivity can be engineered from electron to hole selective depending on the deposition conditions, post deposition annealing and the contact material covering the TiOx layer. For both the electron and hole contacts, an open-circuit voltage (Voc) of ~ >650 mV is obtained. The fact that the Voc is correlated with the (asymmetric) induced c-Si band bending suggests that carrier selectivity ismore » mainly governed by the effective work function and/or the fixed charge rather than by the asymmetric band offsets at the Si/TiOx interface, which provides important insight into the basic function of metal-oxide-based contact systems.« less

Demonstration of asymmetric electron conduction in pseudosymmetrical photosynthetic reaction centre proteins in an electrical circuit

PubMed Central

Kamran, Muhammad; Friebe, Vincent M.; Delgado, Juan D.; Aartsma, Thijs J.; Frese, Raoul N.; Jones, Michael R.

2015-01-01

Photosynthetic reaction centres show promise for biomolecular electronics as nanoscale solar-powered batteries and molecular diodes that are amenable to atomic-level re-engineering. In this work the mechanism of electron conduction across the highly tractable Rhodobacter sphaeroides reaction centre is characterized by conductive atomic force microscopy. We find, using engineered proteins of known structure, that only one of the two cofactor wires connecting the positive and negative termini of this reaction centre is capable of conducting unidirectional current under a suitably oriented bias, irrespective of the magnitude of the bias or the applied force at the tunnelling junction. This behaviour, strong functional asymmetry in a largely symmetrical protein–cofactor matrix, recapitulates the strong functional asymmetry characteristic of natural photochemical charge separation, but it is surprising given that the stimulus for electron flow is simply an externally applied bias. Reasons for the electrical resistance displayed by the so-called B-wire of cofactors are explored. PMID:25751412

Atomic switch networks-nanoarchitectonic design of a complex system for natural computing.

PubMed

Demis, E C; Aguilera, R; Sillin, H O; Scharnhorst, K; Sandouk, E J; Aono, M; Stieg, A Z; Gimzewski, J K

2015-05-22

Self-organized complex systems are ubiquitous in nature, and the structural complexity of these natural systems can be used as a model to design new classes of functional nanotechnology based on highly interconnected networks of interacting units. Conventional fabrication methods for electronic computing devices are subject to known scaling limits, confining the diversity of possible architectures. This work explores methods of fabricating a self-organized complex device known as an atomic switch network and discusses its potential utility in computing. Through a merger of top-down and bottom-up techniques guided by mathematical and nanoarchitectonic design principles, we have produced functional devices comprising nanoscale elements whose intrinsic nonlinear dynamics and memorization capabilities produce robust patterns of distributed activity and a capacity for nonlinear transformation of input signals when configured in the appropriate network architecture. Their operational characteristics represent a unique potential for hardware implementation of natural computation, specifically in the area of reservoir computing-a burgeoning field that investigates the computational aptitude of complex biologically inspired systems.

Demonstration of asymmetric electron conduction in pseudosymmetrical photosynthetic reaction centre proteins in an electrical circuit.

PubMed

Kamran, Muhammad; Friebe, Vincent M; Delgado, Juan D; Aartsma, Thijs J; Frese, Raoul N; Jones, Michael R

2015-03-09

Photosynthetic reaction centres show promise for biomolecular electronics as nanoscale solar-powered batteries and molecular diodes that are amenable to atomic-level re-engineering. In this work the mechanism of electron conduction across the highly tractable Rhodobacter sphaeroides reaction centre is characterized by conductive atomic force microscopy. We find, using engineered proteins of known structure, that only one of the two cofactor wires connecting the positive and negative termini of this reaction centre is capable of conducting unidirectional current under a suitably oriented bias, irrespective of the magnitude of the bias or the applied force at the tunnelling junction. This behaviour, strong functional asymmetry in a largely symmetrical protein-cofactor matrix, recapitulates the strong functional asymmetry characteristic of natural photochemical charge separation, but it is surprising given that the stimulus for electron flow is simply an externally applied bias. Reasons for the electrical resistance displayed by the so-called B-wire of cofactors are explored.

Structure-Property Relationship of Phenylene-Based Self-Assembled-Monolayers for Record Low Work Function of Indium Tin Oxide.

PubMed

Benneckendorf, Frank S; Hillebrandt, Sabina; Ullrich, Florian; Rohnacher, Valentina; Hietzschold, Sebastian; Jänsch, Daniel; Freudenberg, Jan; Beck, Sebastian; Mankel, Eric; Jaegermann, Wolfram; Pucci, Annemarie; Bunz, Uwe H F; Müllen, Klaus

2018-06-20

Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids we report self-assembled monolayers with a significant decrease of the work function (WF) of indium-tin oxide (ITO) electrodes. While the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N,N dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease of ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

Band-gap corrected density functional theory calculations for InAs/GaSb type II superlattices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jianwei; Zhang, Yong

2014-12-07

We performed pseudopotential based density functional theory (DFT) calculations for GaSb/InAs type II superlattices (T2SLs), with bandgap errors from the local density approximation mitigated by applying an empirical method to correct the bulk bandgaps. Specifically, this work (1) compared the calculated bandgaps with experimental data and non-self-consistent atomistic methods; (2) calculated the T2SL band structures with varying structural parameters; (3) investigated the interfacial effects associated with the no-common-atom heterostructure; and (4) studied the strain effect due to lattice mismatch between the two components. This work demonstrates the feasibility of applying the DFT method to more exotic heterostructures and defect problemsmore » related to this material system.« less

Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

NASA Astrophysics Data System (ADS)

Jiménez-Díaz, Laura M.; Pérez, Luis A.

2018-03-01

In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

Microfluidic Imaging Flow Cytometry by Asymmetric-detection Time-stretch Optical Microscopy (ATOM).

PubMed

Tang, Anson H L; Lai, Queenie T K; Chung, Bob M F; Lee, Kelvin C M; Mok, Aaron T Y; Yip, G K; Shum, Anderson H C; Wong, Kenneth K Y; Tsia, Kevin K

2017-06-28

Scaling the number of measurable parameters, which allows for multidimensional data analysis and thus higher-confidence statistical results, has been the main trend in the advanced development of flow cytometry. Notably, adding high-resolution imaging capabilities allows for the complex morphological analysis of cellular/sub-cellular structures. This is not possible with standard flow cytometers. However, it is valuable for advancing our knowledge of cellular functions and can benefit life science research, clinical diagnostics, and environmental monitoring. Incorporating imaging capabilities into flow cytometry compromises the assay throughput, primarily due to the limitations on speed and sensitivity in the camera technologies. To overcome this speed or throughput challenge facing imaging flow cytometry while preserving the image quality, asymmetric-detection time-stretch optical microscopy (ATOM) has been demonstrated to enable high-contrast, single-cell imaging with sub-cellular resolution, at an imaging throughput as high as 100,000 cells/s. Based on the imaging concept of conventional time-stretch imaging, which relies on all-optical image encoding and retrieval through the use of ultrafast broadband laser pulses, ATOM further advances imaging performance by enhancing the image contrast of unlabeled/unstained cells. This is achieved by accessing the phase-gradient information of the cells, which is spectrally encoded into single-shot broadband pulses. Hence, ATOM is particularly advantageous in high-throughput measurements of single-cell morphology and texture - information indicative of cell types, states, and even functions. Ultimately, this could become a powerful imaging flow cytometry platform for the biophysical phenotyping of cells, complementing the current state-of-the-art biochemical-marker-based cellular assay. This work describes a protocol to establish the key modules of an ATOM system (from optical frontend to data processing and visualization backend), as well as the workflow of imaging flow cytometry based on ATOM, using human cells and micro-algae as the examples.

Measurement of complete and continuous Wigner functions for discrete atomic systems

NASA Astrophysics Data System (ADS)

Tian, Yali; Wang, Zhihui; Zhang, Pengfei; Li, Gang; Li, Jie; Zhang, Tiancai

2018-01-01

We measure complete and continuous Wigner functions of a two-level cesium atom in both a nearly pure state and highly mixed states. We apply the method [T. Tilma et al., Phys. Rev. Lett. 117, 180401 (2016), 10.1103/PhysRevLett.117.180401] of strictly constructing continuous Wigner functions for qubit or spin systems. We find that the Wigner function of all pure states of a qubit has negative regions and the negativity completely vanishes when the purity of an arbitrary mixed state is less than 2/3 . We experimentally demonstrate these findings using a single cesium atom confined in an optical dipole trap, which undergoes a nearly pure dephasing process. Our method can be applied straightforwardly to multi-atom systems for measuring the Wigner function of their collective spin state.

Optical Properties of Free and Embedded Small Nanoparticles

NASA Astrophysics Data System (ADS)

Idrobo, Juan

2008-03-01

It is well known that the absorption spectra, as well as the effective dielectric function, of nanoparticles in vacuum or surrounded by a dielectric medium can be obtained by classical Mie and Maxwell-Garnett theories. A limit as to how the particles can be for the theory to apply has not been established. Here I present theoretical results on the optical properties of small Ag, Au, and Si and Ge nanoparticles with tens of atoms in vacuum and in an embedded dielectric medium obtained from first-principles density-functional calculations. In particular, I will discuss the role that d-electron play on the optical properties of Ag and Au nanoparticles, and the cases when classical Mie and Maxwell-Garnett theories can be applied for nanoparticles of just few atoms in size and whose atoms are in bulk-like and not bulk-like positions. Comparison will be made for nanoparticles in vacuum and embedded in an alumina matrix. The quantum-mechanical results indicate that small nanoparticles in alumina can have an imprint on the effective dielectric function that is several times larger than would be predicted by Maxwell-Garnett theory for same-size particles. This work was supported by a GOALI NSF grant, DOE, the Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, and Alcoa Inc. Collaborators: S. ögüt, K. Jackson, J. Jellinek, A. Halabica. R. F. Haglund, R. Magruder, S.J. Pennycook and S.T. Pantelides.

Embedded-atom-method interatomic potentials from lattice inversion.

PubMed

Yuan, Xiao-Jian; Chen, Nan-Xian; Shen, Jiang; Hu, Wangyu

2010-09-22

The present work develops a physically reliable procedure for building the embedded-atom-method (EAM) interatomic potentials for the metals with fcc, bcc and hcp structures. This is mainly based on Chen-Möbius lattice inversion (Chen et al 1997 Phys. Rev. E 55 R5) and first-principles calculations. Following Baskes (Baskes et al 2007 Phys. Rev. B 75 094113), this new version of the EAM eliminates all of the prior arbitrary choices in the determination of the atomic electron density and pair potential functions. Parameterizing the universal form deduced from the calculations within the density-functional scheme for homogeneous electron gas as the embedding function, the new-type EAM potentials for Cu, Fe and Ti metals have successfully been constructed by considering interatomic interactions up to the fifth neighbor, the third neighbor and the seventh neighbor, respectively. The predictions of elastic constants, structural energy difference, vacancy formation energy and migration energy, activation energy of vacancy diffusion, latent heat of melting and relative volume change on melting all satisfactorily agree with the experimental results available or first-principles calculations. The predicted surface energies for low-index crystal faces and the melting point are in agreement with the experimental data to the same extent as those calculated by other EAM-type potentials such as the FBD-EAM, 2NN MEAM and MS-EAM. In addition, the order among the predicted low-index surface energies is also consistent with the experimental information.

The adsorption of helium atoms on small cationic gold clusters.

PubMed

Goulart, Marcelo; Gatchell, Michael; Kranabetter, Lorenz; Kuhn, Martin; Martini, Paul; Gitzl, Norbert; Rainer, Manuel; Postler, Johannes; Scheier, Paul; Ellis, Andrew M

2018-04-04

Adducts formed between small gold cluster cations and helium atoms are reported for the first time. These binary ions, Aun+Hem, were produced by electron ionization of helium nanodroplets doped with neutral gold clusters and were detected using mass spectrometry. For a given value of n, the distribution of ions as a function of the number of added helium atoms, m, has been recorded. Peaks with anomalously high intensities, corresponding to so-called magic number ions, are identified and interpreted in terms of the geometric structures of the underlying Aun+ ions. These features can be accounted for by planar structures for Aun+ ions with n ≤ 7, with the addition of helium having no significant effect on the structures of the underlying gold cluster ions. According to ion mobility studies and some theoretical predictions, a 3-D structure is expected for Au8+. However, the findings for Au8+ in this work are more consistent with a planar structure.

Electronic structure engineering in silicene via atom substitution and a new two-dimensional Dirac structure Si3C

NASA Astrophysics Data System (ADS)

Yin, Na; Dai, Ying; Wei, Wei; Huang, Baibiao

2018-04-01

A lot of efforts have been made towards the band gap opening in two-dimensional silicene, the silicon version of graphene. In the present work, the electronic structures of single atom doped (B, N, Al and P) and codoped (B/N and Al/P) silicene monolayers are systematically examined on the base of density functional electronic calculations. Our results demonstrate that single atom doping can realize electron or hole doping in the silicene; while codoping, due to the syergistic effects, results in finite band gap in silicene at the Dirac point without significantly degrading the electronic properties. In addition, the characteristic of band gap shows dependence on the doping concentration. Importantly, we predict a new two-dimensional Dirac structure, the graphene-like Si3C, which also shows linear band dispersion relation around the Fermi level. Our results demonstrates an important perspective to engineer the electronic and optical properties of silicene.

Ab initio scanning tunneling spectroscopy simulation of graphene with metal adatoms: weak and strong coupling regimes

NASA Astrophysics Data System (ADS)

Kim, Gunn; Parq, Jae-Hyeon; Yu, Jaejun; Kwon, Young-Kyun; Kyung Hee University Collaboration; Seoul National University Collaboration

2011-03-01

Metal atoms on graphene, when ionized, can act as a point-charge impurity to probe a charge response of graphene with the Dirac cone band structure. To understand charge and spin polarization in graphene, we present scanning tunneling spectroscopy STS simulations based on density-functional theory calculations. We find that a Cs atom on graphene is fully ionized with a significant band-bending feature in the STS whereas the charge and magnetic states of Ba and La atoms on graphene appear to be complicated due to orbital hybridization and Coulomb interaction. By applying external electric field, we observe changes in charge donations and spin magnetic moments of the metal adsorbates on graphene. This work was supported by the National Research Foundation of Korea through the ARP (Grant No. R17-2008-033- 01000-0) (J.Y.) and the Basic Science Research Program through the NRF of Korea (Grant No. 2010-0007805) (G.K.).

Non-equilibrium thermodynamics of harmonically trapped bosons

NASA Astrophysics Data System (ADS)

Ángel García-March, Miguel; Fogarty, Thomás; Campbell, Steve; Busch, Thomas; Paternostro, Mauro

2016-10-01

We apply the framework of non-equilibrium quantum thermodynamics to the physics of quenched small-sized bosonic quantum gases in a one-dimensional harmonic trap. We show that dynamical orthogonality can occur in these few-body systems with strong interactions after a quench and we find its occurrence analytically for an infinitely repulsive pair of atoms. We further show this phenomena is related to the fundamental excitations that dictate the dynamics from the spectral function. We establish a clear qualitative link between the amount of (irreversible) work performed on the system and the establishment of entanglement. We extend our analysis to multipartite systems by examining the case of three trapped atoms. We show the initial (pre-quench) interactions play a vital role in determining the dynamical features, while the qualitative features of the two particle case appear to remain valid. Finally, we propose the use of the atomic density profile as a readily accessible indicator of the non-equilibrium properties of the systems in question.

Combined Molecular and Spin Dynamics Simulation of Lattice Vacancies in BCC Iron

NASA Astrophysics Data System (ADS)

Mudrick, Mark; Perera, Dilina; Eisenbach, Markus; Landau, David P.

Using an atomistic model that treats translational and spin degrees of freedom equally, combined molecular and spin dynamics simulations have been performed to study dynamic properties of BCC iron at varying levels of defect impurity. Atomic interactions are described by an empirical many-body potential, and spin interactions with a Heisenberg-like Hamiltonian with a coordinate dependent exchange interaction. Equations of motion are solved numerically using the second-order Suzuki-Trotter decomposition for the time evolution operator. We analyze the spatial and temporal correlation functions for atomic displacements and magnetic order to obtain the effect of vacancy defects on the phonon and magnon excitations. We show that vacancy clusters in the material cause splitting of the characteristic transverse spin-wave excitations, indicating the production of additional excitation modes. Additionally, we investigate the coupling of the atomic and magnetic modes. These modes become more distinct with increasing vacancy cluster size. This material is based upon work supported by the U.S. Department of Energy Office of Science Graduate Student Research (SCGSR) program.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: probing atomic structure in situ.

PubMed

Wang, Hsiu-Wen; Fanelli, Victor R; Reiche, Helmut M; Larson, Eric; Taylor, Mark A; Xu, Hongwu; Zhu, Jinlong; Siewenie, Joan; Page, Katharine

2014-12-01

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO2 measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H2 and natural gas uptake/storage.

Comparing Residue Clusters from Thermophilic and Mesophilic Enzymes Reveals Adaptive Mechanisms.

PubMed

Sammond, Deanne W; Kastelowitz, Noah; Himmel, Michael E; Yin, Hang; Crowley, Michael F; Bomble, Yannick J

2016-01-01

Understanding how proteins adapt to function at high temperatures is important for deciphering the energetics that dictate protein stability and folding. While multiple principles important for thermostability have been identified, we lack a unified understanding of how internal protein structural and chemical environment determine qualitative or quantitative impact of evolutionary mutations. In this work we compare equivalent clusters of spatially neighboring residues between paired thermophilic and mesophilic homologues to evaluate adaptations under the selective pressure of high temperature. We find the residue clusters in thermophilic enzymes generally display improved atomic packing compared to mesophilic enzymes, in agreement with previous research. Unlike residue clusters from mesophilic enzymes, however, thermophilic residue clusters do not have significant cavities. In addition, anchor residues found in many clusters are highly conserved with respect to atomic packing between both thermophilic and mesophilic enzymes. Thus the improvements in atomic packing observed in thermophilic homologues are not derived from these anchor residues but from neighboring positions, which may serve to expand optimized protein core regions.

Comparing Residue Clusters from Thermophilic and Mesophilic Enzymes Reveals Adaptive Mechanisms

PubMed Central

Sammond, Deanne W.; Kastelowitz, Noah; Himmel, Michael E.; Yin, Hang; Crowley, Michael F.; Bomble, Yannick J.

2016-01-01

Understanding how proteins adapt to function at high temperatures is important for deciphering the energetics that dictate protein stability and folding. While multiple principles important for thermostability have been identified, we lack a unified understanding of how internal protein structural and chemical environment determine qualitative or quantitative impact of evolutionary mutations. In this work we compare equivalent clusters of spatially neighboring residues between paired thermophilic and mesophilic homologues to evaluate adaptations under the selective pressure of high temperature. We find the residue clusters in thermophilic enzymes generally display improved atomic packing compared to mesophilic enzymes, in agreement with previous research. Unlike residue clusters from mesophilic enzymes, however, thermophilic residue clusters do not have significant cavities. In addition, anchor residues found in many clusters are highly conserved with respect to atomic packing between both thermophilic and mesophilic enzymes. Thus the improvements in atomic packing observed in thermophilic homologues are not derived from these anchor residues but from neighboring positions, which may serve to expand optimized protein core regions. PMID:26741367

Entanglement with negative Wigner function of almost 3,000 atoms heralded by one photon.

PubMed

McConnell, Robert; Zhang, Hao; Hu, Jiazhong; Ćuk, Senka; Vuletić, Vladan

2015-03-26

Quantum-mechanically correlated (entangled) states of many particles are of interest in quantum information, quantum computing and quantum metrology. Metrologically useful entangled states of large atomic ensembles have been experimentally realized, but these states display Gaussian spin distribution functions with a non-negative Wigner quasiprobability distribution function. Non-Gaussian entangled states have been produced in small ensembles of ions, and very recently in large atomic ensembles. Here we generate entanglement in a large atomic ensemble via an interaction with a very weak laser pulse; remarkably, the detection of a single photon prepares several thousand atoms in an entangled state. We reconstruct a negative-valued Wigner function--an important hallmark of non-classicality--and verify an entanglement depth (the minimum number of mutually entangled atoms) of 2,910 ± 190 out of 3,100 atoms. Attaining such a negative Wigner function and the mutual entanglement of virtually all atoms is unprecedented for an ensemble containing more than a few particles. Although the achieved purity of the state is slightly below the threshold for entanglement-induced metrological gain, further technical improvement should allow the generation of states that surpass this threshold, and of more complex Schrödinger cat states for quantum metrology and information processing. More generally, our results demonstrate the power of heralded methods for entanglement generation, and illustrate how the information contained in a single photon can drastically alter the quantum state of a large system.

An atomic finite element model for biodegradable polymers. Part 1. Formulation of the finite elements.

PubMed

Gleadall, Andrew; Pan, Jingzhe; Ding, Lifeng; Kruft, Marc-Anton; Curcó, David

2015-11-01

Molecular dynamics (MD) simulations are widely used to analyse materials at the atomic scale. However, MD has high computational demands, which may inhibit its use for simulations of structures involving large numbers of atoms such as amorphous polymer structures. An atomic-scale finite element method (AFEM) is presented in this study with significantly lower computational demands than MD. Due to the reduced computational demands, AFEM is suitable for the analysis of Young's modulus of amorphous polymer structures. This is of particular interest when studying the degradation of bioresorbable polymers, which is the topic of an accompanying paper. AFEM is derived from the inter-atomic potential energy functions of an MD force field. The nonlinear MD functions were adapted to enable static linear analysis. Finite element formulations were derived to represent interatomic potential energy functions between two, three and four atoms. Validation of the AFEM was conducted through its application to atomic structures for crystalline and amorphous poly(lactide). Copyright © 2015 Elsevier Ltd. All rights reserved.

Characterization of Generalized Young Measures Generated by Symmetric Gradients

NASA Astrophysics Data System (ADS)

De Philippis, Guido; Rindler, Filip

2017-06-01

This work establishes a characterization theorem for (generalized) Young measures generated by symmetric derivatives of functions of bounded deformation (BD) in the spirit of the classical Kinderlehrer-Pedregal theorem. Our result places such Young measures in duality with symmetric-quasiconvex functions with linear growth. The "local" proof strategy combines blow-up arguments with the singular structure theorem in BD (the analogue of Alberti's rank-one theorem in BV), which was recently proved by the authors. As an application of our characterization theorem we show how an atomic part in a BD-Young measure can be split off in generating sequences.

Polarization asymmetry in two-electron photodetachment - A cogent test of the ionization threshold law

NASA Technical Reports Server (NTRS)

Temkin, A.; Bhatia, A. K.

1988-01-01

A very sensitive test of the electron-atom ionization threshold law is suggested: for spin-aligned heavy negative ions it consists of measuring the polarization asymmetry A(PA) coming from double detachment by left- versus right-circularly polarized light. The respective yields are worked out for the Te(-) (5p)5 2P(3/2) ion. The Coulomb-dipole theory predicts A(PA) to be the ratio of two oscillating functions in sharp contrast to any power law (specifically that of Wannier, 1953) for which the ratio is expected to be a smooth function of energy.

On the elimination of the electronic structure bottleneck in on the fly nonadiabatic dynamics for small to moderate sized (10-15 atom) molecules using fit diabatic representations based solely on ab initio electronic structure data: The photodissociation of phenol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Xiaolei, E-mail: virtualzx@gmail.com; Yarkony, David R., E-mail: yarkony@jhu.edu

2016-01-14

In this work, we demonstrate that for moderate sized systems, here a system with 13 atoms, global coupled potential energy surfaces defined for several electronic states over a wide energy range and for distinct regions of nuclear coordinate space characterized by distinct electron configurations, can be constructed with precise energetics and an excellent description of non-adiabatic interactions in all regions. This is accomplished using a recently reported algorithm for constructing quasi-diabatic representations, H{sup d}, of adiabatic electronic states coupled by conical intersections. In this work, the algorithm is used to construct an H{sup d} to describe the photodissociation of phenolmore » from its first and second excited electronic states. The representation treats all 33 internal degrees of freedom in an even handed manner. The ab initio adiabatic electronic structure data used to construct the fit are obtained exclusively from multireference configuration interaction with single and double excitation wave functions comprised of 88 × 10{sup 6} configuration state functions, at geometries determined by quasi-classical trajectories. Since the algorithm uses energy gradients and derivative couplings in addition to electronic energies to construct H{sup d}, data at only 7379 nuclear configurations are required to construct a representation, which describes all nuclear configurations involved in H atom photodissociation to produce the phenoxyl radical in its ground or first excited electronic state, with a mean unsigned energy error of 202.9 cm{sup −1} for electronic energies <60 000 cm{sup −1}.« less

Theoretical investigation of structures and energetics of sodium adatom and its dimer on graphene: DFT study

NASA Astrophysics Data System (ADS)

Kaur, Gagandeep; Gupta, Shuchi; Rani, Pooja; Dharamvir, Keya

2015-11-01

Extensive ab initio calculations have been performed to study the energetics of a sodium (Na) atom and its dimer adsorbed on graphene using the SIESTA package Soler et al. (2002) [1] which works within a DFT(density functional theory)-GGA (generalized gradient approximation) pseudopotential framework. The adsorption energy, geometry, charge transfer, ionization potential and density of states (DOS), partial density states (PDOS) of adatom/dimer-graphene system have been calculated. After considering various sites for adsorption of Na on graphene, the center of a hexagonal ring of carbon atoms is found to be the preferred site of adsorption while the Na2 dimer prefers to rest parallel to the graphene sheet. We find insignificant energy differences among adsorption configurations involving different possible sites in parallel orientation, which implies high mobility of the dimer on the graphene sheet. We also notice only a slight distortion of the graphene sheet perpendicular to its plane upon adatom adsorption. However, some lateral displacements seen are more perceptible. Summary The adsorption energy, geometry, charge transfer, ionization potential and density of states (DOS) and PDOS of adatom/dimer-graphene system have been calculated using SIESTA package Soler et al. (2002) [1] which works within a DFT(density functional theory)-GGA (generalized gradient approximation) pseudopotential framework. Preferred site for adsorption of a sodium atom on graphene is the hollow site. For the Na dimer adsorption, we found that horizontal orientation is favored over the vertical one. From DOS plots, it is clear that graphene's states are nearly unaffected by the adsorption of Na adatom and Interaction between sodium and graphene is predominantly ionic

Spatial Imaging of Strongly Interacting Rydberg Atoms

NASA Astrophysics Data System (ADS)

Thaicharoen, Nithiwadee

The strong interactions between Rydberg excitations can result in spatial correlations between the excitations. The ability to control the interaction strength and the correlations between Rydberg atoms is applicable in future technological implementations of quantum computation. In this thesis, I investigates how both the character of the Rydberg-Rydberg interactions and the details of the excitation process affect the nature of the spatial correlations and the evolution of those correlations in time. I first describes the experimental apparatus and methods used to perform high-magnification Rydberg-atom imaging, as well as three experiments in which these methods play an important role. The obtained Rydberg-atom positions reveal the correlations in the many-body Rydberg-atom system and their time dependence with sub-micron spatial resolution. In the first experiment, atoms are excited to a Rydberg state that experiences a repulsive van der Waals interaction. The Rydberg excitations are prepared with a well-defined initial separation, and the effect of van der Waals forces is observed by tracking the interatomic distance between the Rydberg atoms. The atom trajectories and thereby the interaction coefficient C6 are extracted from the pair correlation functions of the Rydberg atom positions. In the second experiment, the Rydberg atoms are prepared in a highly dipolar state by using adiabatic state transformation. The atom-pair kinetics that follow from the strong dipole-dipole interactions are observed. The pair correlation results provide the first direct visualization of the electric-dipole interaction and clearly exhibit its anisotropic nature. In both the first and the second experiment, results of semi-classical simulations of the atom-pair trajectories agree well with the experimental data. In the analysis, I use energy conservation and measurements of the initial positions and the terminal velocities of the atom pairs to extract the C6 and C 3 interaction coefficients. The final experiment demonstrates the ability to enhance or suppress the degree of spatial correlation in a system of Rydberg excitations, using a rotary-echo excitation process in concert with particular excitation laser detunings. The work in this thesis demonstrates an ability to control long-range interactions between Rydberg atoms, which paves the way towards preparing and studying increasingly complex many-body systems.

Nanoscopic electrode molecular probes

DOEpatents

Krstic, Predrag S [Knoxville, TN; Meunier, Vincent [Knoxville, TN

2012-05-22

The present invention relates to a method and apparatus for enhancing the electron transport property measurements of a molecule when the molecule is placed between chemically functionalized carbon-based nanoscopic electrodes to which a suitable voltage bias is applied. The invention includes selecting a dopant atom for the nanoscopic electrodes, the dopant atoms being chemically similar to atoms present in the molecule, and functionalizing the outer surface and terminations of the electrodes with the dopant atoms.

The Stark Effect on the Wave Function of Tritium in Relativistic Condition

NASA Astrophysics Data System (ADS)

Supriadi, B.; Prastowo, S. H. B.; Bahri, S.; Ridlo, Z. R.; Prihandono, T.

2018-03-01

Tritium Atom is one of the isotopes of Hydrogen that has two Neutrons in the nucleus and an electron that surrounds the nucleus. The Stark Effect is an effect of a shift or polarization of the atomic spectrum caused by the external electrostatic field. The interaction between the electrons and the external electric field can be reviewed using an approximation method of perturbation theory. The perturbation theory used is a time Independent non-degenerate perturbation and reviewed to second order to obtain correction of Tritium Atomic wave function. The condition that used in the system is a relativistic condition by reviewing the movement of electrons within the Atom. The effects of relativity also affect the correction of the wave function of Atom Tritium in the ground state. Tritium is radioactive material that is still relatively safe, and one of the applications of Tritium Atom is on the battery of betavoltaics (Nano Tritium Battery).

76 FR 58049 - Atomic Safety and Licensing Board; Honeywell International, Inc.; Metropolis Works Uranium...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-19

... NUCLEAR REGULATORY COMMISSION [Docket No. 40-3392-MLA; ASLBP No. 11-910-01-MLA-BD01] Atomic Safety and Licensing Board; Honeywell International, Inc.; Metropolis Works Uranium Conversion Facility... assurance for its Metropolis Works uranium conversion facility in Metropolis, Illinois. \\1\\ LBP-11-19, 74...

Wave-function functionals

NASA Astrophysics Data System (ADS)

Pan, Xiao-Yin; Slamet, Marlina; Sahni, Viraht

2010-04-01

We extend our prior work on the construction of variational wave functions ψ that are functionals of functions χ:ψ=ψ[χ] rather than simply being functions. In this manner, the space of variations is expanded over those of traditional variational wave functions. In this article we perform the constrained search over the functions χ chosen such that the functional ψ[χ] satisfies simultaneously the constraints of normalization and the exact expectation value of an arbitrary single- or two-particle Hermitian operator, while also leading to a rigorous upper bound to the energy. As such the wave function functional is accurate not only in the region of space in which the principal contributions to the energy arise but also in the other region of the space represented by the Hermitian operator. To demonstrate the efficacy of these ideas, we apply such a constrained search to the ground state of the negative ion of atomic hydrogen H-, the helium atom He, and its positive ions Li+ and Be2+. The operators W whose expectations are obtained exactly are the sum of the single-particle operators W=∑irin,n=-2,-1,1,2, W=∑iδ(ri), W=-(1)/(2)∑i∇i2, and the two-particle operators W=∑nun,n=-2,-1,1,2, where u=|ri-rj|. Comparisons with the method of Lagrangian multipliers and of other constructions of wave-function functionals are made. Finally, we present further insights into the construction of wave-function functionals by studying a previously proposed construction of functionals ψ[χ] that lead to the exact expectation of arbitrary Hermitian operators. We discover that analogous to the solutions of the Schrödinger equation, there exist ψ[χ] that are unphysical in that they lead to singular values for the expectations. We also explain the origin of the singularity.

Lithium effect on the electronic properties of porous silicon for energy storage applications: a DFT study.

PubMed

González, I; Sosa, A N; Trejo, A; Calvino, M; Miranda, A; Cruz-Irisson, M

2018-05-23

Theoretical studies on the effect of Li on the electronic properties of porous silicon are still scarce; these studies could help us in the development of Li-ion batteries of this material which overcomes some limitations that bulk silicon has. In this work, the effect of interstitial and surface Li on the electronic properties of porous Si is studied using the first-principles density functional theory approach and the generalised gradient approximation. The pores are modeled by removing columns of atoms of an otherwise perfect Si crystal, dangling bonds of all surfaces are passivated with H atoms, and then Li is inserted on interstitial positions on the pore wall and compared with the replacement of H atoms with Li. The results show that the interstitial Li creates effects similar to n-type doping where the Fermi level is shifted towards the conduction band with band crossings of the said level thus acquiring metallic characteristics. The surface Li introduces trap-like states in the electronic band structures which increase as the number of Li atom increases with a tendency to become metallic. These results could be important for the application of porous Si nanostructures in Li-ion batteries technology.

Structural and thermodynamic properties of WB at high pressure and high temperature

NASA Astrophysics Data System (ADS)

Chen, Hai-Hua; Bi, Yan; Cheng, Yan; Ji, Guangfu; Peng, Fang; Hu, Yan-Fei

2012-12-01

The structure parameters and electronic structures of tungsten boride (WB) have been investigated by using the density functional theory (DFT). Our calculating results display the bulk modulus of WB are 352±2 GPa (K‧0=4.29) and 322±3 GPa (K‧0=4.21) by LDA and GGA methods, respectively. We have analyzed the probable reason of the discrepancy from the bulk modulus between theoretical and experimental results. The compression behavior of the unit cell axes is anisotropic, with the c-axis being more compressible than the a-axis. By analyzing the bond lengths information, it also demonstrated that WB has a lower compressibility at high pressure. From the partial densities of states (PDOS) of WB, we found that the Fermi lever is mostly contributed by the d states of W atom and p states of B atom and that the contributions from the s, p states of W atom and s states of B atom are small. Moreover, using the Gibbs 2 program, the thermodynamic properties of WB are obtained in a wide temperature range at high pressure for the first time in this work.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-03-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Polarity control of GaN epitaxial films grown on LiGaO2(001) substrates and its mechanism.

PubMed

Zheng, Yulin; Wang, Wenliang; Li, Xiaochan; Li, Yuan; Huang, Liegen; Li, Guoqiang

2017-08-16

The polarity of GaN epitaxial films grown on LiGaO 2 (001) substrates by pulsed laser deposition has been well controlled. It is experimentally proved that the GaN epitaxial films grown on nitrided LiGaO 2 (001) substrates reveal Ga-polarity, while the GaN epitaxial films grown on non-nitrided LiGaO 2 (001) substrates show N-polarity. The growth mechanisms for these two cases are systematically studied by first-principles calculations based on density functional theory. Theoretical calculation presents that the adsorption of a Ga atom preferentially occurs at the center of three N atoms stacked on the nitrided LiGaO 2 (001) substrates, which leads to the formation of Ga-polarity GaN. Whereas the adsorption of a Ga atom preferentially deposits at the top of a N atom stacked on the non-nitrided LiGaO 2 (001) substrates, which results in the formation of N-polarity GaN. This work of controlling the polarity of GaN epitaxial films is of paramount importance for the fabrication of group-III nitride devices for various applications.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-06-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Study of Cs/NF3 adsorption on GaN (0 0 1) surface

NASA Astrophysics Data System (ADS)

Diao, Yu; Liu, Lei; Xia, Sihao; Kong, Yike

2017-03-01

To investigate the optoelectronics properties of Cs/NF3 adsorption on GaN (0 0 1) photocathode surface, different adsorption models of Cs-only, Cs/O, Cs/NF3 adsorption on GaN clean surface were established, respectively. Atomic structures, work function, adsorption energy, E-Mulliken charge distribution, density of states and optical properties of all these adsorption systems were calculated using first principles. Compared with Cs/O co-adsorption, Cs/NF3 co-adsorption show better stability and more decline of work function, which is more beneficial for photoemission efficiency. Besides, surface band structures of Cs/NF3 co-adsorption system exhibit metal properties, implying good conductivity. Meanwhile, near valence band minimum of Cs/NF3 co-adsorption system, more acceptor levels emerges to form a p-type emission surface, which is conductive to the escape of photoelectrons. In addition, imaginary part of dielectric function curve and absorption curve of Cs/NF3 co-adsorption system both move towards lower energy side. This work can direct the optimization of activation process of NEA GaN photocathode.

Wigner functions for nonclassical states of a collection of two-level atoms

NASA Technical Reports Server (NTRS)

Agarwal, G. S.; Dowling, Jonathan P.; Schleich, Wolfgang P.

1993-01-01

The general theory of atomic angular momentum states is used to derive the Wigner distribution function for atomic angular momentum number states, coherent states, and squeezed states. These Wigner functions W(theta,phi) are represented as a pseudo-probability distribution in spherical coordinates theta and phi on the surface of a sphere of radius the square root of j(j +1) where j is the total angular momentum.

The calculation of the viscosity from the autocorrelation function using molecular and atomic stress tensors

NASA Astrophysics Data System (ADS)

Cui, S. T.

The stress-stress correlation function and the viscosity of a united-atom model of liquid decane are studied by equilibrium molecular dynamics simulation using two different formalisms for the stress tensor: the atomic and the molecular formalisms. The atomic and molecular correlation functions show dramatic difference in short-time behaviour. The integrals of the two correlation functions, however, become identical after a short transient period whichis significantly shorter than the rotational relaxation time of the molecule. Both reach the same plateau value in a time period corresponding to this relaxation time. These results provide a convenient guide for the choice of the upper integral time limit in calculating the viscosity by the Green-Kubo formula.

The Dynamics of a Five-level (Double Λ)-type Atom Interacting with Two-mode Field in a Cross Kerr-like Medium

NASA Astrophysics Data System (ADS)

Obada, A.-S. F.; Ahmed, M. M. A.; Farouk, Ahmed M.

2018-04-01

In this paper, we propose a new transition scheme (Double Λ) for the interaction between a five-level atom and an electromagnetic field and study its dynamics in the presence of a cross Kerr-like medium in the exact-resonance case. The wave function is derived when the atom is initially prepared in its upper most state, and the field is initially prepared in the coherent state. We studied the atomic population inversion, the coherence degree by studying the second-order correlation function, Cauchy-Schwartz inequality (CSI) and the relation with P-function. Finally, we investigate the effect of Kerr-like medium on the evolution of Husimi Q-function of the considered system.

Reactions of Azine Anions with Nitrogen and Oxygen Atoms: Implications for Titan's Upper Atmosphere and Interstellar Chemistry.

PubMed

Wang, Zhe-Chen; Cole, Callie A; Demarais, Nicholas J; Snow, Theodore P; Bierbaum, Veronica M

2015-08-26

Azines are important in many extraterrestrial environments, from the atmosphere of Titan to the interstellar medium. They have been implicated as possible carriers of the diffuse interstellar bands in astronomy, indicating their persistence in interstellar space. Most importantly, they constitute the basic building blocks of DNA and RNA, so their chemical reactivity in these environments has significant astrobiological implications. In addition, N and O atoms are widely observed in the ISM and in the ionospheres of planets and moons. However, the chemical reactions of molecular anions with abundant interstellar and atmospheric atomic species are largely unexplored. In this paper, gas-phase reactions of deprotonated anions of benzene, pyridine, pyridazine, pyrimidine, pyrazine, and s-triazine with N and O atoms are studied both experimentally and computationally. In all cases, the major reaction channel is associative electron detachment; these reactions are particularly important since they control the balance between negative ions and free electron densities. The reactions of the azine anions with N atoms exhibit larger rate constants than reactions of corresponding chain anions. The reactions of azine anions with O atoms are even more rapid, with complex product patterns for different reactants. The mechanisms are studied theoretically by employing density functional theory; spin conversion is found to be important in determining some product distributions. The rich gas-phase chemistry observed in this work provides a better understanding of ion-atom reactions and their contributions to ionospheric chemistry as well as the chemical processing that occurs in the boundary layers between diffuse and dense interstellar clouds.

PREDICTION OF FORBIDDEN ULTRAVIOLET AND VISIBLE EMISSIONS IN COMET 67P/CHURYUMOV–GERASIMENKO

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raghuram, Susarla; Galand, Marina; Bhardwaj, Anil, E-mail: raghuramsusarla@gmail.com

Remote observation of spectroscopic emissions is a potential tool for the identification and quantification of various species in comets. The CO Cameron band (to trace CO{sub 2}) and atomic oxygen emissions (to trace H{sub 2}O and/or CO{sub 2}, CO) have been used to probe neutral composition in the cometary coma. Using a coupled-chemistry-emission model, various excitation processes controlling the CO Cameron band and different atomic oxygen and atomic carbon emissions have been modeled in comet 67P/Churyumov–Gerasimenko at 1.29 AU (perihelion) and at 3 AU heliocentric distances, which is being explored by ESA's Rosetta mission. The intensities of the CO Cameronmore » band, atomic oxygen, and atomic carbon emission lines as a function of projected distance are calculated for different CO and CO{sub 2} volume mixing ratios relative to water. Contributions of different excitation processes controlling these emissions are quantified. We assess how CO{sub 2} and/or CO volume mixing ratios with respect to H{sub 2}O can be derived based on the observed intensities of the CO Cameron band, atomic oxygen, and atomic carbon emission lines. The results presented in this work serve as baseline calculations to understand the behavior of low out-gassing cometary coma and compare them with the higher gas production rate cases (e.g., comet Halley). Quantitative analysis of different excitation processes governing the spectroscopic emissions is essential to study the chemistry of inner coma and to derive neutral gas composition.« less

Observation of hidden atomic order at the interface between Fe and topological insulator Bi2Te3.

PubMed

Sánchez-Barriga, Jaime; Ogorodnikov, Ilya I; Kuznetsov, Mikhail V; Volykhov, Andrey A; Matsui, Fumihiko; Callaert, Carolien; Hadermann, Joke; Verbitskiy, Nikolay I; Koch, Roland J; Varykhalov, Andrei; Rader, Oliver; Yashina, Lada V

2017-11-22

To realize spintronic devices based on topological insulators (TIs), well-defined interfaces between magnetic metals and TIs are required. Here, we characterize atomically precisely the interface between the 3d transition metal Fe and the TI Bi 2 Te 3 at different stages of its formation. Using photoelectron diffraction and holography, we show that after deposition of up to 3 monolayers Fe on Bi 2 Te 3 at room temperature, the Fe atoms are ordered at the interface despite the surface disorder revealed by our scanning-tunneling microscopy images. We find that Fe occupies two different sites: a hollow adatom deeply relaxed into the Bi 2 Te 3 quintuple layers and an interstitial atom between the third (Te) and fourth (Bi) atomic layers. For both sites, our core-level photoemission spectra and density-functional theory calculations demonstrate simultaneous chemical bonding of Fe to both Te and Bi atoms. We further show that upon deposition of Fe up to a thickness of 20 nm, the Fe atoms penetrate deeper into the bulk forming a 2-5 nm interface layer containing FeTe. In addition, excessive Bi is pushed down into the bulk of Bi 2 Te 3 leading to the formation of septuple layers of Bi 3 Te 4 within a distance of ∼25 nm from the interface. Controlling the magnetic properties of the complex interface structures revealed by our work will be of critical importance when optimizing the efficiency of spin injection in TI-based devices.

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

PubMed

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Computer Models of Proteins

NASA Technical Reports Server (NTRS)

2000-01-01

Dr. Marc Pusey (seated) and Dr. Craig Kundrot use computers to analyze x-ray maps and generate three-dimensional models of protein structures. With this information, scientists at Marshall Space Flight Center can learn how proteins are made and how they work. The computer screen depicts a proten structure as a ball-and-stick model. Other models depict the actual volume occupied by the atoms, or the ribbon-like structures that are crucial to a protein's function.

Investigation of Material Problems for High Temperature, High Power Space Energy-Conversion Systems.

DTIC Science & Technology

1986-07-01

Microplastic Deformation in Molybdenum with Grain-Boundary Segregations of Nickel, Phys. Met. Metall. 54, 180, 1982. 76. C. Lea, B. Muddle and D...8217-- *. ~a.-. ~ ~ ~ .. . ~ . ~ . .*.. -- ~ .. 25 93. T. Noda, T. Kainuma and M. Okada: Oxygen Desorption from Grain Boundaries of Molybdenum During Vacuu...behavior of this work function climb was explained by the desorption of atoms adsorbed or, the surface. The test result of the present W-Re samples showed

1978 bibliography of atomic and molecular processes. [Bibliography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Not Available

This annotated bibliography lists 2557 works on atomic and molecular processes reported in publications dated 1978. Sources include scientific journals, conference proceedings, and books. Each entry is designated by one or more of the 114 categories of atomic and molecular processes used by the Controlled Fusion Atomic Data Center to classify data. Also indicated is whether the work was experimental or theoretical, what energy range was covered, what reactants were investigated, and the country of origin of the first author. Following the bibliographical listing are indexes of reactants and authors.

1979 bibliography of atomic and molecular processes. [Bibliography

DOE Office of Scientific and Technical Information (OSTI.GOV)

None

1980-08-01

This annotated bibliography lists 2146 works on atomic and molecular processes reported in publications dated 1979. Sources include scientific journals, conference proceedings, and books. Each entry is designated by one or more of the 114 categories of atomic and molecular processes used by the Controlled Fusion Atomic Data Center, Oak Ridge National Laboratory, to classify data. Also indicated is whether the work was experimental or theoretical, what energy range was covered, what reactants were investigated, and the country of origin of the first author. Following the bibliographical listing are indexes of reactants and authors.

Role of oxygen adsorption in modification of optical and surface electronic properties of MoS2

NASA Astrophysics Data System (ADS)

Shakya, Jyoti; Kumar, Sanjeev; Mohanty, Tanuja

2018-04-01

In this work, the effect of surface oxidation of molybdenum disulfide (MoS2) nanosheets induced by hydrogen peroxide (H2O2) on the work function and bandgap of MoS2 has been investigated for tuning its optical and electronic properties. Transmission electron microscopy studies reveal the existence of varying morphologies of few layers of MoS2 as well as quantum dots due to the different absorbing effects of two mixed solvents on MoS2. The X-ray diffraction, electron paramagnetic resonance, and Raman studies indicate the presence of physical as well as chemical adsorption of oxygen atoms in MoS2. The photoluminescence spectra show the tuning of bandgap arising from the passivation of trapping centers leading to radiative recombination of excitons. The value of work function obtained from scanning Kelvin probe microscopy of MoS2 in mixed solvents of H2O2 and N-methyl-2-pyrrolidone increases with an increase in the concentration of H2O2. A linear relationship could be established between H2O2 content in mixed solvent and measured values of work function. This work gives the alternative route towards the commercial use of defect engineered transition metal dichalcogenide materials in diverse fields.

Understanding the atomic-level Green-Kubo stress correlation function for a liquid through phonons in a model crystal

NASA Astrophysics Data System (ADS)

Levashov, V. A.

2014-11-01

In order to gain insight into the connection between the vibrational dynamics and the atomic-level Green-Kubo stress correlation function in liquids, we consider this connection in a model crystal instead. Of course, vibrational dynamics in liquids and crystals are quite different and it is not expected that the results obtained on a model crystal should be valid for liquids. However, these considerations provide a benchmark to which the results of the previous molecular dynamics simulations can be compared. Thus, assuming that vibrations are plane waves, we derive analytical expressions for the atomic-level stress correlation functions in the classical limit and analyze them. These results provide, in particular, a recipe for analysis of the atomic-level stress correlation functions in Fourier space and extraction of the wave-vector and frequency-dependent information. We also evaluate the energies of the atomic-level stresses. The energies obtained are significantly smaller than the energies previously determined in molecular dynamics simulations of several model liquids. This result suggests that the average energies of the atomic-level stresses in liquids and glasses are largely determined by the structural disorder. We discuss this result in the context of equipartition of the atomic-level stress energies. Analysis of the previously published data suggests that it is possible to speak about configurational and vibrational contributions to the average energies of the atomic-level stresses in a glass state. However, this separation in a liquid state is problematic. We also introduce and briefly consider the atomic-level transverse current correlation function. Finally, we address the broadening of the peaks in the pair distribution function with increase of distance. We find that the peaks' broadening (by ≈40 % ) occurs due to the transverse vibrational modes, while contribution from the longitudinal modes does not change with distance.

Hybrid Systems: Cold Atoms Coupled to Micro Mechanical Oscillators =

NASA Astrophysics Data System (ADS)

Montoya Monge, Cris A.

Micro mechanical oscillators can serve as probes in precision measurements, as transducers to mediate photon-phonon interactions, and when functionalized with magnetic material, as tools to manipulate spins in quantum systems. This dissertation includes two projects where the interactions between cold atoms and mechanical oscillators are studied. In one of the experiments, we have manipulated the Zeeman state of magnetically trapped Rubidium atoms with a magnetic micro cantilever. The results show a spatially localized effect produced by the cantilever that agrees with Landau-Zener theory. In the future, such a scalable system with highly localized interactions and the potential for single-spin sensitivity could be useful for applications in quantum information science or quantum simulation. In a second experiment, work is in progress to couple a sample of optically trapped Rubidium atoms to a levitated nanosphere via an optical lattice. This coupling enables the cooling of the center-of-mass motion of the nanosphere by laser cooling the atoms. In this system, the atoms are trapped in the optical lattice while the sphere is levitated in a separate vacuum chamber by a single-beam optical tweezer. Theoretical analysis of such a system has determined that cooling the center-of-mass motion of the sphere to its quantum ground state is possible, even when starting at room temperature, due to the excellent environmental decoupling achievable in this setup. Nanospheres cooled to the quantum regime can provide new tests of quantum behavior at mesoscopic scales and have novel applications in precision sensing.

Observation of dynamic atom-atom correlation in liquid helium in real space.

PubMed

Dmowski, W; Diallo, S O; Lokshin, K; Ehlers, G; Ferré, G; Boronat, J; Egami, T

2017-05-04

Liquid 4 He becomes superfluid and flows without resistance below temperature 2.17 K. Superfluidity has been a subject of intense studies and notable advances were made in elucidating the phenomenon by experiment and theory. Nevertheless, details of the microscopic state, including dynamic atom-atom correlations in the superfluid state, are not fully understood. Here using a technique of neutron dynamic pair-density function (DPDF) analysis we show that 4 He atoms in the Bose-Einstein condensate have environment significantly different from uncondensed atoms, with the interatomic distance larger than the average by about 10%, whereas the average structure changes little through the superfluid transition. DPDF peak not seen in the snap-shot pair-density function is found at 2.3 Å, and is interpreted in terms of atomic tunnelling. The real space picture of dynamic atom-atom correlations presented here reveal characteristics of atomic dynamics not recognized so far, compelling yet another look at the phenomenon.

Reassessment of Atomic Mobilities in fcc Cu-Ag-Sn System Aiming at Establishment of an Atomic Mobility Database in Sn-Ag-Cu-In-Sb-Bi-Pb Solder Alloys

NASA Astrophysics Data System (ADS)

Xu, Huixia; Zhang, Lijun; Cheng, Kaiming; Chen, Weimin; Du, Yong

2017-04-01

To establish an accurate atomic mobility database in solder alloys, a reassessment of atomic mobilities in the fcc (face centered cubic) Cu-Ag-Sn system was performed as reported in the present work. The work entailed initial preparation of three fcc Cu-Sn diffusion couples, which were used to determine the composition-dependent interdiffusivities at 873 K, 923 K, and 973 K, to validate the literature data and provide new experimental data at low temperatures. Then, atomic mobilities in three boundary binaries, fcc Cu-Sn, fcc Ag-Sn, and fcc Cu-Ag, were updated based on the data for various experimental diffusivities obtained from the literature and the present work, together with the available thermodynamic database for solder alloys. Finally, based on the large number of interdiffusivities recently measured from the present authors, atomic mobilities in the fcc Cu-Ag-Sn ternary system were carefully evaluated. A comprehensive comparison between various calculated/model-predicted diffusion properties and the experimental data was used to validate the reliability of the obtained atomic mobilities in ternary fcc Cu-Ag-Sn alloys.

Determination of wave-function functionals: The constrained-search variational method

NASA Astrophysics Data System (ADS)

Pan, Xiao-Yin; Sahni, Viraht; Massa, Lou

2005-09-01

In a recent paper [Phys. Rev. Lett. 93, 130401 (2004)], we proposed the idea of expanding the space of variations in variational calculations of the energy by considering the approximate wave function ψ to be a functional of functions χ , ψ=ψ[χ] , rather than a function. A constrained search is first performed over all functions χ such that the wave-function functional ψ[χ] satisfies a physical constraint or leads to the known value of an observable. A rigorous upper bound to the energy is then obtained via the variational principle. In this paper we generalize the constrained-search variational method, applicable to both ground and excited states, to the determination of arbitrary Hermitian single-particle operators as applied to two-electron atomic and ionic systems. We construct analytical three-parameter ground-state functionals for the H- ion and the He atom through the constraint of normalization. We present the results for the total energy E , the expectations of the single-particle operators W=∑irin , n=-2,-1,1,2 , W=∑iδ(ri) , and W=∑iδ(ri-r) , the structure of the nonlocal Coulomb hole charge ρc(rr') , and the expectations of the two particle operators u2,u,1/u,1/u2 , where u=∣ri-rj∣ . The results for all the expectation values are remarkably accurate when compared with the 1078-parameter wave function of Pekeris, and other wave functions that are not functionals. We conclude by describing our current work on how the constrained-search variational method in conjunction with quantal density-functional theory is being applied to the many-electron case.

Ab Initio Density Functional Calculations and Infra-Red Study of CO Interaction with Pd Atoms on θ-Al2O3 (010) Surface.

PubMed

Narula, Chaitanya K; Allard, Lawrence F; Wu, Zili

2017-07-24

The ab initio density functional theoretical studies show that energetics favor CO oxidation on single Pd atoms supported on θ-alumina. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show that carbonates are formed as intermediates when single supported Pd atoms are exposed to a gaseous mixture of CO + O 2 . The rapid agglomeration of Pd atoms under CO oxidation conditions even at 6 °C leads to the presence of Pd particles along with single atoms during CO oxidation experiments. Thus, the observed CO oxidation has contributions from both single Pd atoms and Pd particles.

Automatic Molecular Design using Evolutionary Techniques

NASA Technical Reports Server (NTRS)

Globus, Al; Lawton, John; Wipke, Todd; Saini, Subhash (Technical Monitor)

1998-01-01

Molecular nanotechnology is the precise, three-dimensional control of materials and devices at the atomic scale. An important part of nanotechnology is the design of molecules for specific purposes. This paper describes early results using genetic software techniques to automatically design molecules under the control of a fitness function. The fitness function must be capable of determining which of two arbitrary molecules is better for a specific task. The software begins by generating a population of random molecules. The population is then evolved towards greater fitness by randomly combining parts of the better individuals to create new molecules. These new molecules then replace some of the worst molecules in the population. The unique aspect of our approach is that we apply genetic crossover to molecules represented by graphs, i.e., sets of atoms and the bonds that connect them. We present evidence suggesting that crossover alone, operating on graphs, can evolve any possible molecule given an appropriate fitness function and a population containing both rings and chains. Prior work evolved strings or trees that were subsequently processed to generate molecular graphs. In principle, genetic graph software should be able to evolve other graph representable systems such as circuits, transportation networks, metabolic pathways, computer networks, etc.

Rhodium clustering process on defective (8,0) SWCNT: Analysis of chemical and physical properties using density functional theory

NASA Astrophysics Data System (ADS)

Ambrusi, Ruben E.; Luna, C. Romina; Sandoval, Mario G.; Bechthold, Pablo; Pronsato, M. Estela; Juan, Alfredo

2017-12-01

The Spin-polarized density functional theory is used to study the effect of a single vacancy in a (8,0) single-walled carbon nanotube (SWCNT) on the Rh clustering process. The vacancy is considered oxygenated and non-oxygenated and, in each case, different Rhn cluster sizes (n = 1-4) are taken into account. For the analysis of these systems some physical and chemical properties are calculated, such as binding energy (Eb), work function (WF), magnetic moment, charge transfer, bond length, band gap (Eg), and density of state (DOS). From this analysis it can be concluded that: a single Rh atom and Rh2 dimer are adsorbed on vacancy without oxygen, whereas Rh3 and Rh4 clusters prefer to be adsorbed on oxygenated vacancy. In all cases, Rh adsorption induces a magnetic moment. When the Rh atom and Rh2 dimer are bonded to the defective SWCNT, it has been found that they show a semiconductor behavior that could be interesting to use in the spintronic area. In the case of Rh3 and Rh4 clusters our results show a metallic behavior suggesting that these systems are good candidates for nanotube contact.

Communication: Near-locality of exchange and correlation density functionals for 1- and 2-electron systems

NASA Astrophysics Data System (ADS)

Sun, Jianwei; Perdew, John P.; Yang, Zenghui; Peng, Haowei

2016-05-01

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin density approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.

Diffusion Mechanisms of Ag atom in ZnO crystal: A First Principles Study

NASA Astrophysics Data System (ADS)

Masoumi, Saeed; Noori, Amirreza; Nadimi, Ebrahim

2017-12-01

Zinc oxide (ZnO) is currently under intensive investigation, as a result of its various applications in micro, nano and optoelectronics. However, a stable and reproducible p-type doping of ZnO is still a main challenging issue. Group IB elements such as Au, Cu and Ag, are promising candidates for p-type doping. Particularly, Ag atoms has been shown to be able to easily diffuse through the crystal structure of ZnO and lead to the p-type doping of the host crystal. However, the current understanding of Ag defects and their mobility in the ZnO crystal is still not fully explored. In this work, we report the results of our first-principles calculations based on density functional theory for Ag defects, particularly the interstitial and substitutional defects in ZnO crystal. Defect formation energies are calculated in different charged states as a function of Fermi energy in order to clarify the p-type behaviour of Ag-doped ZnO. We also investigate the diffusion behaviour and migration paths of Ag in ZnO crystal in the framework of density functional theory applying climbing image (CI) nudged elastic band method (NEB).

Efficiency of Cs-free materials for negative ion production in H2 and D2 plasmas

NASA Astrophysics Data System (ADS)

Friedl, R.; Kurutz, U.; Fantz, U.

2017-08-01

High power negative ion sources use caesium to reduce the work function of the converter surface which significantly increases the negative ion yield. Caesium, however, is a very reactive alkali-metal and shows complex redistribution dynamics in consequence of plasma-surface-interaction. Thus, maintaining a stable and homogenous low work function surface is a demanding task, which is not easily compatible with the RAMI issues (reliability, availability, maintainability, inspectability) for a future DEMO fusion reactor. Hence, Cs-free alternative materials for efficient negative ion formation are desirable. At the laboratory experiment HOMER materials which are referred to as promising are investigated under identical and ion source relevant parameters: the refractory metals Ta and W, non-doped and boron-doped diamond as well as materials with inherent low work function (lanthanum-doped molybdenum, MoLa and lanthanum hexaboride, LaB6). The results are compared to the effect of in-situ caesiation, which at HOMER leads to a maximal increase of the negative ion density by a factor of 2.5. Among the examined samples low work function materials are most efficient. In particular, MoLa leads to an increase of almost 50 % compared to pure volume formation. The difference to a caesiated surface can be attributed to the still higher work function of MoLa, which is expected to be slightly below 3 eV. Using deuterium instead of hydrogen leads to increased atomic and positive ion densities, while comparable negative ion densities are achieved. In contrast to the low work function materials, bulk samples of the refractory metals as well as carbon based materials have no enhancing effect on H-, where the latter materials furthermore show severe erosion due to the hydrogen plasma.

13. Elevations, 233S, U.S. Atomic Energy Commission, Hanford Works, General ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

13. Elevations, 233-S, U.S. Atomic Energy Commission, Hanford Works, General Electric Company, Dwg. No. H-2-7203, 1956. - Reduction-Oxidation Complex, Plutonium Concentration Facility, 200 West Area, Richland, Benton County, WA

Atomically resolved structure of ligand-protected Au{sub 9} clusters on TiO{sub 2} nanosheets using aberration-corrected STEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Al Qahtani, Hassan S.; Andersson, Gunther G., E-mail: gunther.andersson@flinders.edu.au, E-mail: nakayama.tomonobu@nims.go.jp; Kimoto, Koji

2016-03-21

Triphenylphosphine ligand-protected Au{sub 9} clusters deposited onto titania nanosheets show three different atomic configurations as observed by scanning transmission electron microscopy. The configurations observed are a 3-dimensional structure, corresponding to the previously proposed Au{sub 9} core of the clusters, and two pseudo-2-dimensional (pseudo-2D) structures, newly found by this work. With the help of density functional theory (DFT) calculations, the observed pseudo-2D structures are attributed to the low energy, de-ligated structures formed through interaction with the substrate. The combination of scanning transmission electron microscopy with DFT calculations thus allows identifying whether or not the deposited Au{sub 9} clusters have been de-ligatedmore » in the deposition process.« less

The OI/1S/ state - Its quenching by O2 and formation by the dissociative recombination of vibrationally excited O2/+/ ions

NASA Technical Reports Server (NTRS)

Zipf, E. C.

1979-01-01

The rate coefficient for the quenching of metastable O(1S) atoms by O2 was measured as a function of temperature from 250 to 550 K. The resulting Arrhenius expression correlates well with previous laboratory work. It is suggested that the much larger value of the rate coefficient inferred from an analysis of artificial auroral experiment, Precede, may be explained by overestimation of the contribution of O(1S) production from O2(+) dissociative recombination. The possibility that O(1S) atoms are produced only by the dissociative recombination of vibrationally excited O2(+) ions is examined; such excited ions would not exist in the Precede experiment because of the rapid cooling of the ions by resonant charge transfer processes.

Current-induced changes of migration energy barriers in graphene and carbon nanotubes.

PubMed

Obodo, J T; Rungger, I; Sanvito, S; Schwingenschlögl, U

2016-05-21

An electron current can move atoms in a nanoscale device with important consequences for the device operation and breakdown. We perform first principles calculations aimed at evaluating the possibility of changing the energy barriers for atom migration in carbon-based systems. In particular, we consider the migration of adatoms and defects in graphene and carbon nanotubes. Although the current-induced forces are large for both the systems, in graphene the force component along the migration path is small and therefore the barrier height is little affected by the current flow. In contrast, the same barrier is significantly reduced in carbon nanotubes as the current increases. Our work also provides a real-system numerical demonstration that current-induced forces within density functional theory are non-conservative.

Sequence-Dependent Structure/Function Relationships of Catalytic Peptide-Enabled Gold Nanoparticles Generated under Ambient Synthetic Conditions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bedford, Nicholas M.; Hughes, Zak E.; Tang, Zhenghua

Peptide-enabled nanoparticle (NP) synthesis routes can create and/or assemble functional nanomaterials under environmentally friendly conditions, with properties dictated by complex interactions at the biotic/abiotic interface. Manipulation of this interface through sequence modification can provide the capability for material properties to be tailored to create enhanced materials for energy, catalysis, and sensing applications. Fully realizing the potential of these materials requires a comprehensive understanding of sequence-dependent structure/function relationships that is presently lacking. In this work, the atomic-scale structures of a series of peptide-capped Au NPs are determined using a combination of atomic pair distribution function analysis of high-energy X-ray diffraction datamore » and advanced molecular dynamics (MD) simulations. The Au NPs produced with different peptide sequences exhibit varying degrees of catalytic activity for the exemplar reaction 4-nitrophenol reduction. The experimentally derived atomic-scale NP configurations reveal sequence-dependent differences in structural order at the NP surface. Replica exchange with solute-tempering MD simulations are then used to predict the morphology of the peptide overlayer on these Au NPs and identify factors determining the structure/catalytic properties relationship. We show that the amount of exposed Au surface, the underlying surface structural disorder, and the interaction strength of the peptide with the Au surface all influence catalytic performance. A simplified computational prediction of catalytic performance is developed that can potentially serve as a screening tool for future studies. Our approach provides a platform for broadening the analysis of catalytic peptide-enabled metallic NP systems, potentially allowing for the development of rational design rules for property enhancement.« less

Physics in Screening Environments

NASA Astrophysics Data System (ADS)

Certik, Ondrej

In the current study, we investigated atoms in screening environments like plasmas. It is common practice to extract physical data, such as temperature and electron densities, from plasma experiments. We present results that address inherent computational difficulties that arise when the screening approach is extended to include the interaction between the atomic electrons. We show that there may arise an ambiguity in the interpretation of physical properties, such as temperature and charge density, from experimental data due to the opposing effects of electron-nucleus screening and electron-electron screening. The focus of the work, however, is on the resolution of inherent computational challenges that appear in the computation of two-particle matrix elements. Those enter already at the Hartree-Fock level. Furthermore, as examples of post Hartree-Fock calculations, we show second-order Green's function results and many body perturbation theory results of second order. A self-contained derivation of all necessary equations has been included. The accuracy of the implementation of the method is established by comparing standard unscreened results for various atoms and molecules against literature for Hartree-Fock as well as Green's function and many body perturbation theory. The main results of the thesis are presented in the chapter called Screened Results, where the behavior of several atomic systems depending on electron-electron and electron-nucleus Debye screening was studied. The computer code that we have developed has been made available for anybody to use. Finally, we present and discuss results obtained for screened interactions. We also examine thoroughly the computational details of the calculations and particular implementations of the method.

Research on Spectroscopy, Opacity, and Atmospheres

NASA Technical Reports Server (NTRS)

Kurucz, Robert L.

1999-01-01

A web site has been set up to make the calculations accessible; (i.e., cfakus.harvard.edu) This data can also be accessed by FTP. It has all of the atomic and diatomic molecular data, tables of distribution function opacities, grids of model atmospheres, colors, fluxes, etc, programs that are ready for distribution, and most of recent papers developed during this grant. Atlases and computed spectra will be added as they are completed. New atomic and molecular calculations will be added as they are completed. The atomic programs that had been running on a Cray at the San Diego Supercomputer Center can now run on the Vaxes and Alpha. The work started with Ni and Co because there were new laboratory analyses that included isotopic and hyperfine splitting. Those calculations are described in the appended abstract for the 6th Atomic Spectroscopy and oscillator Strengths meeting in Victoria last summer. A surprising finding is that quadrupole transitions have been grossly in error because mixing with higher levels has not been included. All levels up through n=9 for Fe I and II, the spectra for which the most information is available, are now included. After Fe I and Fe II, all other spectra are "easy". ATLAS12, the opacity sampling program for computing models with arbitrary abundances, has been put on the web server. A new distribution function opacity program for workstations that replaces the one used on the Cray at the San Diego Supercomputer Center has been written. Each set of abundances would take 100 Cray hours costing $100,000.

Surface morphology of ultrathin graphene oxide films obtained by the SAW atomization

NASA Astrophysics Data System (ADS)

Balachova, Olga V.; Balashov, Sergey M.; Costa, Carlos A. R.; Pavani Filho, A.

2015-08-01

Lately, graphene oxide (GO) thin films have attracted much attention: they can be used as humidity-sensitive coatings in the surface acoustic wave (SAW) sensors; being functionalized, they can be used in optoelectronic or biodevices, etc. In this research we study surface morphology of small-area thin GO films obtained on Si and quartz substrates by deposition of very small amounts of H2O-GO aerosols produced by the SAW atomizer. An important feature of this method is the ability to work with submicrovolumes of liquids during deposition that provides relatively good control over the film thickness and quality, in particular, minimization of the coffee ring effect. The obtained films were examined using AFM and electron microscopy. Image analysis showed that the films consist of GO sheets of different geometry and sizes and may form discrete or continuous coatings at the surface of the substrates with the minimum thickness of 1.0-1.8 nm which corresponds to one or two monolayers of GO. The thickness and quality of the deposited films depend on the parameters of the SAW atomization (number of atomized droplets, a volume of the initial droplet, etc.) and on sample surface preparation (activation in oxygen plasma). We discuss the structure of the obtained films, uniformity and the surface coverage as a function of parameters of the film deposition process and sample preparation. Qualitative analysis of adhesion of GO films is made by rinsing the samples in DI water and subsequent evaluation of morphology of the remained films.

Excitation of the hydrogen atom by fast-electron impact in the presence of a laser field

NASA Astrophysics Data System (ADS)

Bhattacharya, Manabesh; Sinha, C.; Sil, N. C.

1991-08-01

An approach has been developed to study the excitation of a ground-state H atom to the n=2 level under the simultaneous action of fast-electron impact and a monochromatic, linearly polarized, homogeneous laser beam. The laser frequency is assumed to be low (soft-photon limit) so that a stationary-state perturbation theory can be applied as is done in the adiabatic theory. An elegant method has been developed in the present work to construct the dressed excited-state wave functions of the H atom using first-order perturbation theory in the parabolic coordinate representation. By virtue of this method, the problem arising due to the degeneracy of the excited states of the H atom has been successfully overcome. The main advantage of the present approach is that the dressed wave function has been obtained in terms of a finite number of Laguerre polynomials instead of an infinite summation occurring in the usual perturbative treatment. The amplitude for direct excitation (without exchange) has been obtained in closed form. Numerical results for differential cross sections are presented for individual excitations to different Stark manifolds as well as for excitations to the n=2 level at high energies (100 and 200 eV) and for field directions both parallel and perpendicular to the incident electron momentum. Extension to a higher order of perturbation is also possible in the present approach for the construction of the dressed states, and the electron-exchange effect can also be taken into account without any further approximation.

Sparse and Adaptive Diffusion Dictionary (SADD) for recovering intra-voxel white matter structure.

PubMed

Aranda, Ramon; Ramirez-Manzanares, Alonso; Rivera, Mariano

2015-12-01

On the analysis of the Diffusion-Weighted Magnetic Resonance Images, multi-compartment models overcome the limitations of the well-known Diffusion Tensor model for fitting in vivo brain axonal orientations at voxels with fiber crossings, branching, kissing or bifurcations. Some successful multi-compartment methods are based on diffusion dictionaries. The diffusion dictionary-based methods assume that the observed Magnetic Resonance signal at each voxel is a linear combination of the fixed dictionary elements (dictionary atoms). The atoms are fixed along different orientations and diffusivity profiles. In this work, we present a sparse and adaptive diffusion dictionary method based on the Diffusion Basis Functions Model to estimate in vivo brain axonal fiber populations. Our proposal overcomes the following limitations of the diffusion dictionary-based methods: the limited angular resolution and the fixed shapes for the atom set. We propose to iteratively re-estimate the orientations and the diffusivity profile of the atoms independently at each voxel by using a simplified and easier-to-solve mathematical approach. As a result, we improve the fitting of the Diffusion-Weighted Magnetic Resonance signal. The advantages with respect to the former Diffusion Basis Functions method are demonstrated on the synthetic data-set used on the 2012 HARDI Reconstruction Challenge and in vivo human data. We demonstrate that improvements obtained in the intra-voxel fiber structure estimations benefit brain research allowing to obtain better tractography estimations. Hence, these improvements result in an accurate computation of the brain connectivity patterns. Copyright © 2015 Elsevier B.V. All rights reserved.

Dispersion-correcting potentials can significantly improve the bond dissociation enthalpies and noncovalent binding energies predicted by density-functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

DiLabio, Gino A., E-mail: Gino.DiLabio@nrc.ca; Department of Chemistry, University of British Columbia, Okanagan, 3333 University Way, Kelowna, British Columbia V1V 1V7; Koleini, Mohammad

2014-05-14

Dispersion-correcting potentials (DCPs) are atom-centered Gaussian functions that are applied in a manner that is similar to effective core potentials. Previous work on DCPs has focussed on their use as a simple means of improving the ability of conventional density-functional theory methods to predict the binding energies of noncovalently bonded molecular dimers. We show in this work that DCPs developed for use with the LC-ωPBE functional along with 6-31+G(2d,2p) basis sets are capable of simultaneously improving predicted noncovalent binding energies of van der Waals dimer complexes and covalent bond dissociation enthalpies in molecules. Specifically, the DCPs developed herein for themore » C, H, N, and O atoms provide binding energies for a set of 66 noncovalently bonded molecular dimers (the “S66” set) with a mean absolute error (MAE) of 0.21 kcal/mol, which represents an improvement of more than a factor of 10 over unadorned LC-ωPBE/6-31+G(2d,2p) and almost a factor of two improvement over LC-ωPBE/6-31+G(2d,2p) used in conjunction with the “D3” pairwise dispersion energy corrections. In addition, the DCPs reduce the MAE of calculated X-H and X-Y (X,Y = C, H, N, O) bond dissociation enthalpies for a set of 40 species from 3.2 kcal/mol obtained with unadorned LC-ωPBE/6-31+G(2d,2p) to 1.6 kcal/mol. Our findings demonstrate that broad improvements to the performance of DFT methods may be achievable through the use of DCPs.« less

Pseudopotential theoretical study of the alkali metals under arbitrary pressure: Density, bulk modulus, and shear moduli

NASA Astrophysics Data System (ADS)

Rasky, Daniel J.; Milstein, Frederick

1986-02-01

Milstein and Hill previously derived formulas for computing the bulk and shear moduli, κ, μ, and μ', at arbitrary pressures, for cubic crystals in which interatomic interaction energies are modeled by pairwise functions, and they carried out the moduli computations using the complete family of Morse functions. The present study extends their work to a pseudopotential description of atomic binding. Specifically: (1) General formulas are derived for determining these moduli under hydrostatic loading within the framework of a pseudopotential model. (2) A two-parameter pseudopotential model is used to describe atomic binding of the alkali metals, and the two parameters are determined from experimental data (the model employs the Heine-Abarenkov potential with the Taylor dielectric function). (3) For each alkali metal (Li, Na, K, Rb, and Cs), the model is used to compute the pressure-versus-volume behavior and, at zero pressure, the binding energy, the density, and the elastic moduli and their pressure derivatives; the theoretical behavior is found to be in excellent agreement with experiment. (4) Calculations are made of κ, μ, and μ' of the bcc alkali metals over wide ranges of hydrostatic compression and expansion. (5) The pseudopotential results are compared with those of arbitrary-central-force models (wherein κ-(2/3)μ=μ'+2P) and with the specific Morse-function results. The pressures, bulk moduli, and zero-pressure shear moduli (as determined for the Morse and pseudopotential models) are in excellent agreement, but important differences appear in the shear moduli under high compressions. The computations in the present paper are for the bcc metals; a subsequent paper will extend this work to include both the bcc and fcc structures, at compressions and expansions where elastic stability or lattice cohesion is, in practice, lost.

Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

NASA Astrophysics Data System (ADS)

Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

2017-03-01

The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

Dichlorocarbene-Functionalized Fluorographene: Synthesis and Reaction Mechanism.

PubMed

Lazar, Petr; Chua, Chun Kiang; Holá, Kateřina; Zbořil, Radek; Otyepka, Michal; Pumera, Martin

2015-08-01

Halogen functionalization of graphene is an important branch of graphene research as it provides opportunities to tailor the band gap and catalytic properties of graphene. Monovalent C-X bond obviates pitfalls of functionalization with atoms of groups 13, 15, and 16, which can introduce various poorly defined groups. Here, the preparation of functionalized graphene containing both fluorine and chlorine atoms is shown. The starting material, fluorographite, undergoes a reaction with dichlorocarbene to provide dichlorocarbene-functionalized fluorographene (DCC-FG). The material is characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, and high-resolution transmission electron microscopy with X-ray dispersive spectroscopy. It is found that the chlorine atoms in DCC-FG are distributed homogeneously over the entire area of the fluorographene sheet. Further density functional theory calculations show that the mechanism of dichlorocarbene attack on fluorographene sheet is a two-step process. Dichlorocarbene detaches fluorine atoms from fluorographene sheet and subsequently adds to the newly formed sp(2) carbons. Halogenated graphene consisting of two (or eventually three) types of halogen atoms is envisioned to find its way as new graphene materials with tailored properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Probing the dielectric response of the interfacial buffer layer in epitaxial graphene via optical spectroscopy

NASA Astrophysics Data System (ADS)

Hill, Heather M.; Rigosi, Albert F.; Chowdhury, Sugata; Yang, Yanfei; Nguyen, Nhan V.; Tavazza, Francesca; Elmquist, Randolph E.; Newell, David B.; Hight Walker, Angela R.

2017-11-01

Monolayer epitaxial graphene (EG) is a suitable candidate for a variety of electronic applications. One advantage of EG growth on the Si face of SiC is that it develops as a single crystal, as does the layer below, referred to as the interfacial buffer layer (IBL), whose properties include an electronic band gap. Although much research has been conducted to learn about the electrical properties of the IBL, not nearly as much work has been reported on the optical properties of the IBL. In this work, we combine measurements from Mueller matrix ellipsometry, differential reflectance contrast, atomic force microscopy, and Raman spectroscopy, as well as calculations from Kramers-Kronig analyses and density-functional theory, to determine the dielectric function of the IBL within the energy range of 1 eV to 8.5 eV.

Fine-structure excitation of Fe II and Fe III due to collisions with electrons

NASA Astrophysics Data System (ADS)

Wan, Yier; Qi, Yueying; Favreau, Connor; Loch, Stuart; Stancil, P.; Ballance, Connor; McLaughlin, Brendan

2018-06-01

Atomic data of iron peak elements are of great importance in astronomical observations. Among all the ionization stages of iron, Fe II and Fe III are of particular importance because of the high cosmic abundance, relatively low ionization potential and complex open d-shell atomic structure. Fe II and Fe III emission are observed from nearly all classes of astronomical objects over a wide spectral range from the infrared to the ultraviolet. To meaningfully interpret these spectra, astronomers have to employ highly complex modeling codes with reliable collision data to simulate the astrophysical observations. The major aim of this work is to provide reliable atomic data for diagnostics. We present new collision strengths and effective collisions for electron impact excitation of Fe II and Fe III for the forbidden transitions among the fine-structure levels of the ground terms. A very fine energy mesh is used for the collision strengths and the effective collision strengths are calculated over a wide range of electron temperatures of astrophysical importance (10-2000 K). The configuration interaction state wave functions are generated with a scaled Thomas-Fermi-Dirac-Amaldi (TFDA) potential, while the R-matrix plus intermediate coupling frame transformation (ICFT), Breit-Pauli R-matrix and Dirac R-matrix packages are used to obtain collision strengths. Influences of the different methods and configuration expansions on the collisional data are discussed. Comparison is made with earlier theoretical work and differences are found to occur at the low temperatures considered here.This work was funded by NASA grant NNX15AE47G.

About Essence of the Wave Function on Atomic Level and in Superconductors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nikulov, A. V.

The wave function was proposed for description of quantum phenomena on the atomic level. But now it is well known that quantum phenomena are observed not only on atomic level and the wave function is used for description of macroscopic quantum phenomena, such as superconductivity. The essence of the wave function on level elementary particles was and is the subject of heated argument among founders of quantum mechanics and other physicists. This essence seems more clear in superconductor. But impossibility of probabilistic interpretation of wave function in this case results to obvious contradiction of quantum principles with some fundamental principlesmore » of physics.« less

Photoionization of Atoms and Ions: Application of Time-Dependent Response Method within the Density Functional Theory.

DTIC Science & Technology

1987-10-13

AD-A±95 686 PHOTOIONIZATION OF ATOMS AND IONS: APPLICATION OF III TIME-DEPENDENT RESPONSE..(U) NAVAL RESEARCH LAB WASHINGTON DC U GUPTA ET AL. 13 OCT...on revere if ncemy and idmntify by block number) FIELD GROUP SUBGROUP Photoionization Density functional Atoms Time dependent 1 S. (Continue on...reverse if necenary and identify by block numnbw) The photoionization cross-section of several atoms (AT, Xe, Rn, Cs) and ions (Ne-like Ar, H-like and Li

Atomic Covalent Functionalization of Graphene

PubMed Central

Johns, James E.; Hersam, Mark C.

2012-01-01

Conspectus Although graphene’s physical structure is a single atom thick, two-dimensional, hexagonal crystal of sp2 bonded carbon, this simple description belies the myriad interesting and complex physical properties attributed to this fascinating material. Because of its unusual electronic structure and superlative properties, graphene serves as a leading candidate for many next generation technologies including high frequency electronics, broadband photodetectors, biological and gas sensors, and transparent conductive coatings. Despite this promise, researchers could apply graphene more routinely in real-world technologies if they could chemically adjust graphene’s electronic properties. For example, the covalent modification of graphene to create a band gap comparable to silicon (~1 eV) would enable its use in digital electronics, and larger band gaps would provide new opportunities for graphene-based photonics. Towards this end, researchers have focused considerable effort on the chemical functionalization of graphene. Due to its high thermodynamic stability and chemical inertness, new methods and techniques are required to create covalent bonds without promoting undesirable side reactions or irreversible damage to the underlying carbon lattice. In this Account, we review and discuss recent theoretical and experimental work studying covalent modifications to graphene using gas phase atomic radicals. Atomic radicals have sufficient energy to overcome the kinetic and thermodynamic barriers associated with covalent reactions on the basal plane of graphene but lack the energy required to break the C-C sigma bonds that would destroy the carbon lattice. Furthermore, because they are atomic species, radicals substantially reduce the likelihood of unwanted side reactions that confound other covalent chemistries. Overall, these methods based on atomic radicals show promise for the homogeneous functionalization of graphene and the production of new classes of two-dimensional materials with fundamentally different electronic and physical properties. Specifically, we focus on recent studies of the addition of atomic hydrogen, fluorine, and oxygen to the basal plane of graphene. In each of these reactions a high energy, activating step initiates the process, breaking the local π structure and distorting the surrounding lattice. Scanning tunneling microscopy experiments reveal that substrate mediated interactions often dominate when the initial binding event occurs. We then compare these substrate effects with the results of theoretical studies that typically assume a vacuum environment. As the surface coverage increases, clusters often form around the initial distortion, and the stoichiometric composition of the saturated end product depends strongly on both the substrate and reactant species. In addition to these chemical and structural observations, we review how covalent modification can extend the range of physical properties that are achievable in two-dimensional materials. PMID:23030800

STM study on the surface structures and defects of SnSe

NASA Astrophysics Data System (ADS)

Kim, Jungdae; Duvjir, Ganbat; Ly, Trinh Thi; Min, Taewon; Kim, Taehoon; Kim, Sang Hwa; Duong, Anh-Tuan; Rhim, S. H.; Cho, Sunglae; Lee, Jaekwang

Tin selenide (SnSe) is a IV-VI semiconductor with a band gap of 1.0 eV, and also one of layered chalcogenide materials (LCMs) where each layer is coupled by weak van der Waals interactions. SnSe has been widely studied due to its many potential applications that take advantage of its excellent thermoelectric, photovoltaic, and optoelectronic properties. However, experimental investigations into the microscopic structure of SnSe remain largely unexplored. The atomic and electronic structures of SnSe surfaces are studied by a home-built low temperature scanning tunneling microscope (STM). The cleaved surface of SnSe is comprised of covalently bonded Se and Sn atoms in zigzag patterns. However, rectangular periodicity was observed in the atomic images of SnSe surfaces for filled and empty state probing. Detailed atomic structures are analyzed by density functional theory (DFT) calculations, indicating that the bright extrusions of both filled and empty state images are mostly located at the positions of Sn atoms. We also report the origin of p-type behavior in SnSe by investigating three dominant intrinsic defects (Sn, Se, and Se-Sn-Se vacancies) using STM and DFT calculations. This work was supported by the National Research Foundation of Korea (NRF-2015R1D1A1A01057271, NRF-2009-0093818, and NRF-2014R1A4A1071686).

Introducing new reactivity descriptors: "Bond reactivity indices." Comparison of the new definitions and atomic reactivity indices.

PubMed

Sánchez-Márquez, Jesús

2016-11-21

A new methodology to obtain reactivity indices has been defined. This is based on reactivity functions such as the Fukui function or the dual descriptor and makes it possible to project the information of reactivity functions over molecular orbitals instead of the atoms of the molecule (atomic reactivity indices). The methodology focuses on the molecule's natural bond orbitals (bond reactivity indices) because these orbitals (with physical meaning) have the advantage of being very localized, allowing the reaction site of an electrophile or nucleophile to be determined within a very precise molecular region. This methodology gives a reactivity index for every Natural Bond Orbital (NBO), and we have verified that they have equivalent information to the reactivity functions. A representative set of molecules has been used to test the new definitions. Also, the bond reactivity index has been related with the atomic reactivity one, and complementary information has been obtained from the comparison. Finally, a new atomic reactivity index has been defined and compared with previous definitions.

Nonmetallic electronegativity equalization and point-dipole interaction model including exchange interactions for molecular dipole moments and polarizabilities.

PubMed

Smalø, Hans S; Astrand, Per-Olof; Jensen, Lasse

2009-07-28

The electronegativity equalization model (EEM) has been combined with a point-dipole interaction model to obtain a molecular mechanics model consisting of atomic charges, atomic dipole moments, and two-atom relay tensors to describe molecular dipole moments and molecular dipole-dipole polarizabilities. The EEM has been phrased as an atom-atom charge-transfer model allowing for a modification of the charge-transfer terms to avoid that the polarizability approaches infinity for two particles at infinite distance and for long chains. In the present work, these shortcomings have been resolved by adding an energy term for transporting charges through individual atoms. A Gaussian distribution is adopted for the atomic charge distributions, resulting in a damping of the electrostatic interactions at short distances. Assuming that an interatomic exchange term may be described as the overlap between two electronic charge distributions, the EEM has also been extended by a short-range exchange term. The result is a molecular mechanics model where the difference of charge transfer in insulating and metallic systems is modeled regarding the difference in bond length between different types of system. For example, the model is capable of modeling charge transfer in both alkanes and alkenes with alternating double bonds with the same set of carbon parameters only relying on the difference in bond length between carbon sigma- and pi-bonds. Analytical results have been obtained for the polarizability of a long linear chain. These results show that the model is capable of describing the polarizability scaling both linearly and nonlinearly with the size of the system. Similarly, a linear chain with an end atom with a high electronegativity has been analyzed analytically. The dipole moment of this model system can either be independent of the length or increase linearly with the length of the chain. In addition, the model has been parametrized for alkane and alkene chains with data from density functional theory calculations, where the polarizability behaves differently with the chain length. For the molecular dipole moment, the same two systems have been studied with an aldehyde end group. Both the molecular polarizability and the dipole moment are well described as a function of the chain length for both alkane and alkene chains demonstrating the power of the presented model.

Photoionization of rare gas clusters

NASA Astrophysics Data System (ADS)

Zhang, Huaizhen

This thesis concentrates on the study of photoionization of van der Waals clusters with different cluster sizes. The goal of the experimental investigation is to understand the electronic structure of van der Waals clusters and the electronic dynamics. These studies are fundamental to understand the interaction between UV-X rays and clusters. The experiments were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory. The experimental method employs angle-resolved time-of-flight photoelectron spectrometry, one of the most powerful methods for probing the electronic structure of atoms, molecules, clusters and solids. The van der Waals cluster photoionization studies are focused on probing the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. The angular distribution has been known to be a sensitive probe of the electronic structure in atoms and molecules. However, it has not been used in the case of van der Waals clusters. We carried out outer-valence levels, inner-valence levels and core-levels cluster photoionization experiments. Specifically, this work reports on the first quantitative measurements of the angular distribution parameters of rare gas clusters as a function of average cluster sizes. Our findings for xenon clusters is that the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the corresponding free atoms. However, distinct differences in the angular distribution point at cluster-size-dependent effects were found. For krypton clusters, in the photon energy range where atomic photoelectrons have a high angular anisotropy, our measurements show considerably more isotropic angular distributions for the cluster photoelectrons, especially right above the 3d and 4p thresholds. For the valence electrons, a surprising difference between the two spin-orbit components was found. For argon clusters, we found that the angular distribution parameter values of the two-spin-orbit components from Ar 2p clusters are slightly different. When comparing the beta values for Ar between atoms and clusters, we found different results between Ar 3s atoms and clusters, and between Ar 3p atoms and clusters. Argon cluster resonance from surface and bulk were also measured. Furthermore, the angular distribution parameters of Ar cluster photoelectrons and Ar atom photoelectrons in the 3s → np ionization region were obtained.

Effects of mode profile on tunneling and traversal of ultracold atoms through vacuum-induced potentials

NASA Astrophysics Data System (ADS)

Badshah, Fazal; Irfan, Muhammad; Qamar, Sajid; Qamar, Shahid

2016-04-01

We consider the resonant interaction of an ultracold two-level atom with an electromagnetic field inside a high-Q micromaser cavity. In particular, we study the tunneling and traversal of ultracold atoms through vacuum-induced potentials for secant hyperbolic square and sinusoidal cavity mode functions. The phase time which may be considered as an appropriate measure of the time required for the atoms to cross the cavity, significantly modifies with the change of cavity mode profile. For example, switching between the sub and superclassical behaviors in phase time can occur due to the mode function. Similarly, negative phase time appears for the transmission of the two-level atoms in both excited and ground states for secant hyperbolic square mode function which is in contrast to the mesa mode case.

General contraction of Gaussian basis sets. II - Atomic natural orbitals and the calculation of atomic and molecular properties

NASA Technical Reports Server (NTRS)

Almlof, Jan; Taylor, Peter R.

1990-01-01

A recently proposed scheme for using natural orbitals from atomic configuration interaction wave functions as a basis set for linear combination of atomic orbitals (LCAO) calculations is extended for the calculation of molecular properties. For one-electron properties like multipole moments, which are determined largely by the outermost regions of the molecular wave function, it is necessary to increase the flexibility of the basis in these regions. This is most easily done by uncontracting the outermost Gaussian primitives, and/or by adding diffuse primitives. A similar approach can be employed for the calculation of polarizabilities. Properties which are not dominated by the long-range part of the wave function, such as spectroscopic constants or electric field gradients at the nucleus, can generally be treated satisfactorily with the original atomic natural orbital sets.

Thulium-170 heat source

DOEpatents

Walter, Carl E.; Van Konynenburg, Richard; VanSant, James H.

1992-01-01

An isotopic heat source is formed using stacks of thin individual layers of a refractory isotopic fuel, preferably thulium oxide, alternating with layers of a low atomic weight diluent, preferably graphite. The graphite serves several functions: to act as a moderator during neutron irradiation, to minimize bremsstrahlung radiation, and to facilitate heat transfer. The fuel stacks are inserted into a heat block, which is encased in a sealed, insulated and shielded structural container. Heat pipes are inserted in the heat block and contain a working fluid. The heat pipe working fluid transfers heat from the heat block to a heat exchanger for power conversion. Single phase gas pressure controls the flow of the working fluid for maximum heat exchange and to provide passive cooling.

Semiclassical neutral atom as a reference system in density functional theory.

PubMed

Constantin, Lucian A; Fabiano, E; Laricchia, S; Della Sala, F

2011-05-06

We use the asymptotic expansions of the semiclassical neutral atom as a reference system in density functional theory to construct accurate generalized gradient approximations (GGAs) for the exchange-correlation and kinetic energies without any empiricism. These asymptotic functionals are among the most accurate GGAs for molecular systems, perform well for solid state, and overcome current GGA state of the art in frozen density embedding calculations. Our results also provide evidence for the conjointness conjecture between exchange and kinetic energies of atomic systems.

Secondary scattering on the intensity dependence of the capture velocity in a magneto-optical trap

NASA Astrophysics Data System (ADS)

Loos, M. R.; Massardo, S. B.; de S. Zanon, R. A.; de Oliveira, A. L.

2005-08-01

In this work, we consider a three-dimensional model to simulate the capture velocity behavior in a sample of cold-trapped sodium atoms as a function of the trapping laser intensity. We expand on previous work [V. S. Bagnato, L. G. Marcassa, S. G. Miranda, S. R. Muniz, and A. L. de Oliveira, Phys. Rev. A 62, 013404 (2000)] by calculating the capture velocity over a broad range of light intensities considering the secondary scattering in a magneto-optical trap. Our calculations are in a good agreement with recent measured values [S. R. Muniz , Phys. Rev. A 65, 015402 (2001)].

Metal Ion Reactions with Ozone and Atomic Oxygen.

DTIC Science & Technology

1979-04-05

EEEI 3 6 ....... Ii. MICROCOP Y RESOLUTION TEST CHART] / I. ~< 4 . A ’~ N ~ ~’ ~ ~. ~ ~ 4 ~ ~ ~. A ............................. ~ i, .1.’~~ AU 5 <j~1...aluminum-containing compound is ap- plied directly to a surface with high work function. Upon heating the sur- face, Al+ ions are evolved. In the...present experiments the compound was aluminum chloride, prepared by dissolving aluminum metal in hydrochloric *1 acid. The solution was then applied to the

Impact of Alloy Fluctuations on Radiative and Auger Recombination in InGaN Quantum Wells

NASA Astrophysics Data System (ADS)

Jones, Christina; Teng, Chu-Hsiang; Yan, Qimin; Ku, Pei-Cheng; Kioupakis, Emmanouil

Light-emitting diodes (LEDs) based on indium gallium nitride (InGaN) are important for efficient solid-state lighting (2014 Nobel Prize in Physics). Despite its many successes, InGaN suffers from issues that reduce the efficiency of devices at high power, such as the green gap and efficiency droop. The origin of the droop has been attributed to Auger recombination, mediated by carrier scattering due to phonons and alloy disorder. Additionally, InGaN exhibits atomic-scale composition fluctuations that localize carriers and may affect the efficiency. In this work, we study the effect of local composition fluctuations on the radiative recombination rate, Auger recombination rate, and efficiency of InGaN/GaN quantum wells. We apply k.p calculations to simulate band edges and wave functions of quantum wells with fluctuating alloy distributions based on atom probe tomography data, and we evaluate double and triple overlaps of electron and hole wave functions. We compare results for quantum wells with fluctuating alloy distributions to those with uniform alloy compositions and to published work. Our results demonstrate that alloy-composition fluctuations aggravate the efficiency-droop and green-gap problems and further reduce LED efficiency at high power. We acknowledge the NSF CAREER award DMR-1254314, the NSF Graduate Research Fellowship Program DGE-1256260, and the DOE NERSC facility (DE-AC02-05CH11231).

The role of plasma chemistry on functional silicon nitride film properties deposited at low-temperature by mixing two frequency powers using PECVD.

PubMed

Sahu, B B; Yin, Y Y; Tsutsumi, T; Hori, M; Han, Jeon G

2016-05-14

Control of the plasma densities and energies of the principal plasma species is crucial to induce modification of the plasma reactivity, chemistry, and film properties. This work presents a systematic and integrated approach to the low-temperature deposition of hydrogenated amorphous silicon nitride films looking into optimization and control of the plasma processes. Radiofrequency (RF) and ultrahigh frequency (UHF) power are combined to enhance significantly the nitrogen plasma and atomic-radical density to enforce their effect on film properties. This study presents an extensive investigation of the influence of combining radiofrequency (RF) and ultrahigh frequency (UHF) power as a power ratio (PR = RF : UHF), ranging from 4 : 0 to 0 : 4, on the compositional, structural, and optical properties of the synthesized films. The data reveal that DF power with a characteristic bi-Maxwellian electron energy distribution function (EEDF) is effectively useful for enhancing the ionization and dissociation of neutrals, which in turn helps in enabling high rate deposition with better film properties than that of SF operations. Utilizing DF PECVD, a wide-bandgap of ∼3.5 eV with strong photoluminescence features can be achieved only by using a high-density plasma and high nitrogen atom density at room temperature. The present work also proposes the suitability of the DF PECVD approach for industrial applications.

Kinetic model of the bichromatic dark trap for atoms

NASA Astrophysics Data System (ADS)

Krasnov, I. V.

2017-08-01

A kinetic model of atom confinement in a bichromatic dark trap (BDT) is developed with the goal of describing its dissipative properties. The operating principle of the deep BDT is based on using the combination of multiple bichromatic cosine-Gaussian optical beams (CGBs) for creating high-potential barriers, which is described in our previous work (Krasnov 2016 Laser Phys. 26 105501). In the indicated work, particle motion in the BDT is described in terms of classical trajectories. In the present study, particle motion is analyzed by means of the Wigner function (phase-space distribution function (DF)), which allows one to properly take into account the quantum fluctuations of optical forces. Besides, we consider an improved scheme of the BDT, where CGBs create, apart from plane potential barriers, a narrow cooling layer. We find an asymptotic solution of the Fokker-Planck equation for the DF and show that the DF of particles deeply trapped in a BDT with a cooling layer is the Tsallis distribution with the effective temperature, which can be considerably lower than in a BDT without a cooling layer. Moreover, it can be adjusted by slightly changing the CGBs’ radii. We also study the effect of particle escape from the trap due to the scattering of resonant photons and show that the particle lifetime in a BDT can exceed several tens of hours when it is limited by photon scattering.

Edge effects on the electronic properties of phosphorene nanoribbons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peng, Xihong, E-mail: xihong.peng@asu.edu; Copple, Andrew; Wei, Qun

2014-10-14

Two dimensional few-layer black phosphorus crystal structures have recently been fabricated and have demonstrated great potential in electronic applications. In this work, we employed first principles density functional theory calculations to study the edge and quantum confinement effects on the electronic properties of the phosphorene nanoribbons (PNR). Different edge functionalization groups, such as H, F, Cl, OH, O, S, and Se, in addition to a pristine case were studied for a series of ribbon widths up to 3.5 nm. It was found that the armchair-PNRs (APNRs) are semiconductors for all edge groups considered in this work. However, the zigzag-PNRs (ZPNRs)more » show either semiconductor or metallic behavior in dependence on their edge chemical species. Family 1 edges (i.e., H, F, Cl, OH) form saturated bonds with P atoms in the APNRs and ZPNRs, and the edge states keep far away from the band gap. However, Family 2 edges (pristine, O, S, Se) form weak unsaturated bonds with the p{sub z} orbital of the phosphorus atoms and bring edge states within the band gap of the ribbons. For the ZPNRs, the edge states of Family 2 are present around the Fermi level within the band gap, which close up the band gap of the ZPNRs. For the APNRs, these edge states are located at the bottom of the conduction band and result in a reduced band gap.« less

Atomic structure of self-organizing iridium induced nanowires on Ge(001)

NASA Astrophysics Data System (ADS)

Kabanov, N. S.; Heimbuch, R.; Zandvliet, H. J. W.; Saletsky, A. M.; Klavsyuk, A. L.

2017-05-01

The atomic structure of self-organizing iridium (Ir) induced nanowires on Ge(001) is studied by density functional theory (DFT) calculations and variable-temperature scanning tunneling microscopy. The Ir induced nanowires are aligned in a direction perpendicular to the Ge(001) substrate dimer rows, have a width of two atoms and are completely kink-less. Density functional theory calculations show that the Ir atoms prefer to dive into the Ge(001) substrate and push up the neighboring Ge substrate atoms. The nanowires are composed of Ge atoms and not Ir atoms as previously assumed. The regions in the vicinity of the nanowires are very dynamic, even at temperatures as low as 77 K. Time-resolved scanning tunneling microscopy measurements reveal that this dynamics is caused by buckled Ge substrate dimers that flip back and forth between their two buckled configurations.

Spin-Multiplet Components and Energy Splittings by Multistate Density Functional Theory.

PubMed

Grofe, Adam; Chen, Xin; Liu, Wenjian; Gao, Jiali

2017-10-05

Kohn-Sham density functional theory has been tremendously successful in chemistry and physics. Yet, it is unable to describe the energy degeneracy of spin-multiplet components with any approximate functional. This work features two contributions. (1) We present a multistate density functional theory (MSDFT) to represent spin-multiplet components and to determine multiplet energies. MSDFT is a hybrid approach, taking advantage of both wave function theory and density functional theory. Thus, the wave functions, electron densities and energy density-functionals for ground and excited states and for different components are treated on the same footing. The method is illustrated on valence excitations of atoms and molecules. (2) Importantly, a key result is that for cases in which the high-spin components can be determined separately by Kohn-Sham density functional theory, the transition density functional in MSDFT (which describes electronic coupling) can be defined rigorously. The numerical results may be explored to design and optimize transition density functionals for configuration coupling in multiconfigurational DFT.

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

Theoretical Investigations of the Electrochemical Reduction of CO on Single Metal Atoms Embedded in Graphene

DOE PAGES

Kirk, Charlotte; Chen, Leanne D.; Siahrostami, Samira; ...

2017-12-18

Single transition metal atoms embedded at single vacancies of graphene provide a unique paradigm for catalytic reactions. We present a density functional theory study of such systems for the electrochemical reduction of CO. Theoretical investigations of CO electrochemical reduction are particularly challenging in that electrochemical activation energies are a necessary descriptor of activity. We determined the electrochemical barriers for key proton–electron transfer steps using a state-of-the-art, fully explicit solvent model of the electrochemical interface. The accuracy of GGA-level functionals in describing these systems was also benchmarked against hybrid methods. We find the first proton transfer to form CHO from COmore » to be a critical step in C 1 product formation. On these single atom sites, the corresponding barrier scales more favorably with the CO binding energy than for 211 and 111 transition metal surfaces, in the direction of improved activity. Intermediates and transition states for the hydrogen evolution reaction were found to be less stable than those on transition metals, suggesting a higher selectivity for CO reduction. We present a rate volcano for the production of methane from CO. We identify promising candidates with high activity, stability, and selectivity for the reduction of CO. As a result, this work highlights the potential of these systems as improved electrocatalysts over pure transition metals for CO reduction.« less

A low temperature investigation of the gas-phase N(2D) + NO reaction. Towards a viable source of N(2D) atoms for kinetic studies in astrochemistry.

PubMed

Nuñez-Reyes, Dianailys; Hickson, Kevin M

2018-06-18

The gas-phase reaction of metastable atomic nitrogen N(2D) with nitric oxide has been investigated over the 296-50 K temperature range using a supersonic flow reactor. As N(2D) could not be produced photolytically in the present work, these excited state atoms were generated instead through the C(3P) + NO → N(2D) + CO reaction while C(3P) atoms were created in situ by the 266 nm pulsed laser photolysis of CBr4 precursor molecules. The kinetics of N(2D) atoms were followed on-resonance by vacuum ultraviolet laser induced fluorescence at 116.7 nm. The measured rate constants for the N(2D) + NO reaction are in excellent agreement with most of the earlier work at room temperature and represent the only available kinetic data for this process below 296 K. The rate constants are seen to increase slightly as the temperature falls to 100 K with a more substantial increase at even lower temperature; a finding which is not reproduced by theoretical work. The prospects for using this chemical source of N(2D) atoms in future studies of a wide range of N(2D) atom reactions are discussed.

H(D) → D(H) + Cu(111) collision system: Molecular dynamics study of surface temperature effects

PubMed Central

Vurdu, Can D.; Güvenç, Ziya B.

2011-01-01

All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London–Eyring–Polanyi–Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared and analyzed as a function of the surface temperatures. PMID:21528959

H(D) → D(H) + Cu(111) collision system: molecular dynamics study of surface temperature effects.

PubMed

Vurdu, Can D; Güvenç, Ziya B

2011-04-28

All the channels of the reaction dynamics of gas-phase H (or D) atoms with D (or H) atoms adsorbed onto a Cu(111) surface have been studied by quasiclassical constant energy molecular dynamics simulations. The surface is flexible and is prepared at different temperature values, such as 30 K, 94 K, and 160 K. The adsorbates were distributed randomly on the surface to create 0.18 ML, 0.28 ML, and 0.50 ML of coverages. The multi-layer slab is mimicked by a many-body embedded-atom potential energy function. The slab atoms can move according to the exerted external forces. Treating the slab atoms non-rigid has an important effect on the dynamics of the projectile atom and adsorbates. Significant energy transfer from the projectile atom to the surface lattice atoms takes place especially during the first impact that modifies significantly the details of the dynamics of the collisions. Effects of the different temperatures of the slab are investigated in this study. Interaction between the surface atoms and the adsorbates is modeled by a modified London-Eyring-Polanyi-Sato (LEPS) function. The LEPS parameters are determined by using the total energy values which were calculated by a density functional theory and a generalized gradient approximation for an exchange-correlation energy for many different orientations, and locations of one- and two-hydrogen atoms on the Cu(111) surface. The rms value of the fitting procedure is about 0.16 eV. Many different channels of the processes on the surface have been examined, such as inelastic reflection of the incident hydrogen, subsurface penetration of the incident projectile and adsorbates, sticking of the incident atom on the surface. In addition, hot-atom and Eley-Rideal direct processes are investigated. The hot-atom process is found to be more significant than the Eley-Rideal process. Furthermore, the rate of subsurface penetration is larger than the sticking rate on the surface. In addition, these results are compared and analyzed as a function of the surface temperatures.

Exchange and correlation in positronium-molecule scattering

NASA Astrophysics Data System (ADS)

Fabrikant, I. I.; Wilde, R. S.

2018-05-01

Exchange and correlations play a particularly important role in positronium (Ps) collisions with atoms and molecules, since the static potential for Ps interaction with a neutral system is zero. Theoretical description of both effects is a very challenging task. In the present work we use the free-electron-gas model to describe exchange and correlations in Ps collisions with molecules similar to the approach widely used in the theory of electron-molecule collisions. The results for exchange and correlation energies are presented as functions of the Fermi momentum of the electron gas and the Ps incident energy. Using the Thomas-Fermi model, these functions can be converted into exchange and correlation potentials for Ps interaction with molecules as functions of the distance between the projectile and the target.

Selectivity switch for nitrogen functionalization of styrene on Au(1 1 1)

NASA Astrophysics Data System (ADS)

Deng, Xingyi; Friend, Cynthia M.

2008-03-01

Functionalization of styrene to form N-containing hydrocarbons, e.g. 2-phenylaziridine, benzonitrile, and benzyl nitrile, is achieved by reaction with adsorbed NH a and N a on Au(1 1 1). Electron-induced decomposition of condensed NH 3 was used to produce NH a, N a and H a on Au(1 1 1) at 110 K. The selectivity of the reactions is strongly dependent on the relative concentrations of the surface species. The addition of NH to styrene results in the production of 2-phenylaziridine, whereas adsorbed N and H atoms lead to the formation of nitriles benzonitrile and benzyl nitrile and, respectively, ethylbenzene. This work clearly establishes the utility of Au for promoting functionalization of olefins with nitrogen.

AtomDB: Expanding an Accessible and Accurate Atomic Database for X-ray Astronomy

NASA Astrophysics Data System (ADS)

Smith, Randall

Since its inception in 2001, the AtomDB has become the standard repository of accurate and accessible atomic data for the X-ray astrophysics community, including laboratory astrophysicists, observers, and modelers. Modern calculations of collisional excitation rates now exist - and are in AtomDB - for all abundant ions in a hot plasma. AtomDB has expanded beyond providing just a collisional model, and now also contains photoionization data from XSTAR as well as a charge exchange model, amongst others. However, building and maintaining an accurate and complete database that can fully exploit the diagnostic potential of high-resolution X-ray spectra requires further work. The Hitomi results, sadly limited as they were, demonstrated the urgent need for the best possible wavelength and rate data, not merely for the strongest lines but for the diagnostic features that may have 1% or less of the flux of the strong lines. In particular, incorporation of weak but powerfully diagnostic satellite lines will be crucial to understanding the spectra expected from upcoming deep observations with Chandra and XMM-Newton, as well as the XARM and Athena satellites. Beyond incorporating this new data, a number of groups, both experimental and theoretical, have begun to produce data with errors and/or sensitivity estimates. We plan to use this to create statistically meaningful spectral errors on collisional plasmas, providing practical uncertainties together with model spectra. We propose to continue to (1) engage the X-ray astrophysics community regarding their issues and needs, notably by a critical comparison with other related databases and tools, (2) enhance AtomDB to incorporate a large number of satellite lines as well as updated wavelengths with error estimates, (3) continue to update the AtomDB with the latest calculations and laboratory measurements, in particular velocity-dependent charge exchange rates, and (4) enhance existing tools, and create new ones as needed to increase the functionality of, and access to, AtomDB.

Variational Monte Carlo Method with Dirichlet Boundary Conditions: Application to the Study of Confined Systems by Impenetrable Surfaces with Different Symmetries.

PubMed

Sarsa, Antonio; Le Sech, Claude

2011-09-13

Variational Monte Carlo method is a powerful tool to determine approximate wave functions of atoms, molecules, and solids up to relatively large systems. In the present work, we extend the variational Monte Carlo approach to study confined systems. Important properties of the atoms, such as the spatial distribution of the electronic charge, the energy levels, or the filling of electronic shells, are modified under confinement. An expression of the energy very similar to the estimator used for free systems is derived. This opens the possibility to study confined systems with little changes in the solution of the corresponding free systems. This is illustrated by the study of helium atom in its ground state (1)S and the first (3)S excited state confined by spherical, cylindrical, and plane impenetrable surfaces. The average interelectronic distances are also calculated. They decrease in general when the confinement is stronger; however, it is seen that they present a minimum for excited states under confinement by open surfaces (cylindrical, planes) around the radii values corresponding to ionization. The ground (2)S and the first (2)P and (2)D excited states of the lithium atom are calculated under spherical constraints for different confinement radii. A crossing between the (2)S and (2)P states is observed around rc = 3 atomic units, illustrating the modification of the atomic energy level under confinement. Finally the carbon atom is studied in the spherical symmetry by using both variational and diffusion Monte Carlo methods. It is shown that the hybridized state sp(3) becomes lower in energy than the ground state (3)P due to a modification and a mixing of the atomic orbitals s, p under strong confinement. This result suggests a model, at least of pedagogical interest, to interpret the basic properties of carbon atom in chemistry.

Surface reconstruction of InAs (001) depending on the pressure and temperature examined by density functional thermodynamics.

PubMed

Yeu, In Won; Park, Jaehong; Han, Gyuseung; Hwang, Cheol Seong; Choi, Jung-Hae

2017-09-06

A detailed understanding of the atomic configuration of the compound semiconductor surface, especially after reconstruction, is very important for the device fabrication and performance. While there have been numerous experimental studies using the scanning probe techniques, further theoretical studies on surface reconstruction are necessary to promote the clear understanding of the origins and development of such subtle surface structures. In this work, therefore, a pressure-temperature surface reconstruction diagram was constructed for the model case of the InAs (001) surface considering both the vibrational entropy and configurational entropy based on the density functional theory. Notably, the equilibrium fraction of various reconstructions was determined as a function of the pressure and temperature, not as a function of the chemical potential, which largely facilitated the direct comparison with the experiments. By taking into account the entropy effects, the coexistence of the multiple reconstructions and the fractional change of each reconstruction by the thermodynamic condition were predicted and were in agreement with the previous experimental observations. This work provides the community with a useful framework for such type of theoretical studies.

General contraction of Gaussian basis sets. Part 2: Atomic natural orbitals and the calculation of atomic and molecular properties

NASA Technical Reports Server (NTRS)

Almloef, Jan; Taylor, Peter R.

1989-01-01

A recently proposed scheme for using natural orbitals from atomic configuration interaction (CI) wave functions as a basis set for linear combination of atomic orbitals (LCAO) calculations is extended for the calculation of molecular properties. For one-electron properties like multipole moments, which are determined largely by the outermost regions of the molecular wave function, it is necessary to increase the flexibility of the basis in these regions. This is most easily done by uncontracting the outmost Gaussian primitives, and/or by adding diffuse primitives. A similar approach can be employed for the calculation of polarizabilities. Properties which are not dominated by the long-range part of the wave function, such as spectroscopic constants or electric field gradients at the nucleus, can generally be treated satisfactorily with the original atomic natural orbital (ANO) sets.

Density functional theory calculations establish the experimental evidence of the DX center atomic structure in CdTe.

PubMed

Lany, Stephan; Wolf, Herbert; Wichert, Thomas

2004-06-04

The In DX center and the DX-like configuration of the Cd host atom in CdTe are investigated using density functional theory. The simultaneous calculation of the atomic structure and the electric field gradient (EFG) allows one to correlate the theoretically predicted structure of the DX center with an experimental observable, namely, the EFG obtained from radioactive 111In/111Cd probe atoms in In doped CdTe. In this way, the experimental identification of the DX center structure is established.

Pathways for tailoring the magnetostructural behavior of FeRh-based systems

NASA Astrophysics Data System (ADS)

Barua, Radhika

2014-03-01

The prediction of phase transition temperatures in functional materials provides dual benefits of supplying insight into fundamental drivers underlying the phase transition, as well as enabling new and improved technological applications that employ the material. In this work, studies focused on understanding the magnetostructural phase transition of FeRh as a function of elemental substitution, provides guidance for tailoring phase transitions in this compound, with possible extensions to other intermetallic-based magnetostructural compounds. Clear trends in the magnetostructural temperatures (Tt) of alloys of composition Fe(Rh1-xMx) or (Fe1-xMx) Rh (M = 3 d, 4 d or 5 d transition metals), as reported in literature since 1961, were identified and confirmed as a function of the valence band electron concentration ((s + d) electrons/atom) of the system. It is observed that substitution of 3 dor 4 delements (x <= 6.5 at%) into B2-ordered FeRh compounds causes Ttto increase to a maximum around a critical valence band electron concentration (ev *) of 8.50 electrons/atom and then decrease. Substitution of 5 delements echoes this trend but with an overall increase in Ttand a shift in ev * to 8.52 electrons/atom. For ev>8.65 electrons/atom, FeRh-based alloys cease to adopt the B2-ordered crystallographic structure in favor of the chemically disordered A1-type structure or the ordered L10-type structure. This phenomenological model has been confirmed through synthesis and characterization of FeRh alloys with Cu, Ni and Au additions. The success of this model in confirming existing data trends in chemically-substituted FeRh and predicting new composition-transition temperature correlations emphasizes the strong interplay between the electronic spin configuration, the electronic band structure, and crystal lattice of this system. Further these results provide pathways for tailoring the magnetostructural behavior and the associated functional response of FeRh-based systems for potential technological applications. Research was performed under the auspices of the U.S. Department of Energy (Contract No. DE-SC0005250).

Locality of correlation in density functional theory.

PubMed

Burke, Kieron; Cancio, Antonio; Gould, Tim; Pittalis, Stefano

2016-08-07

The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that EC → -AC ZlnZ + BCZ as Z → ∞, where Z is the atomic number, AC is known, and we estimate BC to be about 37 mhartree. The local density approximation yields AC exactly, but a very incorrect value for BC, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with BC a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.

Ab-Initio Molecular Dynamics Simulation of Graphene Sheet

NASA Astrophysics Data System (ADS)

Kolev, S.; Balchev, I.; Cvetkov, K.; Tinchev, S.; Milenov, T.

2017-01-01

The study of graphene is important because it is a promising material for a variety of applications in the electronic industry. In the present work, the properties of а 2D periodic graphene sheet are studied with the use of ab initio molecular dynamics. DFT in the generalized gradient approximation is used in order to carry out the dynamical simulations. The PBE functional and DZVP-MOLOPT basis set are implemented in the CP2K/Quickstep package. A periodic box, consisting of 288 carbon atoms is chosen for the simulations. After geometry optimization it has dimensions 2964 x 2964 x 1500 pm and form angles of 90, 90, 60 degrees. The dynamical simulation is run for 1 ps in the NPT ensemble, at temperature T = 298.15 K. The radial distribution function shows a first peak at 142 pm, marking the bond length between carbon atoms. The density of states for the periodic systems is simulated as occupied orbitals represent the valence band and unoccupied ones the conduction band. The calculated bandgap, as expected is close to 0 eV.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Jianwei; Yang, Zenghui; Peng, Haowei

The uniform electron gas and the hydrogen atom play fundamental roles in condensed matter physics and quantum chemistry. The former has an infinite number of electrons uniformly distributed over the neutralizing positively charged background, and the latter only one electron bound to the proton. The uniform electron gas was used to derive the local spin density approximation to the exchange-correlation functional that undergirds the development of the Kohn-Sham density functional theory. We show here that the ground-state exchange-correlation energies of the hydrogen atom and many other 1- and 2-electron systems are modeled surprisingly well by a different local spin densitymore » approximation (LSDA0). LSDA0 is constructed to satisfy exact constraints but agrees surprisingly well with the exact results for a uniform two-electron density in a finite, curved three-dimensional space. We also apply LSDA0 to excited or noded 1-electron densities, where it works less well. Furthermore, we show that the localization of the exact exchange hole for a 1- or 2-electron ground state can be measured by the ratio of the exact exchange energy to its optimal lower bound.« less

Properties of atomic pairs produced in the collision of Bose-Einstein condensates

NASA Astrophysics Data System (ADS)

Ziń, Paweł; Wasak, Tomasz

2018-04-01

During a collision of Bose-Einstein condensates correlated pairs of atoms are emitted. The scattered massive particles, in analogy to photon pairs in quantum optics, might be used in the violation of Bell's inequalities, demonstration of Einstein-Podolsky-Rosen correlations, or sub-shot-noise atomic interferometry. Usually, a theoretical description of the collision relies either on stochastic numerical methods or on analytical treatments involving various approximations. Here, we investigate elastic scattering of atoms from colliding elongated Bose-Einstein condensates within the Bogoliubov method, carefully controlling performed approximations at every stage of the analysis. We derive expressions for the one- and two-particle correlation functions. The obtained formulas, which relate the correlation functions to the condensate wave function, are convenient for numerical calculations. We employ the variational approach for condensate wave functions to obtain analytical expressions for the correlation functions, whose properties we analyze in detail. We also present a useful semiclassical model of the process and compare its results with the quantum one. The results are relevant for recent experiments with excited helium atoms, as well as for planned experiments aimed at investigating the nonclassicality of the system.

Two-probe STM experiments at the atomic level.

PubMed

Kolmer, Marek; Olszowski, Piotr; Zuzak, Rafal; Godlewski, Szymon; Joachim, Christian; Szymonski, Marek

2017-11-08

Direct characterization of planar atomic or molecular scale devices and circuits on a supporting surface by multi-probe measurements requires unprecedented stability of single atom contacts and manipulation of scanning probes over large, nanometer scale area with atomic precision. In this work, we describe the full methodology behind atomically defined two-probe scanning tunneling microscopy (STM) experiments performed on a model system: dangling bond dimer wire supported on a hydrogenated germanium (0 0 1) surface. We show that 70 nm long atomic wire can be simultaneously approached by two independent STM scanners with exact probe to probe distance reaching down to 30 nm. This allows direct wire characterization by two-probe I-V characteristics at distances below 50 nm. Our technical results presented in this work open a new area for multi-probe research, which can be now performed with precision so far accessible only by single-probe scanning probe microscopy (SPM) experiments.

Optical perturbation of atoms in weak localization

NASA Astrophysics Data System (ADS)

Yedjour, A.

2018-01-01

We determine the microscopic transport parameters that are necessary to describe the diffusion process of the atomic gas in optical speckle. We use the self-consistent theory to calculate the self-energy of the atomic gas. We compute the spectral function numerically by an average over disorder realizations in terms of the Greens function. We focus mainly on the behaviour of the energy distribution of the atoms to estimate a correction to the mobility edge. Our results show that the energy distribution of the atoms locates the mobility edge position under the disorder amplitude. This behaviour changes for each disorder parameter. We conclude that the disorder amplitude potential induced modification of the energy distribution of the atoms that plays a major role for the prediction of the mobility edge.

Collisional redistribution of radiation. II - The effects of degeneracy on the equations of motion for the density matrix. III - The equation of motion for the correlation function and the scattered spectrum

NASA Technical Reports Server (NTRS)

Burnett, K.; Cooper, J.

1980-01-01

The effect of correlations between an absorber atom and perturbers in the binary-collision approximation are applied to degenerate atomic systems. A generalized absorption profile which specifies the final state of the atom after an absorption event is related to the total intensities of Rayleigh scattering and fluorescence from the atom. It is suggested that additional dynamical information to that obtainable from ordinary absorption experiments is required in order to describe redistributed atomic radiation. The scattering of monochromatic radiation by a degenerate atom is computed in a binary-collision approximation; an equation of motion is derived for the correlation function which is valid outside the quantum-regression regime. Solutions are given for the weak-field conditions in terms of generalized absorption and emission profiles that depend on the indices of the atomic multipoles.

Quantum conductance oscillation in linear monatomic silicon chains

NASA Astrophysics Data System (ADS)

Liu, Fu-Ti; Cheng, Yan; Yang, Fu-Bin; Chen, Xiang-Rong

2014-02-01

The conductance of linear silicon atomic chains with n=1-8 atoms sandwiched between Au electrodes is investigated by using the density functional theory combined with non-equilibrium Green's function. The results show that the conductance oscillates with a period of two atoms as the number of atoms in the chain is varied. We optimize the geometric structure of nanoscale junctions in different distances, and obtain that the average bond-length of silicon atoms in each chain at equilibrium positions is 2.15±0.03 Å. The oscillation of average Si-Si bond-length can explain the conductance oscillation from the geometric structure of atomic chains. We calculate the transmission spectrum of the chains in the equilibrium positions, and explain the conductance oscillation from the electronic structure. The transport channel is mainly contributed by px and py orbital electrons of silicon atoms. The even-odd oscillation is robust under external voltage up to 1.2 V.

Dynamical Evolution of Properties for Atom and Field in the Process of Two-Photon Absorption and Emission Between Atomic Levels

NASA Astrophysics Data System (ADS)

Wang, Jian-ming; Xu, Xue-xiang

2018-04-01

Using dressed state method, we cleverly solve the dynamics of atom-field interaction in the process of two-photon absorption and emission between atomic levels. Here we suppose that the atom is initially in the ground state and the optical field is initially in Fock state, coherent state or thermal state, respectively. The properties of the atom, including the population in excited state and ground state, the atom inversion, and the properties for optical field, including the photon number distribution, the mean photon number, the second-order correlation function and the Wigner function, are discussed in detail. We derive their analytical expressions and then make numerical analysis for them. In contrast with Jaynes-Cummings model, some similar results, such as quantum Rabi oscillation, revival and collapse, are also exhibit in our considered model. Besides, some novel nonclassical states are generated.

Las Palmeras Molecular Dynamics: A flexible and modular molecular dynamics code

NASA Astrophysics Data System (ADS)

Davis, Sergio; Loyola, Claudia; González, Felipe; Peralta, Joaquín

2010-12-01

Las Palmeras Molecular Dynamics (LPMD) is a highly modular and extensible molecular dynamics (MD) code using interatomic potential functions. LPMD is able to perform equilibrium MD simulations of bulk crystalline solids, amorphous solids and liquids, as well as non-equilibrium MD (NEMD) simulations such as shock wave propagation, projectile impacts, cluster collisions, shearing, deformation under load, heat conduction, heterogeneous melting, among others, which involve unusual MD features like non-moving atoms and walls, unstoppable atoms with constant-velocity, and external forces like electric fields. LPMD is written in C++ as a compromise between efficiency and clarity of design, and its architecture is based on separate components or plug-ins, implemented as modules which are loaded on demand at runtime. The advantage of this architecture is the ability to completely link together the desired components involved in the simulation in different ways at runtime, using a user-friendly control file language which describes the simulation work-flow. As an added bonus, the plug-in API (Application Programming Interface) makes it possible to use the LPMD components to analyze data coming from other simulation packages, convert between input file formats, apply different transformations to saved MD atomic trajectories, and visualize dynamical processes either in real-time or as a post-processing step. Individual components, such as a new potential function, a new integrator, a new file format, new properties to calculate, new real-time visualizers, and even a new algorithm for handling neighbor lists can be easily coded, compiled and tested within LPMD by virtue of its object-oriented API, without the need to modify the rest of the code. LPMD includes already several pair potential functions such as Lennard-Jones, Morse, Buckingham, MCY and the harmonic potential, as well as embedded-atom model (EAM) functions such as the Sutton-Chen and Gupta potentials. Integrators to choose include Euler (if only for demonstration purposes), Verlet and Velocity Verlet, Leapfrog and Beeman, among others. Electrostatic forces are treated as another potential function, by default using the plug-in implementing the Ewald summation method. Program summaryProgram title: LPMD Catalogue identifier: AEHG_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEHG_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: GNU General Public License version 3 No. of lines in distributed program, including test data, etc.: 509 490 No. of bytes in distributed program, including test data, etc.: 6 814 754 Distribution format: tar.gz Programming language: C++ Computer: 32-bit and 64-bit workstation Operating system: UNIX RAM: Minimum 1024 bytes Classification: 7.7 External routines: zlib, OpenGL Nature of problem: Study of Statistical Mechanics and Thermodynamics of condensed matter systems, as well as kinetics of non-equilibrium processes in the same systems. Solution method: Equilibrium and non-equilibrium molecular dynamics method, Monte Carlo methods. Restrictions: Rigid molecules are not supported. Polarizable atoms and chemical bonds (proteins) either. Unusual features: The program is able to change the temperature of the simulation cell, the pressure, cut regions of the cell, color the atoms by properties, even during the simulation. It is also possible to fix the positions and/or velocity of groups of atoms. Visualization of atoms and some physical properties during the simulation. Additional comments: The program does not only perform molecular dynamics and Monte Carlo simulations, it is also able to filter and manipulate atomic configurations, read and write different file formats, convert between them, evaluate different structural and dynamical properties. Running time: 50 seconds on a 1000-step simulation of 4000 argon atoms, running on a single 2.67 GHz Intel processor.

Local structural and chemical ordering of nanosized Pt3±δCo probed by multiple-scattering x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Greco, Giorgia; Witkowska, Agnieszka; Principi, Emiliano; Minicucci, Marco; di Cicco, Andrea

2011-04-01

This work reports a detailed investigation of the local structure and chemical disorder of a Pt3±δCo thin film and Pt3±δCo nanoparticles. We have used a combination of techniques including x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and high-resolution transmission electron microscopy (TEM). High-quality XAS spectra at the Co K edge and Pt L3 edge have been analyzed using double-edge multiple-scattering data analysis. Structural extended x-ray absorption fine structure (EXAFS) refinements have been performed accounting for the reduction of the coordination numbers and degeneracy of three-atom configurations, resulting from the measured size distribution and stoichiometry. The important effect of chemical ordering on pair and three-atom configurations has been studied using computer simulations based on a simple model accounting for substitutional disorder, defined by an order parameter s. It has been found that individual EXAFS signals related to the minority species (Co) are extremely sensitive to substitutional disorder so their intensities, especially those of the collinear three-atom configurations, can be used as a measure of the ordering level. The thin film has been found to be chemically disordered (s⩽0.4), in agreement with previous estimates. The Pt3±δCo nanoalloy has been found to be partially ordered (s=0.6±0.1) while the local structure around Co atoms is characterized by a higher level of structural disorder as compared to the bulk-like thin film. The robust approach for nanomaterial characterization used in this work combining different techniques can, in principle, be applied for structural refinements of any binary nanocrystalline functional system.

Alkali (Li, K and Na) and alkali-earth (Be, Ca and Mg) adatoms on SiC single layer

NASA Astrophysics Data System (ADS)

Baierle, Rogério J.; Rupp, Caroline J.; Anversa, Jonas

2018-03-01

First-principles calculations within the density functional theory (DFT) have been addressed to study the energetic stability, and electronic properties of alkali and alkali-earth atoms adsorbed on a silicon carbide (SiC) single layer. We observe that all atoms are most stable (higher binding energy) on the top of a Si atom, which moves out of the plane (in the opposite direction to the adsorbed atom). Alkali atoms adsorbed give raise to two spin unpaired electronic levels inside the band gap leading the SiC single layer to exhibit n-type semiconductor properties. For alkaline atoms adsorbed there is a deep occupied spin paired electronic level inside the band gap. These finding suggest that the adsorption of alkaline and alkali-earth atoms on SiC layer is a powerful feature to functionalize two dimensional SiC structures, which can be used to produce new electronic, magnetic and optical devices as well for hydrogen and oxygen evolution reaction (HER and OER, respectively). Furthermore, we observe that the adsorption of H2 is ruled by dispersive forces (van der Waals interactions) while the O2 molecule is strongly adsorbed on the functionalized system.

Prediction of conformationally dependent atomic multipole moments in carbohydrates

PubMed Central

Cardamone, Salvatore

2015-01-01

The conformational flexibility of carbohydrates is challenging within the field of computational chemistry. This flexibility causes the electron density to change, which leads to fluctuating atomic multipole moments. Quantum Chemical Topology (QCT) allows for the partitioning of an “atom in a molecule,” thus localizing electron density to finite atomic domains, which permits the unambiguous evaluation of atomic multipole moments. By selecting an ensemble of physically realistic conformers of a chemical system, one evaluates the various multipole moments at defined points in configuration space. The subsequent implementation of the machine learning method kriging delivers the evaluation of an analytical function, which smoothly interpolates between these points. This allows for the prediction of atomic multipole moments at new points in conformational space, not trained for but within prediction range. In this work, we demonstrate that the carbohydrates erythrose and threose are amenable to the above methodology. We investigate how kriging models respond when the training ensemble incorporating multiple energy minima and their environment in conformational space. Additionally, we evaluate the gains in predictive capacity of our models as the size of the training ensemble increases. We believe this approach to be entirely novel within the field of carbohydrates. For a modest training set size of 600, more than 90% of the external test configurations have an error in the total (predicted) electrostatic energy (relative to ab initio) of maximum 1 kJ mol−1 for open chains and just over 90% an error of maximum 4 kJ mol−1 for rings. © 2015 Wiley Periodicals, Inc. PMID:26547500

Prediction of conformationally dependent atomic multipole moments in carbohydrates.

PubMed

Cardamone, Salvatore; Popelier, Paul L A

2015-12-15

The conformational flexibility of carbohydrates is challenging within the field of computational chemistry. This flexibility causes the electron density to change, which leads to fluctuating atomic multipole moments. Quantum Chemical Topology (QCT) allows for the partitioning of an "atom in a molecule," thus localizing electron density to finite atomic domains, which permits the unambiguous evaluation of atomic multipole moments. By selecting an ensemble of physically realistic conformers of a chemical system, one evaluates the various multipole moments at defined points in configuration space. The subsequent implementation of the machine learning method kriging delivers the evaluation of an analytical function, which smoothly interpolates between these points. This allows for the prediction of atomic multipole moments at new points in conformational space, not trained for but within prediction range. In this work, we demonstrate that the carbohydrates erythrose and threose are amenable to the above methodology. We investigate how kriging models respond when the training ensemble incorporating multiple energy minima and their environment in conformational space. Additionally, we evaluate the gains in predictive capacity of our models as the size of the training ensemble increases. We believe this approach to be entirely novel within the field of carbohydrates. For a modest training set size of 600, more than 90% of the external test configurations have an error in the total (predicted) electrostatic energy (relative to ab initio) of maximum 1 kJ mol(-1) for open chains and just over 90% an error of maximum 4 kJ mol(-1) for rings. © 2015 Wiley Periodicals, Inc.

MATCH: An Atom- Typing Toolset for Molecular Mechanics Force Fields

PubMed Central

Yesselman, Joseph D.; Price, Daniel J.; Knight, Jennifer L.; Brooks, Charles L.

2011-01-01

We introduce a toolset of program libraries collectively titled MATCH (Multipurpose Atom-Typer for CHARMM) for the automated assignment of atom types and force field parameters for molecular mechanics simulation of organic molecules. The toolset includes utilities for the conversion from multiple chemical structure file formats into a molecular graph. A general chemical pattern-matching engine using this graph has been implemented whereby assignment of molecular mechanics atom types, charges and force field parameters is achieved by comparison against a customizable list of chemical fragments. While initially designed to complement the CHARMM simulation package and force fields by generating the necessary input topology and atom-type data files, MATCH can be expanded to any force field and program, and has core functionality that makes it extendable to other applications such as fragment-based property prediction. In the present work, we demonstrate the accurate construction of atomic parameters of molecules within each force field included in CHARMM36 through exhaustive cross validation studies illustrating that bond increment rules derived from one force field can be transferred to another. In addition, using leave-one-out substitution it is shown that it is also possible to substitute missing intra and intermolecular parameters with ones included in a force field to complete the parameterization of novel molecules. Finally, to demonstrate the robustness of MATCH and the coverage of chemical space offered by the recent CHARMM CGENFF force field (Vanommeslaeghe, et al., JCC., 2010, 31, 671–690), one million molecules from the PubChem database of small molecules are typed, parameterized and minimized. PMID:22042689

Information-theoretic measures of hydrogen-like ions in weakly coupled Debye plasmas

NASA Astrophysics Data System (ADS)

Zan, Li Rong; Jiao, Li Guang; Ma, Jia; Ho, Yew Kam

2017-12-01

Recent development of information theory provides researchers an alternative and useful tool to quantitatively investigate the variation of the electronic structure when atoms interact with the external environment. In this work, we make systematic studies on the information-theoretic measures for hydrogen-like ions immersed in weakly coupled plasmas modeled by Debye-Hückel potential. Shannon entropy, Fisher information, and Fisher-Shannon complexity in both position and momentum spaces are quantified in high accuracy for the hydrogen atom in a large number of stationary states. The plasma screening effect on embedded atoms can significantly affect the electronic density distributions, in both conjugate spaces, and it is quantified by the variation of information quantities. It is shown that the composite quantities (the Shannon entropy sum and the Fisher information product in combined spaces and Fisher-Shannon complexity in individual space) give a more comprehensive description of the atomic structure information than single ones. The nodes of wave functions play a significant role in the changes of composite information quantities caused by plasmas. With the continuously increasing screening strength, all composite quantities in circular states increase monotonously, while in higher-lying excited states where nodal structures exist, they first decrease to a minimum and then increase rapidly before the bound state approaches the continuum limit. The minimum represents the most reduction of uncertainty properties of the atom in plasmas. The lower bounds for the uncertainty product of the system based on composite information quantities are discussed. Our research presents a comprehensive survey in the investigation of information-theoretic measures for simple atoms embedded in Debye model plasmas.

Symmetrical metallic and magnetic edge states of nanoribbon from semiconductive monolayer PtS2

NASA Astrophysics Data System (ADS)

Liu, Shan; Zhu, Heyu; Liu, Ziran; Zhou, Guanghui

2018-03-01

Transition metal dichalcogenides (TMD) MoS2 or graphene could be designed to metallic nanoribbons, which always have only one edge show metallic properties due to symmetric protection. In present work, a nanoribbon with two parallel metallic and magnetic edges was designed from a noble TMD PtS2 by employing first-principles calculations based on density functional theory (DFT). Edge energy, bonding charge density, band structure, density of states (DOS) and simulated scanning tunneling microscopy (STM) of four possible edge states of monolayer semiconductive PtS2 were systematically studied. Detailed calculations show that only Pt-terminated edge state among four edge states was relatively stable, metallic and magnetic. Those metallic and magnetic properties mainly contributed from 5d orbits of Pt atoms located at edges. What's more, two of those central symmetric edges coexist in one zigzag nanoribbon, which providing two atomic metallic wires thus may have promising application for the realization of quantum effects, such as Aharanov-Bohm effect and atomic power transmission lines in single nanoribbon.

Ab initio calculations for industrial materials engineering: successes and challenges.

PubMed

Wimmer, Erich; Najafabadi, Reza; Young, George A; Ballard, Jake D; Angeliu, Thomas M; Vollmer, James; Chambers, James J; Niimi, Hiroaki; Shaw, Judy B; Freeman, Clive; Christensen, Mikael; Wolf, Walter; Saxe, Paul

2010-09-29

Computational materials science based on ab initio calculations has become an important partner to experiment. This is demonstrated here for the effect of impurities and alloying elements on the strength of a Zr twist grain boundary, the dissociative adsorption and diffusion of iodine on a zirconium surface, the diffusion of oxygen atoms in a Ni twist grain boundary and in bulk Ni, and the dependence of the work function of a TiN-HfO(2) junction on the replacement of N by O atoms. In all of these cases, computations provide atomic-scale understanding as well as quantitative materials property data of value to industrial research and development. There are two key challenges in applying ab initio calculations, namely a higher accuracy in the electronic energy and the efficient exploration of large parts of the configurational space. While progress in these areas is fueled by advances in computer hardware, innovative theoretical concepts combined with systematic large-scale computations will be needed to realize the full potential of ab initio calculations for industrial applications.

Tunable microwave metasurfaces for high-performance operations: dispersion compensation and dynamical switch

PubMed Central

Xu, He-Xiu; Tang, Shiwei; Ma, Shaojie; Luo, Weijie; Cai, Tong; Sun, Shulin; He, Qiong; Zhou, Lei

2016-01-01

Controlling the phase distributions on metasurfaces leads to fascinating effects such as anomalous light refraction/reflection, flat-lens focusing, and optics-vortex generation. However, metasurfaces realized so far largely reply on passive resonant meta-atoms, whose intrinsic dispersions limit such passive meta-devices’ performances at frequencies other than the target one. Here, based on tunable meta-atoms with varactor diodes involved, we establish a scheme to resolve these issues for microwave metasurfaces, in which the dispersive response of each meta-atom is precisely controlled by an external voltage imparted on the diode. We experimentally demonstrate two effects utilizing our scheme. First, we show that a tunable gradient metasurface exhibits single-mode high-efficiency operation within a wide frequency band, while its passive counterpart only works at a single frequency but exhibits deteriorated performances at other frequencies. Second, we demonstrate that the functionality of our metasurface can be dynamically switched from a specular reflector to a surface-wave convertor. Our approach paves the road to achieve dispersion-corrected and switchable manipulations of electromagnetic waves. PMID:27901088

C6 Coefficients and Dipole Polarizabilities for All Atoms and Many Ions in Rows 1-6 of the Periodic Table.

PubMed

Gould, Tim; Bučko, Tomáš

2016-08-09

Using time-dependent density functional theory (TDDFT) with exchange kernels, we calculate and test imaginary frequency-dependent dipole polarizabilities for all atoms and many ions in rows 1-6 of the periodic table. These are then integrated over frequency to produce C6 coefficients. Results are presented under different models: straight TDDFT calculations using two different kernels; "benchmark" TDDFT calculations corrected by more accurate quantum chemical and experimental data; and "benchmark" TDDFT with frozen orbital anions. Parametrizations are presented for 411+ atoms and ions, allowing results to be easily used by other researchers. A curious relationship, C6,XY ∝ [αX(0)αY(0)](0.73), is found between C6 coefficients and static polarizabilities α(0). The relationship C6,XY = 2C6,XC6,Y/[(αX/αY)C6,Y + (αY/αX)C6,X] is tested and found to work well (<5% errors) in ∼80% of the cases, but can break down badly (>30% errors) in a small fraction of cases.

Circular Dichroism Control of Tungsten Diselenide (WSe2) Atomic Layers with Plasmonic Metamolecules.

PubMed

Lin, Hsiang-Ting; Chang, Chiao-Yun; Cheng, Pi-Ju; Li, Ming-Yang; Cheng, Chia-Chin; Chang, Shu-Wei; Li, Lance L J; Chu, Chih-Wei; Wei, Pei-Kuen; Shih, Min-Hsiung

2018-05-09

Controlling circularly polarized (CP) states of light is critical to the development of functional devices for key and emerging applications such as display technology and quantum communication, and the compact circular polarization-tunable photon source is one critical element to realize the applications in the chip-scale integrated system. The atomic layers of transition metal dichalcogenides (TMDCs) exhibit intrinsic CP emissions and are potential chiroptical materials for ultrathin CP photon sources. In this work, we demonstrated CP photon sources of TMDCs with device thicknesses approximately 50 nm. CP photoluminescence from the atomic layers of tungsten diselenide (WSe 2 ) was precisely controlled with chiral metamolecules (MMs), and the optical chirality of WSe 2 was enhanced more than 4 times by integrating with the MMs. Both the enhanced and reversed circular dichroisms had been achieved. Through integrations of the novel gain material and plasmonic structure which are both low-dimensional, a compact device capable of efficiently manipulating emissions of CP photon was realized. These ultrathin devices are suitable for important applications such as the optical information technology and chip-scale biosensing.

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hsiu-Wen; Fanelli, Victor R.; Reiche, Helmut M.

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO{sub 2}more » measurements. The new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO{sub 2} sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H{sub 2} and natural gas uptake/storage.« less

Pressure/temperature fluid cell apparatus for the neutron powder diffractometer instrument: Probing atomic structure in situ

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Hsiu -Wen; Fanelli, Victor R.; Reiche, Helmut M.

This contribution describes a new local structure compatible gas/liquid cell apparatus for probing disordered materials at high pressures and variable temperatures in the Neutron Powder Diffraction instrument at the Lujan Neutron Scattering Center, Los Alamos National Laboratory. The new sample environment offers choices for sample canister thickness and canister material type. Finite element modeling is utilized to establish maximum allowable working pressures of 414 MPa at 15 K and 121 MPa at 600 K. High quality atomic pair distribution function data extraction and modeling have been demonstrated for a calibration standard (Si powder) and for supercritical and subcritical CO 2measurements.more » As a result, the new sample environment was designed to specifically target experimental studies of the local atomic structures involved in geologic CO 2 sequestration, but will be equally applicable to a wide variety of energy applications, including sorption of fluids on nano/meso-porous solids, clathrate hydrate formation, catalysis, carbon capture, and H 2 and natural gas uptake/storage.« less

Tunable microwave metasurfaces for high-performance operations: dispersion compensation and dynamical switch.

PubMed

Xu, He-Xiu; Tang, Shiwei; Ma, Shaojie; Luo, Weijie; Cai, Tong; Sun, Shulin; He, Qiong; Zhou, Lei

2016-11-30

Controlling the phase distributions on metasurfaces leads to fascinating effects such as anomalous light refraction/reflection, flat-lens focusing, and optics-vortex generation. However, metasurfaces realized so far largely reply on passive resonant meta-atoms, whose intrinsic dispersions limit such passive meta-devices' performances at frequencies other than the target one. Here, based on tunable meta-atoms with varactor diodes involved, we establish a scheme to resolve these issues for microwave metasurfaces, in which the dispersive response of each meta-atom is precisely controlled by an external voltage imparted on the diode. We experimentally demonstrate two effects utilizing our scheme. First, we show that a tunable gradient metasurface exhibits single-mode high-efficiency operation within a wide frequency band, while its passive counterpart only works at a single frequency but exhibits deteriorated performances at other frequencies. Second, we demonstrate that the functionality of our metasurface can be dynamically switched from a specular reflector to a surface-wave convertor. Our approach paves the road to achieve dispersion-corrected and switchable manipulations of electromagnetic waves.

Comparing residue clusters from thermophilic and mesophilic enzymes reveals adaptive mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sammond, Deanne W.; Kastelowitz, Noah; Himmel, Michael E.

Understanding how proteins adapt to function at high temperatures is important for deciphering the energetics that dictate protein stability and folding. While multiple principles important for thermostability have been identified, we lack a unified understanding of how internal protein structural and chemical environment determine qualitative or quantitative impact of evolutionary mutations. In this work we compare equivalent clusters of spatially neighboring residues between paired thermophilic and mesophilic homologues to evaluate adaptations under the selective pressure of high temperature. We find the residue clusters in thermophilic enzymes generally display improved atomic packing compared to mesophilic enzymes, in agreement with previous research.more » Unlike residue clusters from mesophilic enzymes, however, thermophilic residue clusters do not have significant cavities. In addition, anchor residues found in many clusters are highly conserved with respect to atomic packing between both thermophilic and mesophilic enzymes. As a result, the improvements in atomic packing observed in thermophilic homologues are not derived from these anchor residues but from neighboring positions, which may serve to expand optimized protein core regions.« less