First principles study of structural stability, electronic structure and mechanical properties of ReN and TcN

NASA Astrophysics Data System (ADS)

Rajeswarapalanichamy, R.; Kavitha, M.; Sudha Priyanga, G.; Iyakutti, K.

2015-03-01

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.

Failure of the Hume-Rothery stabilization mechanism in the Ag(5)Li(8) gamma-brass studied by first-principles FLAPW electronic structure calculations.

PubMed

Mizutani, U; Asahi, R; Sato, H; Noritake, T; Takeuchi, T

2008-07-09

The first-principles FLAPW (full potential linearized augmented plane wave) electronic structure calculations were performed for the Ag(5)Li(8) gamma-brass, which contains 52 atoms in a unit cell and has been known for many years as one of the most structurally complex alloy phases. The calculations were also made for its neighboring phase AgLi B2 compound. The main objective in the present work is to examine if the Ag(5)Li(8) gamma-brass is stabilized at the particular electrons per atom ratio e/a = 21/13 in the same way as some other gamma-brasses like Cu(5)Zn(8) and Cu(9)Al(4), obeying the Hume-Rothery electron concentration rule. For this purpose, the e/a value for the Ag(5)Li(8) gamma-brass as well as the AgLi B2 compound was first determined by means of the FLAPW-Fourier method we have developed. It proved that both the gamma-brass and the B2 compound possess an e/a value equal to unity instead of 21/13. Moreover, we could demonstrate why the Hume-Rothery stabilization mechanism fails for the Ag(5)Li(8) gamma-brass and proposed a new stability mechanism, in which the unique gamma-brass structure can effectively lower the band-structure energy by forming heavily populated bonding states near the bottom of the Ag-4d band.

Anomalous thermodynamic properties and phase stability of δ -Pu1 -xMx (M =Ga andAl ) alloys from first-principles calculations

NASA Astrophysics Data System (ADS)

Li, Chun-Mei; Yang, Rui; Johansson, Börje; Vitos, Levente

2016-12-01

The composition-dependent crystal structure, volume, elastic constants, and electronic structure of δ -Pu1 -xMx (M =Ga and Al,0 ≤x ≤0.1 ) alloys are systematically studied by using first-principles EMTO-CPA calculations. It is shown that the fcc and L 12 structures co-exist in the alloys with x ≤0.04 whereas for x >0.04 , the L 12 structure is more and more preferable and around x =0.1 , it tends to be stabilized alone. The evaluated V ˜x of the L 12 structure, being negative deviation from Vegard's law, turns out to be in good agreement with the experimental result. For x ≤0.04 , the estimated E , G , ν , and Θ of both the fcc and L 12 structures are in line with the measured data, whereas when x >0.04 , only those of the L 12 structure are close to the experimental results. The electronic hybridization between Pu and M atoms is dominated by Pu for the s ,d , and f states but M for the p state. The strong interactions between Pu and M atoms in the same site of the L 12 structure should be responsible for its relative stability in the alloys with x >0.04 . The electron-phonon coupling further decreases the phase stability of δ -Pu1 -xMx with increasing x .

Solvation effect on isomer stability and electronic structures of protonated serotonin

NASA Astrophysics Data System (ADS)

Omidyan, Reza; Amanollahi, Zohreh; Azimi, Gholamhassan

2017-07-01

Microsolvation effect on geometry and transition energies of protonated serotonin has been investigated by MP2 and CC2 quantum chemical methods. Also, conductor-like screening model, implemented recently in the MP2 and ADC(2) methods, was examined to address the bulk water environment's effect on the isomer stability and electronic transition energies of protonated serotonin. It has been predicted that the dipole moment of gas phase isomers plays the main role on the isomer stabilization in water solution and electronic transition shifts. Also, both red- and blue-shift effects have been predicted to take place on electronic transition energies, upon hydration.

Self aligning electron beam gun having enhanced thermal and mechanical stability

DOEpatents

Scarpetti, Jr., Raymond D.; Parkison, Clarence D.; Switzer, Vernon A.; Lee, Young J.; Sawyer, William C.

1995-01-01

A compact, high power electron gun having enhanced thermal and mechanical stability which incorporates a mechanically coupled, self aligning structure for the anode and cathode. The enhanced stability, and reduced need for realignment of the cathode to the anode and downstream optics during operation are achieved by use of a common support structure for the cathode and anode which requires no adjustment screws or spacers. The electron gun of the present invention also incorporates a modular design for the cathode, in which the electron emitter, its support structure, and the hardware required to attach the emitter assembly to the rest of the gun are a single element. This modular design makes replacement of the emitter simpler and requires no realignment after a new emitter has been installed. Compactness and a reduction in the possibility of high voltage breakdown are achieved by shielding the "triple point" where the electrode, insulator, and vacuum meet. The use of electric discharge machining (EDM) for fabricating the emitter allows for the accurate machining of the emitter into intricate shapes without encountering the normal stresses developed by standard emitter fabrication techniques.

Density functional studies of the defect-induced electronic structure modifications in bilayer boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-05-01

The van der Waals interaction-corrected density functional theory is used in this study to investigate the formation, energetic stability, and inter-layer cohesion in bilayer hexagonal boronitrene. The effect of inter-layer separation on the electronic structure is systematically investigated. The formation and energetic stability of intrinsic defects are also investigated at the equilibrium inter-layer separation. It is found that nonstoichiometric defects, and their complexes, that induce excess nitrogen or excess boron, in each case, are relatively more stable in the atmosphere that corresponds to the excess atomic species. The modifications of the electronic structure due to formation of complexes are also investigated. It is shown that van der Waals density functional theory gives an improved description of the cohesive properties but not the electronic structure in bilayer boronitrene compared to other functionals. We identify energetically favourable topological defects that retain the energy gap in the electronic structure, and discuss their implications for band gap engineering in low-n layer boronitrene insulators. The relative strengths and weaknesses of the functionals in predicting the properties of bilayer boronitrene are also discussed.

Temperature effect on the structural stabilities and electronic properties of X22H28 (X=C, Si and Ge) nanocrystals: A first-principles study

NASA Astrophysics Data System (ADS)

Deng, Xiao-Lin; Zhao, Yu-Jun; Wang, Ya-Ting; Liao, Ji-Hai; Yang, Xiao-Bao

2016-12-01

Based on ab initio molecular dynamic simulations, we have theoretically investigated the structural stabilities and electronic properties of X22H28 (X=C, Si, and Ge) nanocrystals, as a function of temperature with consideration of vibrational entropy effects. To compare the relative stabilities of X22H28 isomers, the vibration free energies are obtained according to the calculated phonon spectrum, where the typical modes are shown to be dominant to the structural stabilities. In addition, there is a significant gap reduction as the temperature increases from 0 K to 300 K, where the decrements are 0.2 /0.5 /0.6eV for C/Si/Ge nanocrystals, respectively. The dependence of energy gap on the variance of bond length is also analyzed according to the corresponding atomic attributions to the HOMO and LUMO levels.

The electronic structure of Au25 clusters: between discrete and continuous

NASA Astrophysics Data System (ADS)

Katsiev, Khabiboulakh; Lozova, Nataliya; Wang, Lu; Sai Krishna, Katla; Li, Ruipeng; Mei, Wai-Ning; Skrabalak, Sara E.; Kumar, Challa S. S. R.; Losovyj, Yaroslav

2016-08-01

Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies.Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies. Electronic supplementary information (ESI) available: Experimental details including chemicals, sample preparation, and characterization methods. Computation techniques, SV-AUC, GIWAXS, XPS, UPS, MALDI-TOF, ESI data of Au25 clusters. See DOI: 10.1039/c6nr02374f

Structural electronic and mechanical properties of YM2 (M=Mn, Fe, Co) laves phase compounds: First principle calculations analyzed with datamining approach

NASA Astrophysics Data System (ADS)

Saidi, F.; Sebaa, N.; Mahmoudi, A.; Aourag, H.; Merad, G.; Dergal, M.

2018-06-01

We performed first-principle calculations to investigate structural, phase stability, electronic and mechanical properties for the Laves phases YM2 (M = Mn, Fe, Co) with C15, C14 and C36 structures. We used the density functional theory within the framework of both pseudo-potentials and plane wave basis using VASP (Vienna Ab Initio Software Package). The calculated equilibrium structural parameters are in accordance with available theoretical values. Mechanical properties were calculated, discussed, and analyzed with data mining approach in terms of structure stability. The results reveal that YCo2 is harder than YFe2 and YMn2.

Mossbauer spectroscopic studies in ferroboron

NASA Astrophysics Data System (ADS)

Yadav, Ravi Kumar; Govindaraj, R.; Amarendra, G.

2017-05-01

Mossbauer spectroscopic studies have been carried out in a detailed manner on ferroboron in order to understand the local structure and magnetic properties of the system. Evolution of the local structure and magnetic properties of the amorphous and crystalline phases and their thermal stability have been addressed in a detailed manner in this study. Role of bonding between Fe 4s and/or 4p electrons with valence electrons of boron (2s,2p) in influencing the stability and magnetic properties of Fe-B system is elucidated.

Structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds

NASA Astrophysics Data System (ADS)

Liu, Yangzhen; Xing, Jiandong; Fu, Hanguang; Li, Yefei; Sun, Liang; Lv, Zheng

2017-08-01

The properties of sulfides are important in the design of new iron-steel materials. In this study, first-principles calculations were used to estimate the structural stability, mechanical properties, electronic structures and thermal properties of XS (X = Ti, V, Cr, Mn, Fe, Co, Ni) binary compounds. The results reveal that these XS binary compounds are thermodynamically stable, because their formation enthalpy is negative. The elastic constants, Cij, and moduli (B, G, E) were investigated using stress-strain and Voigt-Reuss-Hill approximation, respectively. The sulfide anisotropy was discussed from an anisotropic index and three-dimensional surface contours. The electronic structures reveal that the bonding characteristics of the XS compounds are a mixture of metallic and covalent bonds. Using a quasi-harmonic Debye approximation, the heat capacity at constant pressure and constant volume was estimated. NiS possesses the largest CP and CV of the sulfides.

Atomic and electronic structure of a copper/graphene interface as prepared and 1.5 years after

NASA Astrophysics Data System (ADS)

Boukhvalov, D. W.; Bazylewski, P. F.; Kukharenko, A. I.; Zhidkov, I. S.; Ponosov, Yu. S.; Kurmaev, E. Z.; Cholakh, S. O.; Lee, Y. H.; Chang, G. S.

2017-12-01

We report the results of X-ray spectroscopy and Raman measurements of as-prepared graphene on a high quality copper surface and the same materials after 1.5 years under different conditions (ambient and low humidity). The obtained results were compared with density functional theory calculations of the formation energies and electronic structures of various structural defects in graphene/Cu interfaces. For evaluation of the stability of the carbon cover, we propose a two-step model. The first step is oxidation of the graphene, and the second is perforation of graphene with the removal of carbon atoms as part of the carbon dioxide molecule. Results of the modeling and experimental measurements provide evidence that graphene grown on high-quality copper substrate becomes robust and stable in time (1.5 years). However, the stability of this interface depends on the quality of the graphene and the number of native defects in the graphene and substrate. The effect of the presence of a metallic substrate with defects on the stability and electronic structure of graphene is also discussed

Effects of electron irradiation on LDPE/MWCNT composites

NASA Astrophysics Data System (ADS)

Yang, Jianqun; Li, Xingji; Liu, Chaoming; Rui, Erming; Wang, Liqin

2015-12-01

In this study, mutiwalled carbon nanotubes (MWCNTs) were incorporated into low density polyethylene (LDPE) in different concentrations (2%, 4% and 8%) using a melt blending process. Structural, thermal stability and tensile property of the unirradiated/irradiated LDPE/MWCNT composites by 110 keV electrons were investigated by means of scanning electron microscopy (SEM), small angle X-ray scattering (SAXS), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, thermogravimetric analysis (TGA) and uniaxial tensile techniques. Experimental results show that the addition of MWCNTs obviously increases the ultimate tensile strength of LDPE and decreases the elongation at break, which is attributed to the homogeneous distribution of the MWCNTs in LDPE and intense interaction between MWCNTs and LDPE matrix. Also, the electron irradiation further increases the ultimate tensile strength of LDPE/MWCNT composites, which can be ascribed to the more intense interaction between MWCNTs and LDPE matrix, and the formation of crosslinking sites in LDPE matrix induced by the electron irradiation. The addition of MWCNTs significantly enhances thermal stability of the LDPE due to the hindering effect and the scavenging free radicals, while the electron irradiation decreases thermal stability of the LDPE/MWCNT composites since the structure of the MWCNTs and LDPE matrix damages.

Specimen charging in X-ray absorption spectroscopy: correction of total electron yield data from stabilized zirconia in the energy range 250-915 eV.

PubMed

Vlachos, Dimitrios; Craven, Alan J; McComb, David W

2005-03-01

The effects of specimen charging on X-ray absorption spectroscopy using total electron yield have been investigated using powder samples of zirconia stabilized by a range of oxides. The stabilized zirconia powder was mixed with graphite to minimize the charging but significant modifications of the intensities of features in the X-ray absorption near-edge fine structure (XANES) still occurred. The time dependence of the charging was measured experimentally using a time scan, and an algorithm was developed to use this measured time dependence to correct the effects of the charging. The algorithm assumes that the system approaches the equilibrium state by an exponential decay. The corrected XANES show improved agreement with the electron energy-loss near-edge fine structure obtained from the same samples.

Systematic research on Ag2X (X = O, S, Se, Te) as visible and near-infrared light driven photocatalysts and effects of their electronic structures

NASA Astrophysics Data System (ADS)

Jiang, Wei; Wu, Zhaomei; Zhu, Yingming; Tian, Wen; Liang, Bin

2018-01-01

Four silver chalcogen compounds, Ag2O, Ag2S, Ag2Se and Ag2Te, can be utilized as visible-light-driven photocatalysts. In this research, the electronic structures of these compounds were analyzed by simulation and experiments to systematically reveal the relationship between photocatalytic performance and energetic structure. All four chalcogenides exhibited interesting photocatalytic activities under ultraviolet, visible and near-infrared light. However, their photocatalytic performances and stability significantly depended on the band gap width, and the valence band and conduct band position, which was determined by their composition. Increasing the X atomic number from O to Te resulted in the upward movement of the valence band top and the conduct band bottom, which resulted in narrower band gaps, a wider absorption spectrum, a weaker photo-oxidization capacity, a higher recombination probability of hole and electron pairs, lower quantum efficiency, and worse stability. Among them, Ag2O has the highest photocatalytic performance and stability due to its widest band gap and lowest position of VB and CB. The combined action of photogenerated holes and different radicals, depending on the different electronic structures, including anion ozone radical, hydroxide radical, and superoxide radical, was observed and understood. The results of experimental observations and simulations of the four silver chalcogen compounds suggested that a proper electronic structure is necessary to obtain a balance between photocatalytic performance and absorbable light region in the development of new photocatalysts.

Structural stability of coplanar 1T-2H superlattice MoS2 under high energy electron beam.

PubMed

Reshmi, S; Akshaya, M V; Satpati, Biswarup; Basu, Palash Kumar; Bhattacharjee, K

2018-05-18

Coplanar heterojunctions composed of van der Waals layered materials with different structural polymorphs have drawn immense interest recently due to low contact resistance and high carrier injection rate owing to low Schottky barrier height. Present research has largely focused on efficient exfoliation of these layered materials and their restacking to achieve better performances. We present here a microwave assisted easy, fast and efficient route to induce high concentration of metallic 1T phase in the original 2H matrix of exfoliated MoS 2 layers and thus facilitating the formation of a 1T-2H coplanar superlattice phase. High resolution transmission electron microscopy (HRTEM) investigations reveal formation of highly crystalline 1T-2H hybridized structure with sharp interface and disclose the evidence of surface ripplocations within the same exfoliated layer of MoS 2 . In this work, the structural stability of 1T-2H superlattice phase during HRTEM measurements under an electron beam of energy 300 keV is reported. This structural stability could be either associated to the change in electronic configuration due to induction of the restacked hybridized phase with 1T- and 2H-regions or to the formation of the surface ripplocations. Surface ripplocations can act as an additional source of scattering centers to the electron beam and also it is possible that a pulse train of propagating ripplocations can sweep out the defects via interaction from specific areas of MoS 2 sheets.

Structural stability of coplanar 1T-2H superlattice MoS2 under high energy electron beam

NASA Astrophysics Data System (ADS)

Reshmi, S.; Akshaya, M. V.; Satpati, Biswarup; Basu, Palash Kumar; Bhattacharjee, K.

2018-05-01

Coplanar heterojunctions composed of van der Waals layered materials with different structural polymorphs have drawn immense interest recently due to low contact resistance and high carrier injection rate owing to low Schottky barrier height. Present research has largely focused on efficient exfoliation of these layered materials and their restacking to achieve better performances. We present here a microwave assisted easy, fast and efficient route to induce high concentration of metallic 1T phase in the original 2H matrix of exfoliated MoS2 layers and thus facilitating the formation of a 1T-2H coplanar superlattice phase. High resolution transmission electron microscopy (HRTEM) investigations reveal formation of highly crystalline 1T-2H hybridized structure with sharp interface and disclose the evidence of surface ripplocations within the same exfoliated layer of MoS2. In this work, the structural stability of 1T-2H superlattice phase during HRTEM measurements under an electron beam of energy 300 keV is reported. This structural stability could be either associated to the change in electronic configuration due to induction of the restacked hybridized phase with 1T- and 2H-regions or to the formation of the surface ripplocations. Surface ripplocations can act as an additional source of scattering centers to the electron beam and also it is possible that a pulse train of propagating ripplocations can sweep out the defects via interaction from specific areas of MoS2 sheets.

First-principles calculations of stability, electronic and elastic properties of the precipitates present in 7055 aluminum alloy

NASA Astrophysics Data System (ADS)

Huang, Cheng; Shao, Hongbang; Ma, Yunlong; Huang, Yuanchun; Xiao, Zhengbing

2018-04-01

The structural stability, electronic structures and elastic properties of the strengthening precipitates, namely Al3Zr, MgZn2, Al2CuMg and Al2Cu, present in 7055 aluminum alloy were investigated by the first-principles calculations based on density functional theory (DFT). The optimized structural parameters are in good agreement with literature values available. It is found that Al3Zr has the strongest alloying ability and structural stability, while for MgZn2, its structural stability is the worst. The calculated electronic results indicate that covalent bonding is the dominant cohesion of Al3Zr, whereas the fractional ionic interactions coexisting with metallic bonding are found in MgZn2, Al2CuMg and Al2Cu. The elastic constants Cij of these precipitates were calculated, and the bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and universal elastic anisotropy were derived. It is suggested that MgZn2 is ductile, whereas Al3Zr, Al2CuMg and Al2Cu are brittle, and the elastic anisotropies of them increase in the following sequence: Al3Zr

Stabilization of non-productive conformations underpins rapid electron transfer to electron-transferring flavoprotein.

PubMed

Toogood, Helen S; van Thiel, Adam; Scrutton, Nigel S; Leys, David

2005-08-26

Crystal structures of protein complexes with electron-transferring flavoprotein (ETF) have revealed a dual protein-protein interface with one region serving as anchor while the ETF FAD domain samples available space within the complex. We show that mutation of the conserved Glu-165beta in human ETF leads to drastically modulated rates of interprotein electron transfer with both medium chain acyl-CoA dehydrogenase and dimethylglycine dehydrogenase. The crystal structure of free E165betaA ETF is essentially identical to that of wild-type ETF, but the crystal structure of the E165betaA ETF.medium chain acyl-CoA dehydrogenase complex reveals clear electron density for the FAD domain in a position optimal for fast interprotein electron transfer. Based on our observations, we present a dynamic multistate model for conformational sampling that for the wild-type ETF. medium chain acyl-CoA dehydrogenase complex involves random motion between three distinct positions for the ETF FAD domain. ETF Glu-165beta plays a key role in stabilizing positions incompatible with fast interprotein electron transfer, thus ensuring high rates of complex dissociation.

Stabilization of Small Boron Cage by Transition Metal Encapsulation

NASA Astrophysics Data System (ADS)

Zhang, Lijun; Lv, Jian; Wang, Yanchao; Ma, Yanming

2015-03-01

The discovery of chemically stable fullerene-like structures formed by elements other than carbon has been long-standing desired. On this aspect significant efforts have centered around boron, only one electron deficient compared with carbon. However, during the past decade a large number of experimental and theoretical studies have established that small boron clusters are either planar/quasi-planar or forming double-ring tubular structures. Until recently, two all-boron fullerenes have been independently discovered: B38 proposed by our structure searching calculations and B40 observed in a joint experimental and theoretical study. Here we extend our work to the even smaller boron clusters and propose an effective routine to stabilize them by transition metal encapsulation. By combining swarm-intelligence structure searching and first-principles calculations, we have systematically investigated the energy landscapes of transition-metal-doped MB24 clusters (M = Ti, Zr, Hf, Cr, Mo, W, Fe, Ru and Os). Two stable symmetric endohedral boron cages, MoB24 and WB24 are identified. The stability of them can be rationalized in terms of their unique 18-electron closed-shell electronic structures. Funded by Recruitment Program of Global Experts of China and China Postdoctoral Science Foundation.

Structural and electronic properties of CdSe/ZnS and ZnS/CdSe core/shell nanowires via first principles study

NASA Astrophysics Data System (ADS)

Rehman, Shafiq Ur; Li, H. M.; Ding, Z. J.

2018-05-01

First principles calculations have been performed to predict the structural stability and electronic structures of hydrogen passivated wurtzite CdSe/ZnS and ZnS/CdSe core/shell nanowires (CSNWs) in the [0001] direction. The calculated binding energy shows that ZnS/CdSe CSNWs are more stable than CdSe/ZnS CSNWs and the stability of ZnS/CdSe CSNWs increases with increasing the thickness of ZnS shell. The modulated electronic band gap demonstrates an increase when the size of both CSNWs is reduced, as a result of the quantum confinement effect. The core-to-shell chemical composition of atoms shows that a strong composition effect also exists in these CSNWs, which in turn affects their electronic properties. Our simulated results show that the photoemission spectra of the CSNWs can be significantly improved by tuning the energy gap of CSNWs.

The effect of relativity on stability of Copernicium phases, their electronic structure and mechanical properties

NASA Astrophysics Data System (ADS)

Čenčariková, Hana; Legut, Dominik

2018-05-01

The phase stability of the various crystalline structures of the super-heavy element Copernicium was determined based on the first-principles calculations with different levels of the relativistic effects. We utilized the Darwin term, mass-velocity, and spin-orbit interaction with the single electron framework of the density functional theory while treating the exchange and correlation effects using local density approximations. It is found that the spin-orbit coupling is the key component to stabilize the body-centered cubic (bcc) structure over the hexagonal closed packed (hcp) structure, which is in accord with Sol. Stat. Comm. 152 (2012) 530, but in contrast to Atta-Fynn and Ray (2015) [11], Gaston et al. (2007) [10], Papaconstantopoulos (2015) [9]. It seems that the main role here is the correct description of the semi-core relativistic 6p1/2 orbitals. The all other investigated structures, i.e. face-centered cubic (fcc) , simple cubic (sc) as well as rhombohedral (rh) structures are higher in energy. The criteria of mechanical stability were investigated based on the calculated elastic constants, identifying the phase instability of fcc and rh structures, but surprisingly confirm the stability of the energetically higher sc structure. In addition, the pressure-induced structural transition between two stable sc and bcc phases has been detected. The ground-state bcc structure exhibits the highest elastic anisotropy from single elements of the Periodic table. At last, we support the experimental findings that Copernicium is a metal.

Electronic Structure Principles and Aromaticity

ERIC Educational Resources Information Center

Chattaraj, P. K.; Sarkar, U.; Roy, D. R.

2007-01-01

The relationship between aromaticity and stability in molecules on the basis of quantities such as hardness and electrophilicity is explored. The findings reveal that aromatic molecules are less energetic, harder, less polarizable, and less electrophilic as compared to antiaromatic molecules, as expected from the electronic structure principles.

Origin of the 20-electron structure of Mg3 MnH7 : Density functional calculations

NASA Astrophysics Data System (ADS)

Gupta, M.; Singh, D. J.; Gupta, R.

2005-03-01

The electronic structure and stability of the 20-electron complex hydride, Mg3MnH7 is studied using density functional calculations. The heat of formation is larger in magnitude than that of MgH2 . The deviation from the 18-electron rule is explained by the predominantly ionic character of the band structure and a large crystal-field splitting of the Mn d bands. In particular, each H provides one deep band accomodating two electrons, while the Mn t2g bands hold an additional six electrons per formula unit.

Structural, stability, and vibrational properties of BinPm clusters

NASA Astrophysics Data System (ADS)

Shen, Wanting; Han, Lihong; Liang, Dan; Zhang, Chunfang; Ruge, Quhe; Wang, Shumin; Lu, Pengfei

2018-04-01

An in-depth investigation is performed on stability mechanisms, electronic and optical properties of III-V semiconductor vapor phases clusters. First principles electronic structure calculations of CAM-B3LYP are performed on neutral BinPm (n + m ≤ 14) clusters. The geometrical evolution of all stable structures remains amorphous as the clusters size increases. Binding energies (BEs), energy gains and highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO-LUMO) gaps confirm that all four-atom structures of BinPm clusters have more stable optical properties. Orbitals composition and vibrational spectra of stable clusters are analyzed. Our calculations will contribute to the study of diluted bismuth alloys and compounds.

Importance of interlayer H bonding structure to the stability of layered minerals

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

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulkmore » and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.« less

Importance of interlayer H bonding structure to the stability of layered minerals

DOE PAGES

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.; ...

2017-10-16

Layered (oxy) hydroxide minerals often possess out-of-plane hydrogen atoms that form hydrogen bonding networks which stabilize the layered structure. However, less is known about how the ordering of these bonds affects the structural stability and solubility of these minerals. Here, we report a new strategy that uses the focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility. In this regard, the dissolution behavior of boehmite (γ-AlOOH) and gibbsite (γ-Al(OH)3) were compared and contrasted in real time via liquid cell electron microscopy. Under identical such conditions, 2D-nanosheets of boehmite (γ-AlOOH) exfoliated from the bulkmore » and then rapidly dissolved, whereas gibbsite was stable. Further, substitution of only 1% Fe(III) for Al(III) in the structure of boehmite inhibited delamination and dissolution. Factors such as pH, radiolytic species, and knock on damage were systematically studied and eliminated as proximal causes for boehmite dissolution. Instead, the creation of electron/hole pairs was considered to be the mechanism that drove dissolution. The widely disparate behaviors of boehmite, gibbsite, and Fe-doped boehmite are discussed in the context of differences in the OH bond strengths, hydrogen bonding networks, and the presence or absence of electron/hole recombination centers.« less

Electronic correlation in magnetic contributions to structural energies

NASA Astrophysics Data System (ADS)

Haydock, Roger

For interacting electrons the density of transitions [see http://arxiv.org/abs/1405.2288] replaces the density of states in calculations of structural energies. Extending previous work on paramagnetic metals, this approach is applied to correlation effects on the structural stability of magnetic transition metals. Supported by the H. V. Snyder Gift to the University of Oregon.

Endohedral fullerenes contaning transition-metal clusters

NASA Astrophysics Data System (ADS)

Bhusal, Shusil; Basurto, Luis; Zope, Rajendra; Baruah, Tunna

We report detailed investigation of structural, electronic, and spectroscopic properties of VSc2N-containing fullerenes in the size range C68 - C96. First, the candidate structures of the ground state are obtained using a systematic approach in which a large number of isomers of endohedral fullerenes were screened for their energetic stability. Stability of some of the most promising isomers were further studied using density functional theory at the all-electron level using large polarized Gaussian basis sets. The effect of the V doping is examined on the structure, spin states and the magnetic properties of the endohedral fullerenes. De-SC0002168, NSF-DMR 125302, DE-SC0006818.

Nanoscale High Energetic Materials: A Polymeric Nitrogen Chain N8 Confined inside a Carbon Nanotube

NASA Astrophysics Data System (ADS)

Abou-Rachid, Hakima; Hu, Anguang; Timoshevskii, Vladimir; Song, Yanfeng; Lussier, Louis-Simon

2008-05-01

We present a theoretical study of a new hybrid material, nanostructured polymeric nitrogen, where a polymeric nitrogen chain is encapsulated in a carbon nanotube. The electronic and structural properties of the new system are studied by means of ab initio electronic structure and molecular dynamics calculations. Finite temperature simulations demonstrate the stability of this nitrogen phase at ambient pressure and room temperature using carbon nanotube confinement. This nanostructured confinement may open a new path towards stabilizing polynitrogen or polymeric nitrogen at ambient conditions.

Self aligning electron beam gun having enhanced thermal and mechanical stability

DOEpatents

Scarpetti, R.D. Jr.; Parkison, C.D.; Switzer, V.A.; Lee, Y.J.; Sawyer, W.C.

1995-05-16

A compact, high power electron gun is disclosed having enhanced thermal and mechanical stability which incorporates a mechanically coupled, self aligning structure for the anode and cathode. The enhanced stability, and reduced need for realignment of the cathode to the anode and downstream optics during operation are achieved by use of a common support structure for the cathode and anode which requires no adjustment screws or spacers. The electron gun of the present invention also incorporates a modular design for the cathode, in which the electron emitter, its support structure, and the hardware required to attach the emitter assembly to the rest of the gun are a single element. This modular design makes replacement of the emitter simpler and requires no realignment after a new emitter has been installed. Compactness and a reduction in the possibility of high voltage breakdown are achieved by shielding the ``triple point`` where the electrode, insulator, and vacuum meet. The use of electric discharge machining (EDM) for fabricating the emitter allows for the accurate machining of the emitter into intricate shapes without encountering the normal stresses developed by standard emitter fabrication techniques. 12 Figs.

Structural and electronic phase transitions of MoTe2 induced by Li ionic gating

NASA Astrophysics Data System (ADS)

Hwang, Jeongwoon; Zhang, Chenxi; Cho, Kyeongjae

2017-12-01

Monolayer MoTe2 has semiconducting and semimetallic phases with small energy difference, and the relative stability is readily reversed by gating. By first-principles calculations, we investigate the changes in atomic structure, electronic structure, and relative stability of two phases induced by Li ionic gating. To model Li ionic gating, we employ two approaches; one is direct adsorption of Li on MoTe2 and the other is introducing non-contacting Li plate over MoTe2. We show phonon instability in H-phase of MoTe2 with increasing the amount of charge transfer from Li, which implies a large electron-phonon coupling in the system resulting in a charge density wave state. Structural distortion is also observed in highly doped T d phase. The transition energy barrier from distorted H phase to distorted T d phase is reduced considerably compared to that of pristine MoTe2.

Cargo-shell and cargo-cargo couplings govern the mechanics of artificially loaded virus-derived cages

NASA Astrophysics Data System (ADS)

Llauró, Aida; Luque, Daniel; Edwards, Ethan; Trus, Benes L.; Avera, John; Reguera, David; Douglas, Trevor; Pablo, Pedro J. De; Castón, José R.

2016-04-01

Nucleic acids are the natural cargo of viruses and key determinants that affect viral shell stability. In some cases the genome structurally reinforces the shell, whereas in others genome packaging causes internal pressure that can induce destabilization. Although it is possible to pack heterologous cargoes inside virus-derived shells, little is known about the physical determinants of these artificial nanocontainers' stability. Atomic force and three-dimensional cryo-electron microscopy provided mechanical and structural information about the physical mechanisms of viral cage stabilization beyond the mere presence/absence of cargos. We analyzed the effects of cargo-shell and cargo-cargo interactions on shell stability after encapsulating two types of proteinaceous payloads. While bound cargo to the inner capsid surface mechanically reinforced the capsid in a structural manner, unbound cargo diffusing freely within the shell cavity pressurized the cages up to ~30 atm due to steric effects. Strong cargo-cargo coupling reduces the resilience of these nanocompartments in ~20% when bound to the shell. Understanding the stability of artificially loaded nanocages will help to design more robust and durable molecular nanocontainers.Nucleic acids are the natural cargo of viruses and key determinants that affect viral shell stability. In some cases the genome structurally reinforces the shell, whereas in others genome packaging causes internal pressure that can induce destabilization. Although it is possible to pack heterologous cargoes inside virus-derived shells, little is known about the physical determinants of these artificial nanocontainers' stability. Atomic force and three-dimensional cryo-electron microscopy provided mechanical and structural information about the physical mechanisms of viral cage stabilization beyond the mere presence/absence of cargos. We analyzed the effects of cargo-shell and cargo-cargo interactions on shell stability after encapsulating two types of proteinaceous payloads. While bound cargo to the inner capsid surface mechanically reinforced the capsid in a structural manner, unbound cargo diffusing freely within the shell cavity pressurized the cages up to ~30 atm due to steric effects. Strong cargo-cargo coupling reduces the resilience of these nanocompartments in ~20% when bound to the shell. Understanding the stability of artificially loaded nanocages will help to design more robust and durable molecular nanocontainers. Electronic supplementary information (ESI) available: 6 figures, 3 tables and theory. See DOI: 10.1039/c6nr01007e

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

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

Lin, Qisheng; Miller, Gordon J.

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization

DOE PAGES

Lin, Qisheng; Miller, Gordon J.

2017-12-18

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e –/atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Furthermore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate.

Atomic and electronic structure of the silicon and silicon-metal Si{sub 20}, Si{sub 20}{sup -}, NaSi{sub 20}, KSi{sub 20} nanoparticles

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

Borshch, N. A., E-mail: ssd18@phys.vsu.ru; Pereslavtseva, N. S.; Kurganskii, S. I.

The results of atomic-structure optimization and calculation of the electronic structure of the Si{sub 20}, Si{sub 20}{sup -}, NaSi{sub 20}, and KSi{sub 20} clusters are reported. The PM3 and AM1 semiempirical methods were used in the calculations. It is shown that the Na and K atoms stabilize the fullerene-like silicon structure. The effect of configuration of the clusters on their electronic structure is analyzed.

Structures, stability and electronic properties of bimetallic Cun-1Sc and Cun-2Sc2 (n = 2-7) clusters

NASA Astrophysics Data System (ADS)

Li, Zhi; Zhao, Zhen; Zhou, Zhonghao; Wang, Qi

2018-02-01

To investigate the interface between the main phases of Cu-Sc alloys, the structures, stability and electronic properties of bimetallic Cun-1Sc and Cun-2Sc2 (n = 2-7) clusters are systematically calculated by the GGA-PW91 functional. The results reveal that the structures of Cun-1Sc and Cun-2Sc2 (n = 2-7) clusters inherited those of pure Cun (n = 2-7) clusters and they maintained higher symmetry. Cu5Sc cluster possesses more stable than its neighbors while Cu2Sc2 cluster is less stable than its neighbors by binding energy. Cu5Sc cluster possesses the highest kinetic stability of Cun-1Sc clusters and CuSc2, Cu3Sc2 and Cu5Sc2 clusters possess higher kinetic stability than their neighbors by HOMO-LUMO gap. NBO analysis reveals that Cu-Sc atoms have less pd orbital hybridization in the Sc doping Cun (n = 2-7) clusters.

Stability enhancement and electronic tunability of two-dimensional SbIV compounds via surface functionalization

NASA Astrophysics Data System (ADS)

Zhou, Wenhan; Guo, Shiying; Liu, Xuhai; Cai, Bo; Song, Xiufeng; Zhu, Zhen; Zhang, Shengli

2018-01-01

We propose a family of hydrogenated- and halogenated-SbIV (SbIVX-2) materials that simultaneously have two-dimensional (2D) structures, high stability and appealing electronic properties. Based on first-principles total-energy and vibrational-spectra calculations, SbIVX-2 monolayers are found both thermally and dynamically stable. Varying IV and X elements can rationally tune the electronic properties of SbIVX-2 monolayers, effectively modulating the band gap from 0 to 3.42 eV. Regarding such superior stability and broad band-gap range, SbIVX-2 monolayers are expected to be synthesized in experiments and taken as promising candidates for low-dimensional electronic and optoelectronic devices, such as blue-to-ultraviolet light-emitting diodes (LED) and photodetectors.

Structural and electronic properties of rectangular CdTe nanowire: A DST study

NASA Astrophysics Data System (ADS)

Khan, Md. Shahzad; Bhatia, Manjeet; Srivastava, Anurag

2018-05-01

CdTe rectangular nanowire of different diameter in zinc-blende phase is investigated using density functional theory. Enhancement of diameter increased stability and improved electronic qualities suitable for device purpose applications. Cohesive energy per atom enhanced on enlarging diameter advocating the stability. Large diameter nanowire (22.62Å) exhibits bandgap of 1.21eV and electronic effective mass is observed to be 0.51me. The bonding between Cd-Te atoms are predominantly observed as covalent assuring its inertness towards moisture.

Stability and Elastic, Electronic, and Thermodynamic Properties of Fe2TiSi1- x Sn x Compounds

NASA Astrophysics Data System (ADS)

Jong, Ju-Yong; Yan, Jihong; Zhu, Jingchuan; Kim, Chol-Jin

2017-10-01

We have systematically studied the structural, phase, and mechanical stability and elastic, electronic, and thermodynamic properties of Fe2TiSi1- x Sn x ( x = 0, 0.25, 0.5, 0.75, 1) compounds using first-principles calculations. The structural and phase stability and elastic properties of Fe2TiSi1- x Sn x ( x = 0, 0.25, 0.5, 0.75, 1) indicated that all of the compounds are thermodynamically and mechanically stable. The shear modulus, bulk modulus, Young's modulus, Poisson's ratio, electronic band structure, density of states, Debye temperature, and Grüneisen parameter of all the substituted compounds were studied. The results show that Sn substitution in Fe2TiSi enhances its stability and mechanical and thermoelectric properties. The Fe2TiSi1- x Sn x compounds have narrow bandgap from 0.144 eV and 0.472 eV for Sn substitution from 0 to 1. The calculated band structure and density of states (DOS) of Fe2TiSi1- x Sn x show that the thermoelectric properties can be improved at substituent concentration x of 0.75. The lattice thermal conductivity was significantly decreased in the Sn-substituted compounds, and all the results indicate that Fe2TiSi0.25Sn0.75 could be a new candidate high-performance thermoelectric material.

Thermoelectric properties and thermal stability of layered chalcogenides, TlScQ2, Q = Se, Te.

PubMed

Aswathy, Vijayakumar Sajitha; Sankar, Cheriyedath Raj; Varma, Manoj Raama; Assoud, Abdeljalil; Bieringer, Mario; Kleinke, Holger

2017-12-12

A few thallium based layered chalcogenides of α-NaFeO 2 structure-type are known for their excellent thermoelectric properties and interesting topological insulator nature. TlScQ 2 belongs to this structural category. In the present work, we have studied the electronic structure, electrical and thermal transport properties and thermal stability of the title compounds within the temperature range 2-600 K. Density functional theory (DFT) predicts a metallic nature for TlScTe 2 and a semiconducting nature for TlScSe 2 . DFT calculations also show significant lowering of energies of frontier bands upon inclusion of spin-orbit coupling contribution in the calculation. The electronic structure also shows the simultaneous occurrence of holes and electron pockets for the telluride. Experiments reveal that the telluride shows a semi-metallic behaviour whereas the selenide is a semiconductor. The thermoelectric properties for both the materials were also investigated. Both these materials possess very low thermal conductivity which is an attractive feature for thermoelectrics. However, they lack thermal stability and decompose upon warming above room temperature, as evidenced from high temperature powder X-ray diffraction and thermal analysis.

Density-functional theory study of the geometries, stabilities, and electronic properties of Au n Rb (n = 1-10) clusters: comparison with pure gold clusters

NASA Astrophysics Data System (ADS)

Hu, Yan-Fei; Jiang, Gang; Meng, Da-Qiao

2012-01-01

The density functional method with the relativistic effective core potential has been employed to investigate systematically the geometric structures, relative stabilities, growth-pattern behavior, and electronic properties of small bimetallic Au n Rb (n = 1-10) and pure gold Au n (n ≤ 11) clusters. For the geometric structures of the Au n Rb (n = 1-10) clusters, the dominant growth pattern is for a Rb-substituted Au n +1 cluster or one Au atom capped on a Au n -1Rb cluster, and the turnover point from a two-dimensional to a three-dimensional structure occurs at n = 4. Moreover, the stability of the ground-state structures of these clusters has been examined via an analysis of the average atomic binding energies, fragmentation energies, and the second-order difference of energies as a function of cluster size. The results exhibit a pronounced even-odd alternation phenomenon. The same pronounced even-odd alternations are found for the HOMO-LUMO gap, VIPs, VEAs, and the chemical hardness. In addition, about one electron charge transfers from the Au n host to the Rb atom in each corresponding Au n Rb cluster.

The electronic structure of Au25 clusters: between discrete and continuous.

PubMed

Katsiev, Khabiboulakh; Lozova, Nataliya; Wang, Lu; Sai Krishna, Katla; Li, Ruipeng; Mei, Wai-Ning; Skrabalak, Sara E; Kumar, Challa S S R; Losovyj, Yaroslav

2016-08-21

Here, an approach based on synchrotron resonant photoemission is employed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states in the vicinity of the Fermi level. These observations are supported by DFT studies.

Atomic scale morphology, growth behaviour and electronic properties of semipolar {101[overline]3} GaN surfaces.

PubMed

Kioseoglou, J; Kalesaki, E; Lymperakis, L; Karakostas, Th; Komninou, Ph

2013-01-30

First-principles calculations relating to the atomic structure and electronic properties of {101[overline]3} GaN surfaces reveal significant differentiations between the two polarity orientations. The (101[overline]3) surface exhibits a remarkable morphological stability, stabilizing a metallic structure (Ga adlayer) over the entire range of the Ga chemical potential. In contrast, the semiconducting, cleaved surface is favoured on (101[overline]3[overline]) under extremely and moderately N-rich conditions, a Ga bilayer is stabilized under corresponding Ga-rich conditions and various transitions between metallic reconstructions take place in intermediate growth stoichiometries. Efficient growth schemes for smooth, two-dimensional GaN layers and the isolation of {101[overline]3} material from parasitic orientations are identified.

The role of zinc on the chemistry of complex intermetallic compounds

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

Xie, Weiwei

2014-01-01

Combining experiments and electronic structure theory provides the framework to design and discover new families of complex intermetallic phases and to understand factors that stabilize both new and known phases. Using solid state synthesis and multiple structural determinations, ferromagnetic β-Mn type Co 8+xZn 12–x was analyzed for their crystal and electronic structures.

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

Manikandan, M.; Santhosh, M.; Rajeswarapalanichamy, R., E-mail: rrpalanichamy@gmail.com

Ab initio calculations are performed to investigate the structural stability, electronic structure and mechanical properties of actinide carbides AnC (An=U, Np) for three different crystal structures, namely NaCl, CsCl and ZnS. Among the considered structures, NaCl structure is found to be the most stable structure for these carbides at normal pressure. A pressure induced structural phase transition from NaCl to ZnS is observed. The electronic structure reveals that these carbides are metals. The calculated elastic constants indicate that these carbides are mechanically stable at normal pressure.

Thermal stability of MBE-grown epitaxial MoSe2 and WSe2 thin films

NASA Astrophysics Data System (ADS)

Chang, Young Jun; Choy, Byoung Ki; Phark, Soo-Hyon; Kim, Minu

Layered transition metal dichalcogenides (TMDs) draw much attention, because of its unique optical properties and band structures depending on the layer thicknesses. However, MBE growth of epitaxial films demands information about thermal stability of stoichiometry and related electronic structure for high temperature range. We grow epitaxial MoSe2 and WSe2 ultrathin films by using molecular beam epitaxy (MBE). We characterize stoichiometry of films grown at various growth temperature by using various methods, XPS, EDX, and TOF-MEIS. We further test high temperature stability of electronic structure for those films by utilizing in-situ ellipsometry attached to UHV chamber. We discuss threshold temperatures up to 700~1000oC, at which electronic phases changes from semiconductor to metal due to selenium deficiency. This information can be useful for potential application of TMDs for fabrication of Van der Waals multilayers and related devices. This research was supported by Nano.Material Technology Development Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT and Future Planning. (2009-0082580), NRF-2014R1A1A1002868.

First-principles study of graphene under c-HfO{sub 2}(111) layers: Electronic structures and transport properties

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

Kaneko, Tomoaki, E-mail: kaneko@flex.phys.tohoku.ac.jp; Materials Research Consortium for Energy Efficient Electronic Devices; Ohno, Takahisa, E-mail: OHNO.Takahisa@nims.go.jp

2016-08-22

We investigated the electronic properties, stability, and transport of graphene under c-HfO{sub 2}(111) layers by performing first-principles calculations with special attention to the chemical bonding between graphene and HfO{sub 2} surfaces. When the interface of HfO{sub 2}/graphene is terminated by an O layer, the linear dispersion of graphene is preserved and the degradation of transport is suppressed. For other interface structures, HfO{sub 2} is tightly adsorbed on graphene and the transport is strictly limited. In terms of the stability of the interface structures, an O-terminated interface is preferable, which is achieved under an O-deficient condition.

When Anatase Nanoparticles Become Bulklike: Properties of Realistic TiO2 Nanoparticles in the 1-6 nm Size Range from All Electron Relativistic Density Functional Theory Based Calculations.

PubMed

Lamiel-Garcia, Oriol; Ko, Kyoung Chul; Lee, Jin Yong; Bromley, Stefan T; Illas, Francesc

2017-04-11

All electron relativistic density functional theory (DFT) based calculations using numerical atom-centered orbitals have been carried out to explore the relative stability, atomic, and electronic structure of a series of stoichiometric TiO 2 anatase nanoparticles explicitly containing up to 1365 atoms as a function of size and morphology. The nanoparticles under scrutiny exhibit octahedral or truncated octahedral structures and span the 1-6 nm diameter size range. Initial structures were obtained using the Wulff construction, thus exhibiting the most stable (101) and (001) anatase surfaces. Final structures were obtained from geometry optimization with full relaxation of all structural parameters using both generalized gradient approximation (GGA) and hybrid density functionals. Results show that, for nanoparticles of a similar size, octahedral and truncated octahedral morphologies have comparable energetic stabilities. The electronic structure properties exhibit a clear trend converging to the bulk values as the size of the nanoparticles increases but with a marked influence of the density functional employed. Our results suggest that electronic structure properties, and hence reactivity, for the largest anatase nanoparticles considered in this study will be similar to those exhibited by even larger mesoscale particles or by bulk systems. Finally, we present compelling evidence that anatase nanoparticles become effectively bulklike when reaching a size of ∼20 nm diameter.

Structural and electronic properties of the alkali metal incommensurate phases

NASA Astrophysics Data System (ADS)

Woolman, Gavin; Naden Robinson, Victor; Marqués, Miriam; Loa, Ingo; Ackland, Graeme J.; Hermann, Andreas

2018-05-01

Under pressure, the alkali elements sodium, potassium, and rubidium adopt nonperiodic structures based on two incommensurate interpenetrating lattices. While all elements form the same "host" lattice, their "guest" lattices are all distinct. The physical mechanism that stabilizes these phases is not known, and detailed calculations are challenging due to the incommensurability of the lattices. Using a series of commensurate approximant structures, we tackle this issue using density functional theory calculations. In Na and K, the calculations prove accurate enough to reproduce not only the stability of the host-guest phases, but also the complicated pressure dependence of the host-guest ratio and the two guest-lattice transitions. We find Rb-IV to be metastable at all pressures, and suggest it is a high-temperature phase. The electronic structure of these materials is unique: they exhibit two distinct, coexisting types of electride behavior, with both fully localized pseudoanions and electrons localized in 1D wells in the host lattice, leading to low conductivity. While all phases feature pseudogaps in the electronic density of states, the perturbative free-electron picture applies to Na, but not to K and Rb, due to significant d -orbital population in the latter.

Improving the Mechanical Performance and Thermal Stability of a PVA-Clay Nanocomposite by Electron Beam Irradiation

NASA Astrophysics Data System (ADS)

Shokuhi Rad, A.; Ebrahimi, D.

2017-07-01

The effects of electron beam irradiation and presence of clay on the mechanical properties and thermal stability of montmorillonite clay-modified polyvinyl alcohol nanocomposites were studied. By using the X-ray diffraction (XRD) and transmission electron microscopy (TEM), the microstructure of the nanocomposites was investigated. The results obtained from TEM and XRD tests showed that montmorillonite clay nanoparticles were located in the polyvinyl alcohol phase. The XRD analysis confirmed the formation of an exfoliated structure in nanocomposites samples. Increasing the amount of clay to 20 wt.% increased the tensile strength and modulus of the nanocomposite. Irradiation up to an absorbed dose of 100 kGy increased its mechanical properties and thermal stability, but at higher irradiation levels, the mechanical strength and thermal stability declined. The sample with 20 wt.% of the nanofiller, exposed to 100 kGy, showed the highest mechanical strength and thermal stability.

Electronegativity and hardness as coordinates in structure stability diagrams.

PubMed Central

Shankar, S; Parr, R G

1985-01-01

With electronegativity and hardness of an atom defined as 1/2(I + A) and 1/2(I - A), respectively, where I and A are the ionization potential and electron affinity, electronegativity difference and hardness sum are proposed as coordinates in structure stability diagrams. With these coordinates a successful topological classification of the crystal structures of octet and suboctet binary compounds is obtained, and a clear delineation of the structural classes portraying chemical periodicity is found. PMID:3855552

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

DOE PAGES

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou; ...

2017-03-18

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

Structure and chemistry of epitaxial ceria thin films on yttria-stabilized zirconia substrates, studied by high resolution electron microscopy

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

Sinclair, Robert; Lee, Sang Chul; Shi, Yezhou

Here, we have applied aberration-corrected transmission electron microscopy (TEM) imaging and electron energy loss spectroscopy (EELS) to study the structure and chemistry of epitaxial ceria thin films, grown by pulsed laser deposition onto (001) yttria-stabilized zirconia (YSZ) substrates. There are few observable defects apart from the expected mismatch interfacial dislocations and so the films would be expected to have good potential for applications. Under high electron beam dose rate (above about 6000 e-/Å 2s) domains of an ordered structure appear and these are interpreted as being created by oxygen vacancy ordering. The ordered structure does not appear at lower losemore » rates (ca. 2600 e-/Å 2s) and can be removed by imaging under 1 mbar oxygen gas in an environmental TEM. EELS confirms that there is both oxygen deficiency and the associated increase in Ce 3+ versus Ce 4+ cations in the ordered domains. In situ high resolution TEM recordings show the formation of the ordered domains as well as atomic migration along the ceria thin film (001) surface.« less

First-principles study of Al2Sm intermetallic compound on structural, mechanical properties and electronic structure

NASA Astrophysics Data System (ADS)

Lin, Jingwu; Wang, Lei; Hu, Zhi; Li, Xiao; Yan, Hong

2017-02-01

The structural, thermodynamic, mechanical and electronic properties of cubic Al2Sm intermetallic compound are investigated by the first-principles method on the basis of density functional theory. In light of the strong on-site Coulomb repulsion between the highly localized 4f electrons of Sm atoms, the local spin density approximation approach paired with additional Hubbard terms is employed to achieve appropriate results. Moreover, to examine the reliability of this study, the experimental value of lattice parameter is procured from the analysis of the TEM image and diffraction pattern of Al2Sm phase in the AZ31 alloy to verify the authenticity of the results originated from the computational method. The value of cohesive energy reveals Al2Sm to be a stable in absolute zero Kelvin. According to the stability criteria, the subject of this work is mechanically stable. Afterward, elastic moduli are deduced by performing Voigt-Reuss-Hill approximation. Furthermore, elastic anisotropy and anisotropy of sound velocity are discussed. Finally, the calculation of electronic density of states is implemented to explore the underlying mechanism of structural stability.

Stability and electronic properties of low-dimensional nanostructures

NASA Astrophysics Data System (ADS)

Guan, Jie

As the devices used in daily life become smaller and more concentrated, traditional three-dimensional (3D) bulk materials have reached their limit in size. Low-dimensional nanomaterials have been attracting more attention in research and getting widely applied in many industrial fields because of their atomic-level size, unique advanced properties, and varied nanostructures. In this thesis, I have studied the stability and mechanical and electronic properties of zero-dimensional (0D) structures including carbon fullerenes, nanotori, metallofullerenes and phosphorus fullerenes, one-dimensional (1D) structures including carbon nanotubes and phosphorus nanotubes, as well as two-dimensional (2D) structures including layered transition metal dichalcogenides (TMDs), phosphorene and phosphorus carbide (PC). I first briefly introduce the scientific background and the motivation of all the work in this thesis. Then the computational techniques, mainly density functional theory (DFT), are reviewed in Chapter 2. In Chapter 3, I investigate the stability and electronic structure of endohedral rare-earth metallofullerene La C60 and the trifluoromethylized La C60(CF3)n with n ≤ 5. Odd n is preferred due to the closed-shell electronic configuration or large HOMO-LUMO gap, which is also meaningful for the separation of C 60-based metallofullerenes. Mechanical and electronic properties of layered materials including TMDs and black phosphorus are studied in Chapter 4 and 5. In Chapter 4, a metallic NbSe2/semiconducting WSe2 bilayer is investigated and besides a rigid band shift associated with charge transfer, the presence of NbSe2 does not modify the electronic structure of WSe2. Structural similarity and small lattice mismatch results in the heterojunction being capable of efficiently transferring charge acrossthe interface. In Chapter 5, I investigate the dependence of stability and electronic band structure on the in-layer strain in bulk black phosphorus. In Chapters 6, 7 and 8, novel 2D structures are predicted theoretically. In Chapter 6, I propose two new stable structural phases of layered phosphorus besides the layered alpha-P (black) and beta-P (blue) phosphorus allotropes. A metal-insulator transition caused by inlayer strain or changing the number of layers is found in the new gamma-P phase. An unforeseen benefit is the possibility to connect different structural phases at no energy cost, which further leads to a paradigm of constructing very stable, faceted phosphorus nanotube and fullerene structures by laterally joining nanoribbons or patches of different planar phosphorene phases, which is discussed in Chapter 7. In Chapter 8, I propose previously unknown allotropes of PC in the stable shape of an atomically thin layer. Different stable geometries, which result from the competition between sp2 bonding found in graphitic C and sp3 bonding found in black P, display different electronic properties including metallic, semi-metallic with an anisotropic Dirac cone, and direct-gap semiconductors with their gap tunable by in-layer strain. In Chapter 9, I propose a fast method to determine the local curvature in 2D systems with arbitrary shape. The curvature information, combined with elastic constants obtained for a planar system, provides an accurate estimate of the local stability in the framework of continuum elasticity theory. This approach can be applied to all 2D structures. Finally, I present general conclusions from the PhD Thesis work in Chapter 10.

Structural phase transition, electronic structure and optical properties of half Heusler alloys LiBeZ (Z = As, Sb)

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

Amudhavalli, A.; Rajeswarapalanichamy, R., E-mail: rajeswarapalanichamy@gmail.com

2016-05-23

Ab initio calculations are performed to investigate the structural stability, electronic structure, mechanical properties and optical properties of half Heusler alloys (LiBeAs and LiBeSb) for three different phases of zinc blende crystal structure. Among the considered phases, α- phase is found to be the most stable phase for these alloys at normal pressure. A pressure induced structural phase transition from α-phase to β- phase is observed for LiBeAs. The electronic structure reveals that these alloys are semiconductors. The optical properties confirm that these alloys are semiconductor in nature.

Opposing effects of stacking faults and antisite domain boundaries on the conduction band edge in kesterite quaternary semiconductors

NASA Astrophysics Data System (ADS)

Park, Ji-Sang; Kim, Sunghyun; Walsh, Aron

2018-01-01

We investigated stability and the electronic structure of extended defects including antisite domain boundaries and stacking faults in the kesterite-structured semiconductors, Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe). Our hybrid density functional theory calculations show that stacking faults in CZTS and CZTSe induce a higher conduction band edge than the bulk counterparts, and thus the stacking faults act as electron barriers. Antisite domain boundaries, however, accumulate electrons as the conduction band edge is reduced in energy, having an opposite role. An Ising model was constructed to account for the stability of stacking faults, which shows the nearest-neighbor interaction is stronger in the case of the selenide.

Clar's sextet rule is a consequence of the sigma-electron framework.

PubMed

Maksić, Zvonimir B; Barić, Danijela; Müller, Thomas

2006-08-24

A number of condensed PAHs are examined to identify the underlying reasons governing empirical Clar's rule taking benzene as a limiting case. It is found that the so-called Clar's structures are the only minima on the MP2(fc) potential energy hypersurfaces, meaning that other conceivable valence isomers are nonexistent. The influence of the electron correlation energies to the stability of Clar's structures is substantial with predominating influence of the sigma-electrons. However, the contributions arising from the sigma- and pi-electron correlation energies are approximately the same, if Clar's structures are compared with some artificial pi-electron localized or graphite-like delocalized planar systems. Analysis of the Hartree-Fock (HF) energies provides a compelling evidence that the origin of stability of Clar's structures lies in a decrease of the positive T, V(ee) and V(nn) energy terms relative to some characteristic virtual "delocalized" or "localized" model geometries. Partitioning of the mixed and terms in the sigma- and pi-type contributions, by using the stockholder (SHR), equipartitioning (EQP) and standard pi (SPI) schemes, unequivocally shows that the driving force leading to Clar's structures are more favorable sigma-type interactions. All these conclusions hold for the archetypal benzene too, which could be considered as a limiting Clar system. Finally, the boundaries of Clar's hypothesis and some common misconceptions are briefly discussed. Perusal of the geometric parameters and pi-bond orders reveals that there are no benzene rings completely "vacant" or "fully occupied" by the pi-electrons, envisaged by Clar in his picture of condensed benzenoid compounds. Instead, there are six-membered rings with higher and lower total pi-electron density. The bond length anisotropy of the former rings is smaller. It is concluded that Clar's proposition is a useful rule of thumb providing qualitative information on the stability of the PAH systems, which in turn should not be overinterpreted.

First principles study of structural, vibrational and electronic properties of graphene-like MX 2 (M=Mo, Nb, W, Ta; X=S, Se, Te) monolayers

NASA Astrophysics Data System (ADS)

Ding, Yi; Wang, Yanli; Ni, Jun; Shi, Lin; Shi, Siqi; Tang, Weihua

2011-05-01

Using first principles calculations, we investigate the structural, vibrational and electronic structures of the monolayer graphene-like transition-metal dichalcogenide (MX 2) sheets. We find the lattice parameters and stabilities of the MX 2 sheets are mainly determined by the chalcogen atoms, while the electronic properties depend on the metal atoms. The NbS 2 and TaS 2 sheets have comparable energetic stabilities to the synthesized MoS 2 and WS 2 ones. The molybdenum and tungsten dichalcogenide (MoX 2 and WX 2) sheets have similar lattice parameters, vibrational modes, and electronic structures. These analogies also exist between the niobium and tantalum dichalcogenide (NbX 2 and TaX 2) sheets. However, the NbX 2 and TaX 2 sheets are metals, while the MoX 2 and WX 2 ones are semiconductors with direct-band gaps. When the Nb and Ta atoms are doped into the MoS 2 and WS 2 sheets, a semiconductor-to-metal transition occurs. Comparing to the bulk compounds, these monolayer sheets have similar structural parameters and properties, but their vibrational and electronic properties are varied and have special characteristics. Our results suggest that the graphene-like MX 2 sheets have potential applications in nano-electronics and nano-devices.

Is the regulation of the electronic properties of organic molecules by polynuclear superhalogens more effective than that by mononuclear superhalogens? A high-level ab initio case study.

PubMed

Li, Miao-Miao; Li, Jin-Feng; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

2015-08-21

The regulation of the electronic properties of organic molecules induced by polynuclear superhalogens is theoretically explored here for sixteen composite structures. It is clearly indicated by the higher vertical electron detachment energy (VDE) that polynuclear superhalogens are more effective in regulating the electronic properties than mononuclear structures. However, this enhanced regulation is not only determined by superhalogens themselves but also related to the distribution of the extra electron of the final composites. The composites, in which the extra electron is mainly aggregated into the superhalogen moiety, will possess higher VDE values, as reported in the case of C1', 7.12 eV at the CCSD(T) level. This is probably due to the fact that, compared with organic molecules, superhalogens possess stronger attraction towards the extra electron and thus should lead to lower energies of the extra electrons and to higher VDE values eventually. Compared with CCSD(T), the Outer Valence Green's Function (OVGF) method fails completely for composite structures containing Cl atoms, while MP2 results are generally consistent in terms of the relative order of VDEs. Actually if the extra electron distribution of the systems could be approximated by the HOMO, the results at the OVGF level will be consistent with the CCSD(T) results. Conversely, the difference in VDEs between OVGF and CCSD(T) is significantly large. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to various fragmentation channels were also investigated for all the composite structures.

Communication: Many-body stabilization of non-covalent interactions: Structure, stability, and mechanics of Ag3Co(CN)6 framework.

PubMed

Liu, Xiaofei; Hermann, Jan; Tkatchenko, Alexandre

2016-12-28

Stimuli-responsive metal-organic frameworks (MOFs) and other framework materials exhibit a broad variety of useful properties, which mainly stem from an interplay of strong covalent bonds within the organic linkers with presumably weak van der Waals (vdW) interactions which determine the overall packing of the framework constituents. Using Ag 3 Co(CN) 6 as a fundamental test case-a system with a colossal positive and negative thermal expansion [A. L. Goodwin et al., Science 319, 794 (2008)]-we demonstrate that its structure, stability, dielectric, vibrational, and mechanical properties are critically influenced by many-body electronic correlation contributions to non-covalent vdW interactions. The Ag 3 Co(CN) 6 framework is a remarkable molecular crystal, being visibly stabilized, rather than destabilized, by many-body vdW correlations. A detailed comparison with H 3 Co(CN) 6 highlights the crucial role of strongly polarized metallophilic interactions in dictating the exceptional properties of denser MOFs. Beyond MOFs, our findings indicate that many-body electronic correlations can substantially stabilize polarizable materials, providing a novel mechanism for tuning the properties of nanomaterials with intricate structural motifs.

Structural, electronic and magnetic properties of Ti n Mo ( n = 1 - 7) clusters

NASA Astrophysics Data System (ADS)

Zhang, Ge; Zhai, Zhongyuan; Sheng, Yong

2017-04-01

The ground state structures of TinMo and Tin+1 (n = 1 - 7) clusters and their structural, electronic and magnetic properties are investigated with the density functional method at B3LYP/LanL2DZ level. One Mo atom substituted Tin+1 structure is the dominant growth pattern, and the TinMo clusters exhibit enhanced structural stabilities according to the averaged binding energies. The electronic properties are also discussed by investigating chemical hardness and HOMO-LUMO energy gap. The results reveal that Ti3Mo and Ti5Mo keep higher chemical stabilities when compared with the other clusters. For all the studied clusters, the Mo atoms always get electrons from Ti atoms and present negative charges. Moreover, the doping of Mo in the bare titanium clusters can alter the magnetic moments of them. Ti3Mo and Ti5Mo show relatively large total magnetic moments, which may be related to the presence of exchange splitting behavior in their densities of states. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-70589-8

Extremely strong self-assembly of a bimetallic salen complex visualized at the single-molecule level.

PubMed

Salassa, Giovanni; Coenen, Michiel J J; Wezenberg, Sander J; Hendriksen, Bas L M; Speller, Sylvia; Elemans, Johannes A A W; Kleij, Arjan W

2012-04-25

A bis-Zn(salphen) structure shows extremely strong self-assembly both in solution as well as at the solid-liquid interface as evidenced by scanning tunneling microscopy, competitive UV-vis and fluorescence titrations, dynamic light scattering, and transmission electron microscopy. Density functional theory analysis on the Zn(2) complex rationalizes the very high stability of the self-assembled structures provoked by unusual oligomeric (Zn-O)(n) coordination motifs within the assembly. This coordination mode is strikingly different when compared with mononuclear Zn(salphen) analogues that form dimeric structures having a typical Zn(2)O(2) central unit. The high stability of the multinuclear structure therefore holds great promise for the development of stable self-assembled monolayers with potential for new opto-electronic materials.

Phase and frequency structure of superradiance pulses generated by relativistic Ka-band backward-wave oscillator

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

Rostov, V. V.; Romanchenko, I. V.; Elchaninov, A. A.

2016-08-15

Phase and frequency stability of electromagnetic oscillations in sub-gigawatt superradiance (SR) pulses generated by an extensive slow-wave structure of a relativistic Ka-band backward-wave oscillator were experimentally investigated. Data on the frequency tuning and radiation phase stability of SR pulses with a variation of the energy and current of electron beam were obtained.

Study of neoclassical effects on the pedestal structure in ELMy H-mode plasmas

NASA Astrophysics Data System (ADS)

Pankin, A. Y.; Bateman, G.; Kritz, A. H.; Rafiq, T.; Park, G. Y.; Ku, S.; Chang, C. S.; Snyder, P. B.

2009-11-01

The neoclassical effects on the H-mode pedestal structure are investigated in this study. First principles' kinetic simulations of the neoclassical pedestal dynamics are combined with the MHD stability conditions for triggering ELM crashes that limit the pedestal width and height in H-mode plasmas. The neoclassical kinetic XGC0 code [1] is used to produce systematic scans over plasma parameters including plasma current, elongation, and triangularity. As plasma profiles evolve, the MHD stability limits of these profiles are analyzed with the ideal MHD stability ELITE code [2]. The scalings of the pedestal width and height are presented as a function of the scanned plasma parameters. Simulations with the XGC0 code, which include coupled ion-electron dynamics, yield predictions for both ion and electron pedestal profiles. Differences in the electron and ion pedestal scalings are investigated. [1] C.S. Chang et al, Phys. Plasmas 11 (2004) 2649. [2] P.B. Snyder et al, Phys. Plasmas, 9 (2002) 2037.

First principles and experimental study of the electronic structure and phase stability of bulk thallium bromide

NASA Astrophysics Data System (ADS)

Smith, Holland M.; Zhou, Yuzhi; Ciampi, Guido; Kim, Hadong; Cirignano, Leonard J.; Shah, Kanai S.; Haller, E. E.; Chrzan, D. C.

2013-08-01

We apply state-of-art first principle calculations to study the polymorphism and electronic structure of three previously reported phases of TlBr. The calculated band structures of NaCl-structure phase and orthorhombic-structure phase have different features than that of commonly observed CsCl-structure phase. We further interpret photoluminescence spectra based on our calculations. Several peaks close to calculated band gap values of the NaCl-structure phase and the orthorhombic-structure phase are found in unpolished TlBr samples.

The Key Ingredients of the Electronic Structure of FeSe

NASA Astrophysics Data System (ADS)

Coldea, Amalia I.; Watson, Matthew D.

2018-03-01

FeSe is a fascinating superconducting material at the frontier of research in condensed matter physics. Here, we provide an overview of the current understanding of the electronic structure of FeSe, focusing in particular on its low-energy electronic structure as determined from angle-resolved photoemission spectroscopy, quantum oscillations, and magnetotransport measurements of single-crystal samples. We discuss the unique place of FeSe among iron-based superconductors, as it is a multiband system exhibiting strong orbitally dependent electronic correlations and unusually small Fermi surfaces and is prone to different electronic instabilities. We pay particular attention to the evolution of the electronic structure that accompanies the tetragonal-orthorhombic structural distortion of the lattice around 90 K, which stabilizes a unique nematic electronic state. Finally, we discuss how the multiband multiorbital nematic electronic structure impacts our understanding of the superconductivity, and show that the tunability of the nematic state with chemical and physical pressure helps to disentangle the role of different competing interactions relevant for enhancing superconductivity.

Two-dimensional titanium carbonitrides and their hydroxylated derivatives: Structural, electronic properties and stability of MXenes Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2} from DFTB calculations

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

Enyashin, A.N.; Ivanovskii, A.L., E-mail: ivanovskii@ihim.uran.ru

2013-11-15

The structural, electronic properties and stability of the new MXene compounds—two-dimensional pristine carbonitrides Ti{sub 3}C{sub 2−x}N{sub x} and their hydroxylated derivatives Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2} are studied by means of DFTB calculations. The genesis of the properties is discussed in the sequence: binary MXenes Ti{sub 3}C{sub 2} (Ti{sub 3}N{sub 2})→hydroxylated forms Ti{sub 3}C{sub 2}(OH){sub 2} (Ti{sub 3}N{sub 2}(OH){sub 2})→pristine MXene Ti{sub 3}C{sub 2−x}N{sub x}→hydroxylated Ti{sub 3}C{sub 2−x}N{sub x}(OH){sub 2}. All examined materials are metallic-like. The most favorable type of OH-covering is presented by the occupation of the hollow sites between three neighboring carbon (nitrogen) atoms. Two-dimensional MXene carbonitrides withmore » random distribution of C and N atoms are found to be thermodynamically more favorable. - Graphical abstract: The side views of the optimized atomic structures of some examined hydroxylated derivatives of MXene Ti{sub 3}CN and their electronic band structures. Display Omitted - Highlights: • Very recently 2D titanium carbonitrides have been synthesized. • Structural, electronic properties and stability for these materials were evaluated. • The hydroxylated derivatives of 2D titanium carbonitrides are examined.« less

Electronic Structure Studies on the Whole Keplerate Family: Predicting New Members.

PubMed

Melgar, Dolores; Bandeira, Nuno A G; Bo, Carles

2017-04-19

A comprehensive study of the electronic structure of nanoscale molecular oxide capsules of the type [{M VI (M VI ) 5 O 21 } 12 {M' V 2 O 2 (μ-X)(μ-Y)(L n- )} 30 ] (12+n)- is presented, where M,M'=Mo,W, and the bridging ligands X,Y=O,S, carried out by means of density functional theory. Discussion of the electronic structure of these derivatives is focused on the thermodynamic stability of each of the structures, the one having the highest HOMO-LUMO gap being M=W, M'=Mo, X=Y=S. For the most well-known structure M=M'=Mo, X=Y=O, [Mo 132 O 372 ] 12- , the chemical bonding of several ligands to the {Mo V 2 O 2 (μ-O) 2 } linker moiety produces negligible effects on its stability, which is evidence of a strong ionic component in these bonds. The existence of a hitherto unknown species, namely W 132 with both bridging alternatives, is discussed and put into context. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density functional study on structure and stability of bimetallic AuNZn (N<=6) clusters and their cations

NASA Astrophysics Data System (ADS)

Tanaka, Hiromasa; Neukermans, Sven; Janssens, Ewald; Silverans, Roger E.; Lievens, Peter

2003-10-01

A systematic study on the structure and stability of zinc doped gold clusters has been performed by density functional theory calculations. All the lowest-energy isomers found have a planar structure and resemble pure gold clusters in shape. Stable isomers tend to equally delocalize valence s electrons of the constituent atoms over the entire structure and maximize the number of Au-Zn bonds in the structure. This is because the Au-Zn bond is stronger than the Au-Au bond and gives an extra σ-bonding interaction by the overlap between vacant Zn 4p and valence Au 6s(5d) orbitals. No three-dimensional isomers were found for Au5Zn+ and Au4Zn clusters containing six delocalized valence electrons. This result reflects that these clusters have a magic number of delocalized electrons for two-dimensional systems. Calculated vertical ionization energies and dissociation energies as a function of the cluster size show odd-even behavior, in agreement with recent mass spectrometric observations [Tanaka et al., J. Am. Chem. Soc. 125, 2862 (2003)].

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

Nelson, A. J.; Voss, L. F.; Beck, P. R.

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Phase stabilities at a glance: Stability diagrams of nickel dipnictides

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

Bachhuber, F.; School of Chemical Sciences, The University of Auckland, Private Bag 92019, Auckland; Rothballer, J.

2013-12-07

In the course of the recent advances in chemical structure prediction, a straightforward type of diagram to evaluate phase stabilities is presented based on an expedient example. Crystal structures and energetic stabilities of dipnictides NiPn{sub 2} (Pn = N, P, As, Sb, Bi) are systematically investigated by first principles calculations within the framework of density functional theory using the generalized gradient approximation to treat exchange and correlation. These dipnictides show remarkable polymorphism that is not yet understood systematically and offers room for the discovery of new phases. Relationships between the concerned structures including the marcasite, the pyrite, the arsenopyrite/CoSb{sub 2},more » and the NiAs{sub 2} types are highlighted by means of common structural fragments. Electronic stabilities of experimentally known and related AB{sub 2} structure types are presented graphically in so-called stability diagrams. Additionally, competing binary phases are taken into consideration in the diagrams to evaluate the stabilities of the title compounds with respect to decomposition. The main purpose of the stability diagrams is the introduction of an image that enables the estimation of phase stabilities at a single glance. Beyond that, some of the energetically favored structure types can be identified as potential new phases.« less

A theoretical and simulation study of the contact discontinuities based on a Vlasov simulation code

NASA Astrophysics Data System (ADS)

Tsai, T. C.; Lyu, L. H.; Chao, J. K.; Chen, M. Q.; Tsai, W. H.

2009-12-01

Contact discontinuity (CD) is the simplest solution that can be obtained from the magnetohydrodynamics (MHD) Rankine-Hugoniot jump conditions. Due to the limitations of the previous kinetic simulation models, the stability of the CD has become a controversial issue in the past 10 years. The stability of the CD is reexamined analytically and numerically. Our theoretical analysis shows that the electron temperature profile and the ion temperature profile must be out of phase across the CD if the CD structure is to be stable in the electron time scale and with zero electron heat flux on either side of the CD. Both a newly developed fourth-order implicit electrostatic Vlasov simulation code and an electromagnetic finite-size particle code are used to examine the stability and the electrostatic nature of the CD structure. Our theoretical prediction is verified by both simulations. Our results of Vlasov simulation also indicate that a simulation with initial electron temperature profile and ion temperature profile varying in phase across the CD will undergo very transient changes in the electron time scale but will relax into a quasi-steady CD structure within a few ion plasma oscillation periods if a real ion-electron mass ratio is used in the simulation and if the boundary conditions allow nonzero heat flux to be presented at the boundaries of the simulation box. The simulation results of this study indicate that the Vlasov simulation is a powerful tool to study nonlinear phenomena with nonperiodic boundary conditions and with nonzero heat flux at the boundaries of the simulation box.

Electronic structure of graphene nanoribbons doped with nitrogen atoms: a theoretical insight.

PubMed

Torres, A E; Fomine, S

2015-04-28

The electronic structure of graphene nanoribbons doped with a graphitic type of nitrogen atoms has been studied using B3LYP, B2PLYP and CAS methods. In all but one case the restricted B3LYP solutions were unstable and the CAS calculations provided evidence for the multiconfigurational nature of the ground state with contributions from two dominant configurations. The relative stability of the doped nanoribbons depends mostly on the mutual position of the dopant atoms and notably less on the position of nitrogen atoms within the nanoribbon. N-graphitic doping affects cationic states much more than anionic ones due the participation of the nitrogen atoms in the stabilization of the positive charge, resulting in a drop in ionization energies (IPs) for N-graphitic doped systems. Nitrogen atoms do not participate in the negative charge stabilization of anionic species and, therefore, the doping does not affect the electron affinities (EAs). The unrestricted B3LYP method is the method of choice for the calculation of IPs and EAs. Restricted B3LYP and B2PLYP produces unreliable results for both IPs and EAs while CAS strongly underestimates the electron affinities. This is also true for the reorganization energies where restricted B3LYP produces qualitatively incorrect results. Doping changes the reorganization energy of the nanoribbons; the hole reorganization energy is generally higher than the corresponding electron reorganization energy due to the participation of nitrogen atoms in the stabilization of the positive charge.

Stability, electronic structures and thermoelectric properties of binary Zn–Sb materials

DOE PAGES

He, Xin; Fu, Yuhao; Singh, David J.; ...

2016-11-03

We report first principles studies of the binary Zn–Sb phases in relation to thermoelectric properties and chemical stability. We identify the unknown structure of the Zn 3Sb 2 phase using particle swarm optimization, finding a tetragonal structure different from the hexagonal Mg 3Sb 2 and the hexagonal or cubic Ca 3Sb 2 phases. All the phases are found to be semiconducting with bandgaps in the range of 0.06–0.77 eV. This semiconducting behavior is understood in Zintl terms as a balance between the Zn:Sb and Sb 3-:½(Sb 2) 4- ratios in the stable crystal structures. With the exception of Zn 3Sbmore » 2, which has a small gap, all the compounds have electronic properties favorable for thermoelectric performance.« less

New frontiers in water purification: highly stable amphopolycarboxyglycinate-stabilized Ag-AgCl nanocomposite and its newly discovered potential

NASA Astrophysics Data System (ADS)

Krutyakov, Yurii A.; Zherebin, Pavel M.; Kudrinskiy, Alexey A.; Zubavichus, Yan V.; Presniakov, Mikhail Yu; Yapryntsev, Alexey D.; Karabtseva, Anastasia V.; Mikhaylov, Dmitry M.; Lisichkin, Georgii V.

2016-09-01

A simple synthetic procedure for high-stable dispersions of porous composite Ag/AgCl nanoparticles stabilized with amphoteric surfactant sodium tallow amphopolycarboxyglycinate has been proposed for the first time. The prepared samples were characterized by UV-vis spectroscopy, x-ray powder diffraction (XRD), x-ray photoelectron spectroscopy, small area electron diffraction (SAED), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electron probe micro-analysis. In addition, measurements (carried out at the Kurchatov synchrotron radiation source stations) of the Ag K-edge extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge structure (XANES) spectra and XRD of the prepared nanoparticles have been performed. The obtained results suggest that small-sized Ag clusters are homogeneously distributed in the mass of the AgCl nanoparticle (~80 nm) formed during the synthesis. The Ag/AgCl dispersion demonstrates photocatalytic activity (with respect to methyl orange) and high bactericidal activity against E. coli. This activity is superior to the activity of both Ag and AgCl nanoparticles stabilized by the same surfactant. Thus, porous composite Ag/AgCl nanoparticles can be used as a multifunctional agent that is able to remove both pollutants and bacterium from water.

Equivalence of electronic and mechanical stresses in structural phase stabilization: A case study of indium wires on Si(111)

NASA Astrophysics Data System (ADS)

Kim, Sun-Woo; Kim, Hyun-Jung; Ming, Fangfei; Jia, Yu; Zeng, Changgan; Cho, Jun-Hyung; Zhang, Zhenyu

2015-05-01

It was recently proposed that the stress state of a material can also be altered via electron or hole doping, a concept termed electronic stress (ES), which is different from the traditional mechanical stress (MS) due to lattice contraction or expansion. Here we demonstrate the equivalence of ES and MS in structural stabilization, using In wires on Si(111) as a prototypical example. Our systematic density-functional theory calculations reveal that, first, for the same degrees of carrier doping into the In wires, the ES of the high-temperature metallic 4 ×1 structure is only slightly compressive, while that of the low-temperature insulating 8 ×2 structure is much larger and highly anisotropic. As a consequence, the intrinsic energy difference between the two phases is significantly reduced towards electronically phase-separated ground states. Our calculations further demonstrate quantitatively that such intriguing phase tunabilities can be achieved equivalently via lattice-contraction induced MS in the absence of charge doping. We also validate the equivalence through our detailed scanning tunneling microscopy experiments. The present findings have important implications for understanding the underlying driving forces involved in various phase transitions of simple and complex systems alike.

Gold nanoparticle assemblies stabilized by bis(phthalocyaninato)lanthanide(III) complexes through van der Waals interactions

NASA Astrophysics Data System (ADS)

Noda, Yuki; Noro, Shin-Ichiro; Akutagawa, Tomoyuki; Nakamura, Takayoshi

2014-01-01

Gold nanoparticle assemblies possess diverse application potential, ranging from industrial nanotechnology to medical biotechnology. Because the structures and properties of assemblies are directly affected by the stabilization mechanism between the organic molecules serving as protecting ligands and the gold nanoparticle surface, it is crucial to find and investigate new stabilization mechanisms. Here, we report that π-conjugated phthalocyanine rings can serve as stabilizing ligands for gold nanoparticles. Bis(phthalocyaninato)lutetium(III) (LuPc2) or bis(phthalocyaninato)terbium(III) (TbPc2), even though complex, do not have specific binding units and stabilize gold nanoparticles through van der Waals interaction between parallel adsorbed phthalocyanine ligands and the gold nanoparticle surface. AC magnetic measurements and the electron-transport properties of the assemblies give direct evidence that the phthalocyanines are isolated from each other. Each nanoparticle shows weak electronic coupling despite the short internanoparticle distance (~1 nm), suggesting Efros-Shklovskii-type variable-range hopping and collective single-electron tunnelling behaviours.

Enhancing the performance of tungsten doped InZnO thin film transistors via sequential ambient annealing

NASA Astrophysics Data System (ADS)

Park, Hyun-Woo; Song, Aeran; Kwon, Sera; Choi, Dukhyun; Kim, Younghak; Jun, Byung-Hyuk; Kim, Han-Ki; Chung, Kwun-Bum

2018-03-01

This study suggests a sequential ambient annealing process as an excellent post-treatment method to enhance the device performance and stability of W (tungsten) doped InZnO thin film transistors (WIZO-TFTs). Sequential ambient annealing at 250 °C significantly enhanced the device performance and stability of WIZO-TFTs, compared with other post-treatment methods, such as air ambient annealing and vacuum ambient annealing at 250 °C. To understand the enhanced device performance and stability of WIZO-TFT with sequential ambient annealing, we investigate the correlations between device performance and stability and electronic structures, such as band alignment, a feature of the conduction band, and band edge states below the conduction band. The enhanced performance of WIZO-TFTs with sequential ambient annealing is related to the modification of the electronic structure. In addition, the dominant mechanism responsible for the enhanced device performance and stability of WIZO-TFTs is considered to be a change in the shallow-level and deep-level band edge states below the conduction band.

Thermal stability enhancement of modified carboxymethyl cellulose films using SnO2 nanoparticles.

PubMed

Baniasad, Arezou; Ghorbani, Mohsen

2016-05-01

In this study, in-situ and ex-situ hydrothermal synthesis procedures were applied to synthesize novel CMC/porous SnO2 nanocomposites from rice husk extracted carboxymethyl cellulose (CMC) biopolymer. In addition, the effects of SnO2 nanoparticles on thermal stability of the prepared nanocomposite were specifically studied. Products were investigated in terms of morphology, particle size, chemical structure, crystallinity and thermal stability by using field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and thermogravimetric analysis (TGA), respectively. Presence of characteristic bands in the FTIR spectra of samples confirmed the successful formation of CMC and CMC/SnO2 nanocomposites. In addition, FESEM images revealed four different morphologies of porous SnO2 nanoparticles including nanospheres, microcubes, nanoflowers and olive-like nanoparticles with hollow cores which were formed on CMC. These nanoparticles possessed d-spacing values of 3.35Å. Thermal stability measurements revealed that introduction of SnO2 nanoparticles in the structure of CMC enhanced stability of CMC to 85%. Copyright © 2016 Elsevier B.V. All rights reserved.

Size versus electronic factors in transition metal carbide and TCP phase stability

NASA Astrophysics Data System (ADS)

Pettifor, D. G.; Seiser, B.; Margine, E. R.; Kolmogorov, A. N.; Drautz, R.

2013-09-01

The contributions of atomic size and electronic factors to the structural stability of transition metal carbides and topologically close-packed (TCP) phases are investigated. The hard-sphere model that has been used by Cottrell to rationalize the occurrence of the octahedral and trigonal local coordination polyhedra within the transition metal carbides is shown to have limitations in TiC since density functional theory (DFT) predicts that the second most metastable phase closest to the B1 (NaCl) ground state takes the B? (BN) structure type with 5-atom local coordination polyhedra with very short Ti-C bond lengths. The importance of electronic factors in the TCP phases is demonstrated by DFT predictions that the A15, ? and ? phases are stabilized between groups VI and VII of the elemental transition metals, whereas the ? and Laves phases are destabilized. The origin of this difference is related to the bimodal shape parameter of the electronic density of states by using the bond-order potential expansion of the structural energy within a canonical tight-binding model. The importance of the size factor in the TCP phases is illustrated by the DFT heats of formation for the binary systems Mo-Re, Mo-Ru, Nb-Re and Nb-Ru which show that the ? and Laves phases become more and more stable compared to A15, ? and ? as the size factor increases from Mo-Re through to Nb-Ru.

Structure and electronic absorption spectra of nematogenic alkoxycinnamic acids - a comparative study based on semiempirical and DFT methods.

PubMed

Praveen, Pogula Lakshmi; Ojha, Durga Prasad

2012-04-01

Structure of nematogenic p-n-Alkoxy cinnamic acids (nOCAC) with various alkyl chain carbon atoms (n = 2, 4, 6, 8) has been optimized using density functional B3LYP with 6-31+G (d) basis set using crystallographic geometry as input. Using the optimized geometry, electronic structure of the molecules has been evaluated using the semiempirical methods and DFT calculations. Molecular charge distribution and phase stability of these systems have been analyzed based on Mulliken and Löwdin population analysis. The electronic absorption spectra of nOCAC molecules have been simulated by employing DFT method, semiempirical CNDO/S and INDO/S parameterizations. Two types of calculations have been performed for model systems containing single and double molecules of nOCAC. UV-Visible spectra have been calculated for all single molecules. The UV stability of the molecules has been discussed in light of the electronic transition oscillator strength (f). The dimer complexes of higher homologues (n = 6, 8) have also been reported to enable the comparison between single and double molecules.

Valence State Driven Site Preference in the Quaternary Compound Ca5MgAgGe5: An Electron-Deficient Phase with Optimized Bonding

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

Ponou, Simeon; Lidin, Sven; Zhang, Yuemei

The quaternary phase Ca5Mg0.95Ag1.05(1)Ge5 (3) was synthesized by high-temperature solid-state techniques, and its crystal structure was determined by single-crystal diffraction methods in the orthorhombic space group Pnma – Wyckoff sequence c12 with a = 23.1481(4) Å, b = 4.4736(1) Å, c = 11.0128(2) Å, V = 1140.43(4) Å3, Z = 4. The crystal structure can be described as linear intergrowths of slabs cut from the CaGe (CrB-type) and the CaMGe (TiNiSi-type; M = Mg, Ag) structures. Hence, 3 is a hettotype of the hitherto missing n = 3 member of the structure series with the general formula R2+nT2X2+n, previously describedmore » with n = 1, 2, and 4. The member with n = 3 was predicted in the space group Cmcm – Wyckoff sequence f5c2. The experimental space group Pnma (in the nonstandard setting Pmcn) corresponds to a klassengleiche symmetry reduction of index two of the predicted space group Cmcm. This transition originates from the switching of one Ge and one Ag position in the TiNiSi-related slab, a process that triggers an uncoupling of each of the five 8f sites in Cmcm into two 4c sites in Pnma. The Mg/Ag site preference was investigated using VASP calculations and revealed a remarkable example of an intermetallic compound for which the electrostatic valency principle is a critical structure-directing force. The compound is deficient by one valence electron according to the Zintl concept, but LMTO electronic structure calculations indicate electronic stabilization and overall bonding optimization in the polyanionic network. Other stability factors beyond the Zintl concept that may account for the electronic stabilization are discussed.« less

Structure and stability of CaH 2 surfaces: on the possibility of electron-rich surfaces in metal hydrides for catalysis

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

Ong, Phuong-Vu; Johnson, Lewis E.; Hosono, Hideo

Structure, thermodynamic stability, and electronic properties of CaH 2 surfaces in (001),(110), and (111) crystallographic orientations are investigated using ab initio modeling. We show that stoichiometric surfaces terminated with a hydrogen atomic plane are the most energetically favorable and discuss properties of hydrogen vacancies (VH) at these surfaces. The average calculated work function of the most stable pristine surfaces (~5.2 eV) is in agree-ment with experimental data for powder samples. Neutral hydrogen vacancies host localized electrons and induce defect states in the band gap, thereby shifting the effective work function to much lower values of ~2.7 eV. Surface VH aremore » predicted to aggregate into dimers and form electron-rich centers (e -)Ca 2+(e -) stable to over 800 K. These results suggest that hydrogen-deficient surfaces of CaH 2 can host a large concentration of localized electrons and, thus, give rise to new catalytic functionalities involving electron transfer between the surface, catalysts supported on it, and reacting species.« less

Thermal and aqueous stability improvement of graphene oxide enhanced diphenylalanine nanocomposites

NASA Astrophysics Data System (ADS)

Ryan, Kate; Neumayer, Sabine M.; Maraka, Harsha Vardhan R.; Buchete, Nicolae-Viorel; Kholkin, Andrei L.; Rice, James H.; Rodriguez, Brian J.

2017-12-01

Nanocomposites of diphenylalanine (FF) and carbon based materials provide an opportunity to overcome drawbacks associated with using FF micro- and nanostructures in nanobiotechnology applications, in particular their poor structural stability in liquid solutions. In this study, FF/graphene oxide (GO) composites were found to self-assemble into layered micro- and nanostructures, which exhibited improved thermal and aqueous stability. Dependent on the FF/GO ratio, the solubility of these structures was reduced to 35.65% after 30 min as compared to 92.4% for pure FF samples. Such functional nanocomposites may extend the use of FF structures to e.g. biosensing, electrochemical, electromechanical or electronic applications.

Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

NASA Astrophysics Data System (ADS)

Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

2017-05-01

Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

Effect of Pressure on the Stability and Electronic Structure of ZnO0.5S0.5 and ZnO0.5Se0.5

NASA Astrophysics Data System (ADS)

Manotum, R.; Klinkla, R.; Phaisangittisakul, N.; Pinsook, U.; Bovornratanaraks, T.

2017-12-01

Structures and high-pressure phase transitions in ZnO0.5S0.5 and ZnO0.5Se0.5 have been investigated using density functional theory calculations. The previously proposed structures of ZnO0.5S0.5 and ZnO0.5Se0.5 which are chalcopyrite ( I\\bar{4}2d ), rocksalt ( Fm3m ), wurtzite ( P63 mc ) and CuAu-I ( P\\bar{4}m2 ) have been fully investigated. Stabilities of these materials have been systematically studied up to 40 GPa using various approaches. We have confirmed the stability of the chalcopyrite structure up to 30 GPa for which the CuAu-I structure has been previously proposed. However, our calculation revealed that CuAu-I is not a stable structure under 32 GPa and 33 GPa for both ZnO0.5S0.5 and ZnO0.5Se0.5, respectively, which could explain the failure in several attempts to fabricate these materials under such conditions. We have also examined the pressure-dependence of the bandgap and electronic structure up to 30 GPa. We can conclude from our PDOS analysis that the applied pressure does not change the atomic state characters of electronic states near the top of valence and the bottom of conduction bands, but mainly modifies the dominant Zn-3d atomic state of the deep Bloch state at -1 eV below Fermi level.

Quantum dots in single electron transistors with ultrathin silicon-on-insulator structures

NASA Astrophysics Data System (ADS)

Ihara, S.; Andreev, A.; Williams, D. A.; Kodera, T.; Oda, S.

2015-07-01

We report on fabrication and transport properties of lithographically defined single quantum dots (QDs) in single electron transistors with ultrathin silicon-on-insulator (SOI) substrate. We observed comparatively large charging energy E C ˜ 20 meV derived from the stability diagram at a temperature of 4.2 K. We also carried out three-dimensional calculations of the capacitance matrix and transport properties through the QD for the real structure geometry and found an excellent quantitative agreement with experiment of the calculated main parameters of stability diagram (charging energy, period of Coulomb oscillations, and asymmetry of the diamonds). The obtained results confirm fabrication of well-defined integrated QDs as designed with ultrathin SOI that makes it possible to achieve relatively large QD charging energies, which is useful for stable and high temperature operation of single electron devices.

3D morphology of Au and Au@Ag nanobipyramids

NASA Astrophysics Data System (ADS)

Burgin, Julien; Florea, Ileana; Majimel, Jérôme; Dobri, Adam; Ersen, Ovidiu; Tréguer-Delapierre, Mona

2012-02-01

The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance.The morphologies of Au and Au@Ag nanobipyramids were investigated using electron tomography. The 3D reconstruction reveals that the Au bipyramids have an irregular six-fold twinning structure with highly stepped dominant {151} facets. These short steps/edges stabilized via surface adsorbed CTAB favor the growth of silver on the lateral facets leading to strong blue shifts in longitudinal plasmon surface resonance. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11454b

First-principles study of the stability, magnetic and electronic properties of Fe and Co monoatomic chains encapsulated into copper nanotube

NASA Astrophysics Data System (ADS)

Ma, Liang-Cai; Ma, Ling; Zhang, Jian-Min

2017-07-01

By using first-principles calculations based on density-functional theory, the stability, magnetic and electronic properties of Fe and Co monoatomic chains encapsulated into copper nanotube are systematically investigated. The binding energies of the hybrid structures are remarkably higher than those of corresponding freestanding TM chains, indicating the TM chains are significantly stabilized after encapsulating into copper nanotube. The formed bonds between outer Cu and inner TM atoms show some degree of covalent bonding character. The magnetic ground states of Fe@CuNW and Co@CuNW hybrid structures are ferromagnetic, and both spin and orbital magnetic moments of inner TM atoms have been calculated. The magnetocrystalline anisotropy energies (MAE) of the hybrid structures are enhanced by nearly fourfold compared to those of corresponding freestanding TM chains, indicating that the hybrid structures can be used in ultrahigh density magnetic storage. Furthermore, the easy magnetization axis switches from that along the axis in freestanding Fe chain to that perpendicular to the axis in Fe@CuNT hybrid structure. The large spin polarization at the Fermi level also makes the hybrid systems interesting as good potential materials for spintronic devices.

Structural, electronic and elastic properties of heavy fermion YbRh2 Laves phase compound

NASA Astrophysics Data System (ADS)

Pawar, Harsha; Shugani, Mani; Aynyas, Mahendra; Sanyal, Sankar P.

2018-05-01

The structural, electronic and elastic properties of YbRh2 Laves phase intermetallic compound which crystallize in cubic (MgCu2-type) structure have been investigated using ab-initio full potential linearized augmented plane wave (FP- LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B') are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for this compound which obeys the stability criteria for cubic system.

Cluster molecular orbital description of the electronic structures of mixed-valence iron oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1986-01-01

A molecular orbital description, based on spin-unrestricted X??-scattered wave calculations, is given for the electronic structures of mixed valence iron oxides and silicates. The cluster calculations show that electron hopping and optical intervalence charge-transger result from weak FeFe bonding across shared edges of FeO6 coordination polyhedra. In agreement with Zener's double exchange model, FeFe bonding is found to stabilize ferromagnetic coupling between Fe2+ and Fe3+ cations. ?? 1986.

The Role of Phase Changes in TiO2/Pt/TiO2 Filaments

NASA Astrophysics Data System (ADS)

Bíró, Ferenc; Hajnal, Zoltán; Dücső, Csaba; Bársony, István

2018-04-01

This work analyses the role of phase changes in TiO2/Pt/TiO2 layer stacks for micro-heater application regarding their stability and reliable operation. The polycrystalline Pt layer wrapped in a TiO2 adhesion layer underwent a continuous recrystallisation in a self-heating operation causing a drift in the resistance ( R) versus temperature ( T) performance. Simultaneously, the TiO2 adhesion layer also deteriorates at high temperature by phase changes from amorphous to anatase and rutile crystallite formation, which not only influences the Pt diffusion in different migration phenomena, but also reduces the cross section of the Pt heater wire. Thorough scanning electron microscopy, energy dispersive spectroscopy, cross-sectional transmission electron microscopy (XTEM) and electron beam diffraction analysis of the structures operated at increasing temperature revealed the elemental structural processes leading to the instabilities and the accelerated degradation, resulting in rapid breakdown of the heater wire. Owing to stability and reliability criteria, the conditions for safe operation of these layer structures could be determined.

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

DOE PAGES

Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel; ...

2017-01-06

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li 1.2Ni 0.13Mn 0.54Co 0.13O 2 crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-definedmore » model system of battery materials. Here, we report the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. Finally, the intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.« less

Insights into geometries, stabilities, electronic structures, reactivity descriptors, and magnetic properties of bimetallic Nim Cun-m (m = 1, 2; n = 3-13) clusters: Comparison with pure copper clusters.

PubMed

Singh, Raman K; Iwasa, Takeshi; Taketsugu, Tetsuya

2018-05-25

A long-range corrected density functional theory (LC-DFT) was applied to study the geometric structures, relative stabilities, electronic structures, reactivity descriptors and magnetic properties of the bimetallic NiCu n -1 and Ni 2 Cu n -2 (n = 3-13) clusters, obtained by doping one or two Ni atoms to the lowest energy structures of Cu n , followed by geometry optimizations. The optimized geometries revealed that the lowest energy structures of the NiCu n -1 and Ni 2 Cu n -2 clusters favor the Ni atom(s) situated at the most highly coordinated position of the host copper clusters. The averaged binding energy, the fragmentation energies and the second-order energy differences signified that the Ni doped clusters can continue to gain an energy during the growth process. The electronic structures revealed that the highest occupied molecular orbital and the lowest unoccupied molecular orbital energies of the LC-DFT are reliable and can be used to predict the vertical ionization potential and the vertical electron affinity of the systems. The reactivity descriptors such as the chemical potential, chemical hardness and electrophilic power, and the reactivity principle such as the minimum polarizability principle are operative for characterizing and rationalizing the electronic structures of these clusters. Moreover, doping of Ni atoms into the copper clusters carry most of the total spin magnetic moment. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

Discovery of a Superconducting High-Entropy Alloy

NASA Astrophysics Data System (ADS)

Koželj, P.; Vrtnik, S.; Jelen, A.; Jazbec, S.; Jagličić, Z.; Maiti, S.; Feuerbacher, M.; Steurer, W.; Dolinšek, J.

2014-09-01

High-entropy alloys (HEAs) are multicomponent mixtures of elements in similar concentrations, where the high entropy of mixing can stabilize disordered solid-solution phases with simple structures like a body-centered cubic or a face-centered cubic, in competition with ordered crystalline intermetallic phases. We have synthesized an HEA with the composition Ta34Nb33Hf8Zr14Ti11 (in at. %), which possesses an average body-centered cubic structure of lattice parameter a =3.36 Å. The measurements of the electrical resistivity, the magnetization and magnetic susceptibility, and the specific heat revealed that the Ta34Nb33Hf8Zr14Ti11 HEA is a type II superconductor with a transition temperature Tc≈7.3 K, an upper critical field μ0Hc2≈8.2 T, a lower critical field μ0Hc1≈32 mT, and an energy gap in the electronic density of states (DOS) at the Fermi level of 2Δ ≈2.2 meV. The investigated HEA is close to a BCS-type phonon-mediated superconductor in the weak electron-phonon coupling limit, classifying it as a "dirty" superconductor. We show that the lattice degrees of freedom obey Vegard's rule of mixtures, indicating completely random mixing of the elements on the HEA lattice, whereas the electronic degrees of freedom do not obey this rule even approximately so that the electronic properties of a HEA are not a "cocktail" of properties of the constituent elements. The formation of a superconducting gap contributes to the electronic stabilization of the HEA state at low temperatures, where the entropic stabilization is ineffective, but the electronic energy gain due to the superconducting transition is too small for the global stabilization of the disordered state, which remains metastable.

Mechanical and thermal stability of graphene and graphene-based materials

NASA Astrophysics Data System (ADS)

Galashev, A. E.; Rakhmanova, O. R.

2014-10-01

Graphene has rapidly become one of the most popular materials for technological applications and a test material for new condensed matter ideas. This paper reviews the mechanical properties of graphene and effects related to them that have recently been discovered experimentally or predicted theoretically or by simulation. The topics discussed are of key importance for graphene's use in integrated electronics, thermal materials, and electromechanical devices and include the following: graphene transformation into other sp^2 hybridization forms; stability to stretching and compression; ion-beam-induced structural modifications; how defects and graphene edges affect the electronic properties and thermal stability of graphene and related composites.

Allotropes of Phosphorus with Remarkable Stability and Intrinsic Piezoelectricity

NASA Astrophysics Data System (ADS)

Li, Zhenqing; He, Chaoyu; Ouyang, Tao; Zhang, Chunxiao; Tang, Chao; Römer, Rudolf A.; Zhong, Jianxin

2018-04-01

We construct a class of two-dimensional (2D) phosphorus allotropes by assembling a previously proposed ultrathin metastable phosphorus nanotube into planar structures in different stacking orientations. Based on first-principles methods, the structures, stabilities, and fundamental electronic properties of these allotropes are systematically investigated. Our results show that these 2D van der Waals phosphorene allotropes possess remarkable stabilities due to the strong intertube van der Waals interactions, which cause an energy release of about 30 - 70 meV /atom , depending on their stacking details. Most of them are confirmed to be energetically more favorable than the experimentally viable α -P and β -P . Three of them, showing a relatively higher probability of being synthesized in the future, are further confirmed to be dynamically stable semiconductors with strain-tunable band gaps and intrinsic piezoelectricity, which may have potential applications in nanosized sensors, piezotronics, and energy harvesting in portable electronic nanodevices.

Ultrastructure Processing and Environmental Stability of Advanced Structural and Electronic Materials.

DTIC Science & Technology

1983-03-01

network dissolution, electron beam simulated desorption, electron signal decay, oxidation, oxide layer , growth kinetics, silicon carbide, assivation...surface layers on silicate glasses are reviewed. A type IIIB glass surface is proposed. The mechanisms of hydrothermal attack of two phase lithia...method to make reliable lifetime predictions. Use of electron beam techniques is essential for understanding surface layers formed on glasses (Section III

Investigation of Thermal Stability of P2-NaxCoO2 Cathode Materials for Sodium Ion Batteries Using Real-Time Electron Microscopy.

PubMed

Hwang, Sooyeon; Lee, Yongho; Jo, Eunmi; Chung, Kyung Yoon; Choi, Wonchang; Kim, Seung Min; Chang, Wonyoung

2017-06-07

Here, we take advantage of in situ transmission electron microscopy (TEM) to investigate the thermal stability of P2-type Na x CoO 2 cathode materials for sodium ion batteries, which are promising candidates for next-generation lithium ion batteries. A double-tilt TEM heating holder was used to directly characterize the changes in the morphology and the crystallographic and electronic structures of the materials with increase in temperature. The electron diffraction patterns and the electron energy loss spectra demonstrated the presence of cobalt oxides (Co 3 O 4 , CoO) and even metallic cobalt (Co) at higher temperatures as a result of reduction of Co ions and loss of oxygen. The bright-field TEM images revealed that the surface of Na x CoO 2 becomes porous at high temperatures. Higher cutoff voltages result in degrading thermal stability of Na x CoO 2 . The observations herein provide a valuable insight that thermal stability is one of the important factors to be considered in addition to the electrochemical properties when developing new electrode materials for novel battery systems.

Investigation of Thermal Stability of P2–Na xCoO 2 Cathode Materials for Sodium Ion Batteries Using Real-Time Electron Microscopy

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

Hwang, Sooyeon; Lee, Yongho; Jo, Eunmi

In this paper, we take advantage of in situ transmission electron microscopy (TEM) to investigate the thermal stability of P2-type Na xCoO 2 cathode materials for sodium ion batteries, which are promising candidates for next-generation lithium ion batteries. A double-tilt TEM heating holder was used to directly characterize the changes in the morphology and the crystallographic and electronic structures of the materials with increase in temperature. The electron diffraction patterns and the electron energy loss spectra demonstrated the presence of cobalt oxides (Co 3O 4, CoO) and even metallic cobalt (Co) at higher temperatures as a result of reduction ofmore » Co ions and loss of oxygen. The bright-field TEM images revealed that the surface of Na xCoO 2 becomes porous at high temperatures. Higher cutoff voltages result in degrading thermal stability of Na xCoO 2. Finally, the observations herein provide a valuable insight that thermal stability is one of the important factors to be considered in addition to the electrochemical properties when developing new electrode materials for novel battery systems.« less

Investigation of Thermal Stability of P2–Na xCoO 2 Cathode Materials for Sodium Ion Batteries Using Real-Time Electron Microscopy

DOE PAGES

Hwang, Sooyeon; Lee, Yongho; Jo, Eunmi; ...

2017-05-11

In this paper, we take advantage of in situ transmission electron microscopy (TEM) to investigate the thermal stability of P2-type Na xCoO 2 cathode materials for sodium ion batteries, which are promising candidates for next-generation lithium ion batteries. A double-tilt TEM heating holder was used to directly characterize the changes in the morphology and the crystallographic and electronic structures of the materials with increase in temperature. The electron diffraction patterns and the electron energy loss spectra demonstrated the presence of cobalt oxides (Co 3O 4, CoO) and even metallic cobalt (Co) at higher temperatures as a result of reduction ofmore » Co ions and loss of oxygen. The bright-field TEM images revealed that the surface of Na xCoO 2 becomes porous at high temperatures. Higher cutoff voltages result in degrading thermal stability of Na xCoO 2. Finally, the observations herein provide a valuable insight that thermal stability is one of the important factors to be considered in addition to the electrochemical properties when developing new electrode materials for novel battery systems.« less

Phase stability and electronic structure of UMo2Al20: A first-principles study

NASA Astrophysics Data System (ADS)

Liu, Peng-Chuang; Xian, Ya-Jiang; Wang, Xin; Zhang, Yu-Ting; Zhang, Peng-Cheng

2017-09-01

In this paper, the phase stability of UMo2Al20 was explored using cluster formula in combination with first-principles calculations. Cluster formula analysis uncovered that the compound was composed of two principal clusters, i.e. [Mo-Al12] and [U-Al16]. The electronic interactions between U, Mo and Al atoms in this compound were discussed using elastic property, Bader charges and energy-resolved local bonding analysis, as well as the electronic interactions between Mo and Al atoms in [Mo-Al12] cluster and between U and Al atoms in [U-Al16] cluster. It revealed that UMo2Al20 satisfied the mechanical stability criterion for cubic system, and exhibited near ionic bonding character with weak bonding directionality. The calculations within both standard DFT and HSE frameworks demonstrated that U and Al atoms acted as an electron donor while Mo atoms acted as electron acceptor. The intrinsic stability of UMo2Al20 mainly stemmed from the bonding states of Mo-Al bonds and Al-Al bonds in [Mo-Al12] cluster. These calculations provide a further insight on the CeCr2Al20-type ternary compounds.

Structural stability and electronic behaviors of Co1-xOsxSi and macroscopic magnetic susceptibilities of CoSi and OsSi: GGA-PBEsol, GW-approximation and QTAIM investigations

NASA Astrophysics Data System (ADS)

Bouafia, H.; Sahli, B.; Timaoui, M. A.; Djebour, B.; Hiadsi, S.; Abidri, B.

2018-02-01

The present work represents a theoretical investigation based on FP-(L)APW + lo method of structural properties, mechanical stability and electronic properties of Co1-xOsxSi as well as the macroscopic magnetic susceptibilities of CoSi and OsSi. The structural properties such as cell parameter, bulk modulus, internal parameters and total energy of non-magnetic NM, ferromagnetic FM and antiferromagnetic AFM phases were predicted by GGA-PBEsol semilocal functional. The obtained results for CoSi and OsSi are in good agreement with those found previously. The spin, orbital and total macroscopic magnetic susceptibilities of CoSi and OsSi have been estimated and confirmed that these compounds are diamagnetic. The total energy of the ferromagnetic phase of Co1-xOsxSi (with x = 0.25, 0.5 and 0.75) is the lowest indicating that they are ferromagnetic materials. The generalized stability criteria indicate that Co1-xOsxSi maintain their mechanical stabilities under a hydrostatic pressure less than 10 GPa. The electronic properties calculated by GW-approximation indicate that CoSi and Co1-xOsxSi (with x = 0.25, 0.50 and 0.75) are semimetals whereas OsSi is a semiconductor with a pseudo-direct band-gap. The topological analysis by QTAIM and the charge density plots indicate that the strong covalent character is predominant for Cosbnd Si, Ossbnd Si and Cosbnd Os bonds.

Design and Synthesis of Novel Block Copolymers for Efficient Opto-Electronic Applications

NASA Technical Reports Server (NTRS)

Sun, Sam-Shajing; Fan, Zhen; Wang, Yiqing; Taft, Charles; Haliburton, James; Maaref, Shahin

2002-01-01

It has been predicted that nano-phase separated block copolymer systems containing electron rich donor blocks and electron deficient acceptor blocks may facilitate the charge carrier separation and migration in organic photovoltaic devices due to improved morphology in comparison to polymer blend system. This paper presents preliminary data describing the design and synthesis of a novel Donor-Bridge-Acceptor (D-B-A) block copolymer system for potential high efficient organic optoelectronic applications. Specifically, the donor block contains an electron donating alkyloxy derivatized polyphenylenevinylene (PPV), the acceptor block contains an electron withdrawing alkyl-sulfone derivatized polyphenylenevinylene (PPV), and the bridge block contains an electronically neutral non-conjugated aliphatic hydrocarbon chain. The key synthetic strategy includes the synthesis of each individual block first, then couple the blocks together. While the donor block stabilizes and facilitates the transport of the holes, the acceptor block stabilizes and facilitates the transport of the electrons, the bridge block is designed to hinder the probability of electron-hole recombination. Thus, improved charge separation and stability are expected with this system. In addition, charge migration toward electrodes may also be facilitated due to the potential nano-phase separated and highly ordered block copolymer ultra-structure.

Electronic and thermodynamic properties of layered Hf2Sfrom first-principles calculations

NASA Astrophysics Data System (ADS)

Nandadasa, Chandani; Yoon, Mina; Kim, Seong-Gon; Erwin, Steve; Kim, Sungho; Kim, Sung Wng; Lee, Kimoon

Theoretically we explored two stable phases of inorganic fullerene-like structure of the layered dihafnium sulfide (Hf2 S) . We investigated structural and electronic properties of the two phases of Hf2 S by using first-principles calculations. Our calculation identifies experimentally observed anti-NbS2 structure of Hf2 S . Our electronic calculation results indicate that the density of states of anti- NbS2 structure of Hf2 S at fermi level is less than that of the other phase of Hf2 S . To study the relative stability of different phases at finite temperature Helmholtz free energies of two phases are obtained using density functional theory and density functional perturbation theory. The free energy of the anti-NbS2 structure of Hf2 S always lies below the free energy of the other phase by confirming the most stable structure of Hf2 S . The phonon dispersion, phonon density of states including partial density of states and total density of states are obtained within density functional perturbation theory. Our calculated zero-pressure phonon dispersion curves confirm that the thermodynamic stability of Hf2 S structures. For further investigation of thermodynamic properties, the temperature dependency of thermal expansion, heat capacities at constant pressure and volume are evaluated within the quasiharmonic approximations (QHA).

Spherical nitrogen-doped hollow mesoporous carbon as an efficient bifunctional electrocatalyst for Zn-air batteries

NASA Astrophysics Data System (ADS)

Hadidi, Lida; Davari, Elaheh; Iqbal, Muhammad; Purkait, Tapas K.; Ivey, Douglas G.; Veinot, Jonathan G. C.

2015-12-01

Materials based upon porous carbon have gained considerable attention due to their high surface area, electric conductivity, thermal and chemical stability, low density, and availability. These superior properties make them ideal for diverse applications. Doping these carbon nanostructures holds promise of designing the properties of these structures and opening the door to practical applications. Herein, we report the preparation of hollow N-doped mesoporous carbon (HMC) spheres fabricated via polymerization and carbonization of dopamine on a sacrificial spherical SiO2 template that is removed upon hydrofluoric acid etching. The morphology and structural features of these HMCs were evaluated using scanning electron microscopy and transmission electron microscopy and the N-doping (7.1 at%) was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen reduction/evolution reaction (ORR/OER) performance of N-doped HMC was evaluated using rotating disk electrode (RDE) voltammetry in an alkaline electrolyte. N-doped HMC demonstrated a high ORR onset potential of -0.055 V (vs. Hg/HgO) and excellent stability. The outstanding bifunctional activity was implemented in a practical Zn-air battery (ZAB), which exhibited a small charge-discharge voltage polarization of 0.89 V and high stability over repeated cycling.Materials based upon porous carbon have gained considerable attention due to their high surface area, electric conductivity, thermal and chemical stability, low density, and availability. These superior properties make them ideal for diverse applications. Doping these carbon nanostructures holds promise of designing the properties of these structures and opening the door to practical applications. Herein, we report the preparation of hollow N-doped mesoporous carbon (HMC) spheres fabricated via polymerization and carbonization of dopamine on a sacrificial spherical SiO2 template that is removed upon hydrofluoric acid etching. The morphology and structural features of these HMCs were evaluated using scanning electron microscopy and transmission electron microscopy and the N-doping (7.1 at%) was confirmed by X-ray photoelectron spectroscopy (XPS). The oxygen reduction/evolution reaction (ORR/OER) performance of N-doped HMC was evaluated using rotating disk electrode (RDE) voltammetry in an alkaline electrolyte. N-doped HMC demonstrated a high ORR onset potential of -0.055 V (vs. Hg/HgO) and excellent stability. The outstanding bifunctional activity was implemented in a practical Zn-air battery (ZAB), which exhibited a small charge-discharge voltage polarization of 0.89 V and high stability over repeated cycling. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06028a

Improving the oxidation resistance and stability of Ag nanoparticles by coating with multilayered reduced graphene oxide

NASA Astrophysics Data System (ADS)

Li, Yahui; Zhang, Huayu; Wu, Bowen; Guo, Zhuo

2017-12-01

A kind of coating nanostructure, Ag nanoparticles coated with multilayered reduced graphene oxide (RGO), is fabricated by employing a three-step reduction method in an orderly manner, which is significantly different from the conventional structures that are simply depositing or doping with Ag nanoparticles on RGO via chemical reduction. The as-prepared nanostructure is investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), selected-area electronic diffraction (SEAD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). The results show that the obtained Ag/RGO nanostructure is observed to be a perfect coating structure with well dispersed Ag particles, which is responsible for the remarkable oxidation resistance. The results of XPS spectra indicate the content of metallic Ag is far greater than that of Ag oxides despite of prolonged exposure to the air, which fully demonstrate the excellent stability of thus coating nanostructure.

Photoelectron spectroscopy of the bis(dithiolene) anions [M(mnt)2]n- (M = Fe - Zn; n = 1, 2): changes in electronic structure with variation of metal center and with oxidation.

PubMed

Waters, Tom; Wang, Xue-Bin; Woo, Hin-Koon; Wang, Lai-Sheng

2006-07-24

A detailed understanding of the electronic structures of transition metal bis(dithiolene) centers is important in the context of their interesting redox, magnetic, and optical properties. The electronic structures of the series [M(mnt)2]n- (M = Fe - Zn; mnt = 1,2-S2C2(CN)2; n = 1, 2) were examined by a combination of photodetachment photoelectron spectroscopy and density functional theory calculations, providing insights into changes in electronic structure with variation of the metal center and with oxidation. Significant changes were observed for the dianions [M(mnt)2]2- due to stabilization of the metal 3d levels from Fe to Zn and the transition from square-planar to tetrahedral coordination about the metal center (Fe-Ni, D(2h) --> Cu D2 --> Zn, D(2d). Changes with oxidation from [M(mnt)2]2- to [M(mnt)2]1- were largely dependent on the nature of the redox-active orbital in the couple [M(mnt)2](2-/1-). In particular, the first detachment feature for [Fe(mnt)2]2- originated from a metal-based orbital (Fe(II) --> Fe(III)) while that for [Fe(mnt)2]1- originated from a ligand-based orbital, a consequence of stabilization of Fe 3d levels in the latter. In contrast, the first detachment feature for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- originated from the same ligand-based orbital in both cases, a result of occupied Ni 3d levels being stabilized relative those of Fe 3d and occurring below the highest energy occupied ligand-based orbital for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- . The combined data illustrate the subtle interplay between metal- and ligand-based redox chemistry in these species and demonstrate changes in their electronic structures with variation of metal center, oxidation, and coordination geometry.

Correlating electronic transport to atomic structures in self-assembled quantum wires.

PubMed

Qin, Shengyong; Kim, Tae-Hwan; Zhang, Yanning; Ouyang, Wenjie; Weitering, Hanno H; Shih, Chih-Kang; Baddorf, Arthur P; Wu, Ruqian; Li, An-Ping

2012-02-08

Quantum wires, as a smallest electronic conductor, are expected to be a fundamental component in all quantum architectures. The electronic conductance in quantum wires, however, is often dictated by structural instabilities and electron localization at the atomic scale. Here we report on the evolutions of electronic transport as a function of temperature and interwire coupling as the quantum wires of GdSi(2) are self-assembled on Si(100) wire-by-wire. The correlation between structure, electronic properties, and electronic transport are examined by combining nanotransport measurements, scanning tunneling microscopy, and density functional theory calculations. A metal-insulator transition is revealed in isolated nanowires, while a robust metallic state is obtained in wire bundles at low temperature. The atomic defects lead to electron localizations in isolated nanowire, and interwire coupling stabilizes the structure and promotes the metallic states in wire bundles. This illustrates how the conductance nature of a one-dimensional system can be dramatically modified by the environmental change on the atomic scale. © 2012 American Chemical Society

Atomically thin transition metal layers: Atomic layer stabilization and metal-semiconductor transition

NASA Astrophysics Data System (ADS)

Hwang, Jeongwoon; Oh, Young Jun; Kim, Jiyoung; Sung, Myung Mo; Cho, Kyeongjae

2018-04-01

We have performed first-principle calculations to explore the possibility of synthesizing atomically thin transition metal (TM) layers. Buckled structures as well as planar structures of elemental 2D TM layers result in significantly higher formation energies compared with sp-bonded elemental 2D materials with similar structures, such as silicene and phosphorene. It is shown that the TM layers can be stabilized by surface passivation with HS, C6H5S2, or O, and O passivation is most effective. The surface oxygen passivation can improve stability leading to thermodynamically stable TM monolayers except Au, which is the most non-reactive metal element. Such stabilized TM monolayers also show an electronic structure transition from metallic state of free-standing TM layer to semiconducting O-passivated Mo and W monolayers with band gaps of 0.20-1.38 eV.

Enhancement of the Device Performance and the Stability with a Homojunction-structured Tungsten Indium Zinc Oxide Thin Film Transistor.

PubMed

Park, Hyun-Woo; Song, Aeran; Choi, Dukhyun; Kim, Hyung-Jun; Kwon, Jang-Yeon; Chung, Kwun-Bum

2017-09-14

Tungsten-indium-zinc-oxide thin-film transistors (WIZO-TFTs) were fabricated using a radio frequency (RF) co-sputtering system with two types of source/drain (S/D)-electrode material of conducting WIZO (homojunction structure) and the indium-tin oxide (ITO) (heterojunction structure) on the same WIZO active-channel layer. The electrical properties of the WIZO layers used in the S/D electrode and the active-channel layer were adjusted through oxygen partial pressure during the deposition process. To explain enhancements of the device performance and stability of the homojunction-structured WIZO-TFT, a systematic investigation of correlation between device performance and physical properties at the interface between the active layer and the S/D electrodes such as the contact resistance, surface/interfacial roughness, interfacial-trap density, and interfacial energy-level alignments was conducted. The homojunction-structured WIZO-TFT exhibited a lower contact resistance, smaller interfacial-trap density, and flatter interfacial roughness than the WIZO-TFT with the heterojunction structure. The 0.09 eV electron barrier of the homojunction-structured WIZO-TFT is lower than the 0.21 eV value that was obtained for the heterojunction-structured WIZO-TFT. This reduced electron barrier may be attributed to enhancements of device performance and stability, that are related to the carrier transport.

The structure, stability, and electronic properties of ultra-thin BC2N nanotubes: a first-principles study.

PubMed

Wang, Yue; Zhang, Juan; Huang, Gang; Yao, Xinhua; Shao, Qingyi

2014-12-01

Rapid developments of the silicon electronics industry have close to the physical limits and nanotube materials are the ideal materials to replace silicon for the preparation of next generation electronic devices. Boron-carbon-nitrogen nanotubes (BCNNT) can be formed by joining carbon nanotube (CNT) and boron nitride nanotube (BNNT) segments, and BC2N nanotubes have been widely and deeply studied. Here, we employed first-principles calculations based on density function theory (DFT) to study the structure, stability, and electronic properties of ultra thin (4 Å diameter) BC2N nanotubes. Our results showed that the cross sections of BC2N nanotubes can transform from round to oval when CNT and BNNT segments are parallel to the tube axis. It results when the curvature of BNNT segments become larger than CNT segments. Further, we found the stability of BC2N nanotubes is sensitive to the number of B-N bonds, and the phase segregation of BNNT and CNT segments is energetically favored. We also obtained that all (3,3) BC2N nanotubes are semiconductor, whereas (5,0) BC2N nanotubes are conductor when CNT and BNNT segments are perpendicular to the tube axis; and semiconductor when CNT and BNNT segments are parallel to the tube axis. These electronic properties are abnormal when compared to the relative big ones.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

PubMed

Kong, Fanjie; Hu, Yanfei

2014-03-01

The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

Structural properties and magic structures in hydrogenated finite and infinite silicon nanowires

NASA Astrophysics Data System (ADS)

Zdetsis, A. D.; Koukaras, E. N.; Garoufalis, C. S.

2007-11-01

Unusual effects such as bending and "canting," related with the stability, have been identified by ab initio real-space calculations for hydrogenated silicon nanowires. We have examined in detail the electronic and structural properties of finite and infinite nanowires as a function of length (and width) and have developed stability and bending rules, demonstrating that "magic" wires do not bend. Reconstructed 2×1 nanowires are practically as stable as the magic ones. Our calculations are in good agreement with the experimental data of Ma et al. [Science 299, 1874 (2003).].

Electronic structure and optical properties of metal doped tetraphenylporphyrins

NASA Astrophysics Data System (ADS)

Shah, Esha V.; Roy, Debesh R.

2018-05-01

A density functional scrutiny on the structure, electronic and optical properties of metal doped tetraphenylporphyrins MTPP (M=Fe, Co, Ni) is performed. The structural stability of the molecules is evaluated based on the electronic parameters like HOMO-LUMO gap (HLG), chemical hardness (η) and binding energy of the central metal atom to the molecular frame etc. The computed UltraViolet-Visible (UV-Vis) optical absorption spectra for all the compounds are also compared. The molecular structures reported are the lowest energy configurations. The entire calculations are carried out with a widely reliable functional, viz. B3LYP with a popular basis set which includes a scaler relativistic effect, viz. LANL2DZ.

Structural, Electronic and Elastic Properties of Heavy Fermion YbTM2 (TM= Ir and Pt) Laves Phase Compounds

NASA Astrophysics Data System (ADS)

Pawar, H.; Shugani, M.; Aynyas, M.; Sanyal, S. P.

2018-02-01

The structural, electronic and elastic properties of YbTM2 (TM = Ir and Pt) Laves phase intermetallic compounds which crystallize in cubic (MgCu2-type) structure, have been investigated using ab-initio full potential linearized augmented plane wave (FP-LAPW) method with LDA and LDA+U approximation. The calculated ground state properties such as lattice parameter (a0), bulk modulus (B) and its pressure derivative (B‧) are in good agreement with available experimental and theoretical data. The electronic properties are analyzed from band structures and density of states. Elastic constants are predicted first time for these compounds which obey the stability criteria for cubic system.

Lithium halide monolayers: Structural, electronic and optical properties by first principles study

NASA Astrophysics Data System (ADS)

Safari, Mandana; Maskaneh, Pegah; Moghadam, Atousa Dashti; Jalilian, Jaafar

2016-09-01

Using first principle study, we investigate the structural, electronic and optical properties of lithium halide monolayers (LiF, LiCl, LiBr). In contrast to graphene and other graphene-like structures that form hexagonal rings in plane, these compounds can form and stabilize in cubic shape interestingly. The type of band structure in these insulators is identified as indirect type and ionic nature of their bonds are illustrated as well. The optical properties demonstrate extremely transparent feature for them as a result of wide band gap in the visible range; also their electron transitions are indicated for achieving a better vision on the absorption mechanism in these kinds of monolayers.

Thermal stability of intermetallic phases in Fe-rich Fe-Cr-Ni-Mo alloys

DOE PAGES

Yang, Ying; Tan, Lizhen; Busby, Jeremy T.

2015-06-12

Understanding the stability of precipitate phases in the Fe-rich Fe-Cr-Ni-Mo alloys is critical to the alloy design and application of Mo-containing Austenitic steels. Coupled with thermodynamic modeling, stability of the chi and Laves phases in two Fe-Cr-Ni-Mo alloys were investigated at 1000, 850 and 700 °C for different annealing time. The morphologies, compositions and crystal structures of the matrix and precipitate phases were carefully examined by Scanning Electron Microscopy, Electron Probe Microanalysis, X-ray diffraction and Transmission Electron Microscopy. The two key findings resulted from this work. One is that the chi phase is stable at high temperature and transformed intomore » the Laves phase at low temperature. The other is that both the chi and Laves phases have large solubilites of Cr, Mo and Ni, among which the Mo solubility has a major role on the relative stability of the precipitate phases. The developed thermodynamic models were then applied to evaluating the Mo effect on the stability of precipitate phases in AISI 316 and NF709 alloys.« less

Theory of phase stabilities and bonding mechanisms in stoichiometric and substoichiometric molybdenum carbide

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

Hugosson, H.W.; Eriksson, O.; Nordstroem, L.

1999-10-01

First principles, total energy methods have been applied to predict the relative stabilities of the four experimentally verified MoC phases: the cubic {delta}(NaCl) phase and the three hexagonal {gamma}(WC), {eta} and {gamma}{sup {prime}}(TiAs) phases. The effect of vacancies on the relative stability of these four phases was investigated using a model structure with ordered vacancies within the carbon sublattice. For stoichiometric MoC, the {gamma} phase was found to be the most stable followed by {gamma}{sup {prime}}, {delta}, and {eta}, but for substoichiometric MoC{sub 0.75}, the order of relative stability was changed and the substoichiometric {delta} phase was found to havemore » the lowest energy followed by {gamma}{sup {prime}} and {gamma}. A study of the electronic structure revealed vacancy induced peaks in the density of state and the electron density attached to these peaks was analyzed and found to emanate from unscreened Mo{endash}Mo bonds through the carbon vacancy site. Finally, the oxygen stabilization of the {gamma}{sup {prime}} MoC phase was studied. {copyright} {ital 1999 American Institute of Physics.}« less

Nuclear magnetic and nuclear quadrupole resonance parameters of β-carboline derivatives calculated using density functional theory

NASA Astrophysics Data System (ADS)

Ahmadinejad, Neda; Tari, Mostafa Talebi

2017-04-01

A density functional theory (DFT) calculations using B3LYP/6-311++G( d,p) method were carried out to investigate the relative stability of the molecules of β-carboline derivatives such as harmaline, harmine, harmalol, harmane and norharmane. Calculated nuclear quadrupole resonance (NQR) parameters were used to determine the 14N nuclear quadrupole coupling constant χ, asymmetry parameter η and EFG tensor ( q zz ). For better understanding of the electronic structure of β-carboline derivatives, natural bond orbital (NBO) analysis, isotropic and anisotropic NMR chemical shieldings were calculated for 14N nuclei using GIAO method for the optimized structures. The NBO analysis shows that pyrrole ring nitrogen (N9) atom has greater tendency than pyridine ring nitrogen (N2) atom to participate in resonance interactions and aromaticity development in the all of these structures. The NMR and NQR parameters were studied in order to find the correlations between electronic structure and the structural stability of the studied molecules.

Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers.

PubMed

Lei, Ting; Wang, Jie-Yu; Pei, Jian

2014-04-15

Conjugated polymers have developed rapidly due to their promising applications in low-cost, lightweight, and flexible electronics. The development of the third-generation donor-acceptor (D-A) polymers greatly improved the device performance in organic solar cells (OSCs) and field-effect transistors (FETs). However, for further improvement of device performance, scientists need to develop new building blocks, in particular electron-deficient aromatics, and gain an in-depth understanding of the structure-property relationships. Recently, isoindigo has been used as a new acceptor of D-A conjugated polymers. An isomer of indigo, isoindigo is a less well-known dye and can be isolated as a by-product from certain biological processes. It has two lactam rings and exhibits strong electron-withdrawing character. This electron deficiency gives isoindigo-based polymers intriguing properties, such as broad absorption and high open circuit voltage in OSCs, as well as high mobility and good ambient stability in FETs. In this Account, we review our recent progress on the design, synthesis, and structure-property relationship study of isoindigo-based polymers for FETs. Starting with some discussion on carrier transport in polymer films, we provide some basic strategies towards high-performance polymer FETs. We discuss the stability issue of devices, the impediment of the alkyl side chains, and the choice of the donor part of conjugated polymers. We demonstrate that introducing the isoindigo core effectively lowers the HOMO levels of polymers and provides FETs with long-time stability. In addition, we have found that when we use inappropriate alkyl side chains or non-centrosymmetric donors, the device performance of isoindigo polymers suffers. To further improve device performance and ambient stability, we propose several design strategies, such as using farther branched alkyl chains, modulating polymer energy levels, and extending π-conjugated backbones. We have found that using farther branched alkyl chains can effectively decrease interchain π-π stacking distance and improve carrier mobility. When we introduce electron-deficient functional groups on the isoindigo core, the LUMO levels of the polymers markedly decrease, which significantly improves the electron mobility and device stability. In addition, we present a new polymer system called BDOPV, which is based on the concept of π-extended isoindigo. By application of some strategies successfully used in isoindigo-based polymers, BDOPV-based polymers exhibit high mobility and good stability both in n-type and in ambipolar FETs. We believe that a synergy of molecular engineering strategies towards the isoindigo core, donor units, and side chains may further improve the performance and broaden the application of isoindigo-based polymers.

Stability condition for the drive bunch in a collinear wakefield accelerator

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

Baturin, S. S.; Zholents, A.

The beam breakup instability of the drive bunch in the structure-based collinear wakefield accelerator is considered and a stabilizing method is proposed. The method includes using the specially designed beam focusing channel, applying the energy chirp along the electron bunch, and keeping energy chirp constant during the drive bunch deceleration. A stability condition is derived that defines the limit on the accelerating field for the witness bunch.

Impurity-doped Si10 cluster: Understanding the structural and electronic properties from first-principles calculations

NASA Astrophysics Data System (ADS)

Majumder, Chiranjib; Kulshreshtha, S. K.

2004-12-01

Structural and electronic properties of metal-doped silicon clusters ( MSi10 , M=Li , Be, B, C, Na, Mg, Al, and Si) have been investigated via ab initio molecular dynamics simulation under the formalism of the density functional theory. The exchange-correlation energy has been calculated using the generalized gradient approximation method. Several stable isomers of MSi10 clusters have been identified based on different initial configurations and their relative stabilities have been analyzed. From the results it is revealed that the location of the impurity atom depends on the nature of interaction between the impurity atom and the host cluster and the size of the impurty atom. Whereas Be and B atoms form stable isomers, the impurity atom being placed at the center of the bicapped tetragonal antiprism structure of the Si10 cluster, all other elements diffuse outside the cage of Si10 cluster. Further, to understand the stability and the chemical bonding, the LCAO-MO based all electron calculations have been carried out for the lowest energy isomers using the hybrid B3LYP energy functional. Based on the interaction energy of the M atoms with Si10 clusters it is found that p-p interaction dominates over the s-p interaction and smaller size atoms interact more strongly. Based on the binding energy, the relative stability of MSi10 clusters is found to follow the order of CSi10>BSi10>BeSi10>Si11>AlSi10>LiSi10>NaSi10>MgSi10 , leading one to infer that while the substitution of C, B and Be enhances the stability of the Si11 cluster, others have an opposite effect. The extra stability of the BeSi10 clusters is due to its encapsulated close packed structure and large energy gap between the HOMO and LUMO energy levels.

Electronic properties of graphene nanoribbons: A density functional investigation

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

Kumar, Sandeep, E-mail: skumar198712@gmail.com; Sharma, Hitesh, E-mail: dr.hitesh.phys@gmail.com

2015-05-15

Density functional theory calculations have been performed on graphene nano ribbons (GNRs) to investigate the electronic properties as a function of chirality, size and hydrogenation on the edges. The calculations were performed on GNRs with armchair and zigzag configurations with 28, 34, 36, 40, 50, 56, 62, 66 carbon atoms. The structural stability of AGNR and ZGNR increases with the size of nanoribbon where as hydrogenation of GNR tends to lowers their structural stability. All GNRs considered have shown semiconducting behavior with HOMO-LUMO gap decreasing with the increase in the GNR size. The hydrogenation of GNR decreases its HOMO-LUMO gapmore » significantly. The results are in agreement with the available experimental and theoretical results.« less

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

DOE PAGES

Nelson, A. J.; Voss, L. F.; Beck, P. R.; ...

2013-01-12

We subjected device-grade TlBr to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl 2, Br:MeOH and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

X-ray photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Lee, J.-S.; Kim, H.; Cirignano, L.; Shah, K.

2013-04-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. As-polished TlBr was treated separately with HCl, SOCl2, Br:MeOH, and HF solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p, and S 2p core lines were used to evaluate surface chemistry and shallow heterojunction formation. Surface chemistry and valence band electronic structure were correlated with the goal of optimizing the long-term stability and radiation response.

Interplay of phase sequence and electronic structure in the modulated martensites of Mn2NiGa from first-principles calculations

NASA Astrophysics Data System (ADS)

Kundu, Ashis; Gruner, Markus E.; Siewert, Mario; Hucht, Alfred; Entel, Peter; Ghosh, Subhradip

2017-08-01

We investigate the relative stability, structural properties, and electronic structure of various modulated martensites of the magnetic shape memory alloy Mn2NiGa by means of density functional theory. We observe that the instability in the high-temperature cubic structure first drives the system to a structure where modulation shuffles with a period of six atomic planes are taken into account. The driving mechanism for this instability is found to be the nesting of the minority band Fermi surface, in a similar way to that established for the prototype system Ni2MnGa . In agreement with experiments, we find 14M modulated structures with orthorhombic and monoclinic symmetries having energies lower than other modulated phases with the same symmetry. In addition, we also find energetically favorable 10M modulated structures which have not been observed experimentally for this system yet. The relative stability of various martensites is explained in terms of changes in the electronic structures near the Fermi level, affected mostly by the hybridization of Ni and Mn states. Our results indicate that the maximum achievable magnetic field-induced strain in Mn2NiGa would be larger than in Ni2MnGa . However, the energy costs for creating nanoscale adaptive twin boundaries are found to be one order of magnitude higher than that in Ni2MnGa .

Unexpected Ground-State Structure and Mechanical Properties of Ir₂Zr Intermetallic Compound.

PubMed

Zhang, Meiguang; Cao, Rui; Zhao, Meijie; Du, Juan; Cheng, Ke

2018-01-10

Using an unbiased structure searching method, a new orthorhombic Cmmm structure consisting of ZrIr 12 polyhedron building blocks is predicted to be the thermodynamic ground-state of stoichiometric intermetallic Ir₂Zr in Ir-Zr systems. The formation enthalpy of the Cmmm structure is considerably lower than that of the previously synthesized Cu₂Mg-type phase, by ~107 meV/atom, as demonstrated by the calculation of formation enthalpy. Meanwhile, the phonon dispersion calculations further confirmed the dynamical stability of Cmmm phase under ambient conditions. The mechanical properties, including elastic stability, rigidity, and incompressibility, as well as the elastic anisotropy of Cmmm -Ir₂Zr intermetallic, have thus been fully determined. It is found that the predicted Cmmm phase exhibits nearly elastic isotropic and great resistance to shear deformations within the (100) crystal plane. Evidence of atomic bonding related to the structural stability for Ir₂Zr were manifested by calculations of the electronic structures.

SU-C-204-03: DFT Calculations of the Stability of DOTA-Based-Radiopharmaceuticals

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

Khabibullin, A.R.; Woods, L.M.; Karolak, A.

2016-06-15

Purpose: Application of the density function theory (DFT) to investigate the structural stability of complexes applied in cancer therapy consisting of the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelated to Ac225, Fr221, At217, Bi213, and Gd68 radio-nuclei. Methods: The possibility to deliver a toxic payload directly to tumor cells is a highly desirable aim in targeted alpha particle therapy. The estimation of bond stability between radioactive atoms and the DOTA chelating agent is the key element in understanding the foundations of this delivery process. Thus, we adapted the Vienna Ab-initio Simulation Package (VASP) with the projector-augmented wave method and a plane-wave basis setmore » in order to study the stability and electronic properties of DOTA ligand chelated to radioactive isotopes. In order to count for the relativistic effect of radioactive isotopes we included Spin-Orbit Coupling (SOC) in the DFT calculations. Five DOTA complex structures were represented as unit cells, each containing 58 atoms. The energy optimization was performed for all structures prior to calculations of electronic properties. Binding energies, electron localization functions as well as bond lengths between atoms were estimated. Results: Calculated binding energies for DOTA-radioactive atom systems were −17.792, −5.784, −8.872, −13.305, −18.467 eV for Ac, Fr, At, Bi and Gd complexes respectively. The displacements of isotopes in DOTA cages were estimated from the variations in bond lengths, which were within 2.32–3.75 angstroms. The detailed representation of chemical bonding in all complexes was obtained with the Electron Localization Function (ELF). Conclusion: DOTA-Gd, DOTA-Ac and DOTA-Bi were the most stable structures in the group. Inclusion of SOC had a significant role in the improvement of DFT calculation accuracy for heavy radioactive atoms. Our approach is found to be proper for the investigation of structures with DOTA-based-radiopharmaceuticals and will enhance our understanding of processes occurring at subatomic levels.« less

Use of CdS quantum dot-functionalized cellulose nanocrystal films for anti-counterfeiting applications

NASA Astrophysics Data System (ADS)

Chen, L.; Lai, C.; Marchewka, R.; Berry, R. M.; Tam, K. C.

2016-07-01

Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications.Structural colors and photoluminescence have been widely used for anti-counterfeiting and security applications. We report for the first time the use of CdS quantum dot (QD)-functionalized cellulose nanocrystals (CNCs) as building blocks to fabricate nanothin films via layer-by-layer (LBL) self-assembly for anti-counterfeiting applications. Both negatively- and positively-charged CNC/QD nanohybrids with a high colloidal stability and a narrow particle size distribution were prepared. The controllable LBL coating process was characterized by scanning electron microscopy and ellipsometry. The rigid structure of CNCs leads to nanoporous structured films on poly(ethylene terephthalate) (PET) substrates with high transmittance (above 70%) over the entire range of visible light and also resulted in increased hydrophilicity (contact angles of ~40 degrees). Nanothin films on PET substrates showed good flexibility and enhanced stability in both water and ethanol. The modified PET films with structural colors from thin-film interference and photoluminescence from QDs can be used in anti-counterfeiting applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03039d

DNA-Based Single-Molecule Electronics: From Concept to Function.

PubMed

Wang, Kun

2018-01-17

Beyond being the repository of genetic information, DNA is playing an increasingly important role as a building block for molecular electronics. Its inherent structural and molecular recognition properties render it a leading candidate for molecular electronics applications. The structural stability, diversity and programmability of DNA provide overwhelming freedom for the design and fabrication of molecular-scale devices. In the past two decades DNA has therefore attracted inordinate amounts of attention in molecular electronics. This review gives a brief survey of recent experimental progress in DNA-based single-molecule electronics with special focus on single-molecule conductance and I-V characteristics of individual DNA molecules. Existing challenges and exciting future opportunities are also discussed.

DNA-Based Single-Molecule Electronics: From Concept to Function

PubMed Central

2018-01-01

Beyond being the repository of genetic information, DNA is playing an increasingly important role as a building block for molecular electronics. Its inherent structural and molecular recognition properties render it a leading candidate for molecular electronics applications. The structural stability, diversity and programmability of DNA provide overwhelming freedom for the design and fabrication of molecular-scale devices. In the past two decades DNA has therefore attracted inordinate amounts of attention in molecular electronics. This review gives a brief survey of recent experimental progress in DNA-based single-molecule electronics with special focus on single-molecule conductance and I–V characteristics of individual DNA molecules. Existing challenges and exciting future opportunities are also discussed. PMID:29342091

Magnetism on a Boron-doped Si(111)-√ 3 × √ 3 Surface

NASA Astrophysics Data System (ADS)

Moon, Chang-Youn; Eom, Daejin; Koo, Ja-Yong

2018-03-01

We perform first-principles calculation to investigate the possible magnetism on the Si(111)-√ 3 × √ 3 surface, which is stabilized for highly boron-doped samples. When the silicon adatom on top of a boron atom is removed to form a defect structure, three silicon dangling bonds are exposed, generating half-filled doubly degenerate energy levels in the band gap, which stabilizes a local magnetic moment of 2 μ B . When many such defect structures are adjacent to one another, they are found to align antiferromagnetically. However, we demonstrate that the ferromagnetism can be stabilized by adjusting the number of electrons in the defects, suggesting a possibility towards spintronic applications for this unique silicon surface structure.

Making sense of the conflicting magic numbers in WSi{sub n} clusters

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

Abreu, Marissa Baddick; Reber, Arthur C.; Khanna, Shiv N.

2015-08-21

First principles studies on the geometric structure, stability, and electronic structure of WSi{sub n} clusters, n = 6-16, have been carried out to show that the observed differing “magic sizes” for WSi{sub n} clusters are associated with the nature of the growth processes. The WSi{sub 12} cluster, observed as a magic species in experiments reacting transition metal ions with silane, is not stable due to a filled shell of 18 electrons, as previously proposed, but due to its atomic structure that arrests further growth because of an endohedral transition metal site. In fact, it is found that all of thesemore » clusters, n = 6-16, have filled 5d shells except for WSi{sub 12}, which has a 5d{sup 8} configuration that is caused by crystal field splitting. The stability of WSi{sub 15}{sup +}, observed as highly stable in clusters generated by vaporizing silicon and metal carbonyls, is shown to be associated with a combination of geometric and electronic features. The findings are compared with previous results on CrSi{sub n} clusters.« less

Importance of interlayer H bonding structure to the stability of layered minerals

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

Conroy, Michele; Soltis, Jennifer A.; Wittman, Rick S.

2017-10-16

The exact atomic structures of layered minerals have been difficult to characterize because the layers often possess out-of-plane hydrogen atoms that cannot be detected by many analytical techniques. However, the ordering of these bonds are thought to play a fundamental role in the structural stability and solubility of layered minerals. We report a new strategy of using the intense radiation field of a focused electron beam to probe the effect of differences in hydrogen bonding networks on mineral solubility while simultaneously imaging the dissolution behavior in real time via liquid cell electron microscopy. We show the loss in hydrogens frommore » interlayers of boehmite (γ-AlOOH) resulted in 2D nanosheets exfoliating from the bulk that subsequently and rapidly dissolved. However gibbsite (γ-Al(OH)3), with its higher concentration of OH terminating groups, was more accommodating to the deprotonation and stable under the beam.« less

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

Rantalainen, Kimmo I.; Christensen, Peter A.; Hafren, Anders

The viral genome-linked protein (VPg) of Potato virus A (PVA) is a multifunctional protein that belongs to a class of intrinsically disordered proteins. Typically, this type of protein gains a more stable structure upon interactions or posttranslational modifications. In a membrane lipid strip overlay binding assay, PVA VPg was found to bind phosphatidylserine (PS), but not phosphatidylcholine (PC). According to circular dichroism spectroscopy, the secondary structure of PVA VPg was stabilized upon interactions with PS and phosphatidylglycerol (PG), but not with PC vesicles. It is possible that this stabilization favored the formation of alpha-helical structures. Limited tryptic digestion showed thatmore » the interaction with anionic vesicles protected certain, otherwise accessible, trypsin cleavage sites. An electron microscopy study revealed that interaction with VPg substantially increased the vesicle diameter and caused the formation of pore or plaque-like electron dense spots on the vesicle surface, which gradually led to disruption of the vesicles.« less

Low-Temperature Bainite: A Thermal Stability Study

NASA Astrophysics Data System (ADS)

Santajuana, Miguel A.; Rementeria, Rosalia; Kuntz, Matthias; Jimenez, Jose A.; Caballero, Francisca G.; Garcia-Mateo, Carlos

2018-06-01

The thermal stability of nanobainitic structures obtained by heat treating two different high-carbon high-silicon steels at temperatures between 200 °C and 600 °C has been investigated by means of three complementary techniques, i.e., field emission gun-scanning electron microscopy, X-ray diffraction, and high-resolution dilatometry. Three main stages have been established, each of them characterized by a distinctive microstructure. Furthermore, the nanocrystalline structure generated by the bainite reaction confers the steel with an extraordinary tempering resistance.

Low-Temperature Bainite: A Thermal Stability Study

NASA Astrophysics Data System (ADS)

Santajuana, Miguel A.; Rementeria, Rosalia; Kuntz, Matthias; Jimenez, Jose A.; Caballero, Francisca G.; Garcia-Mateo, Carlos

2018-04-01

The thermal stability of nanobainitic structures obtained by heat treating two different high-carbon high-silicon steels at temperatures between 200 °C and 600 °C has been investigated by means of three complementary techniques, i.e., field emission gun-scanning electron microscopy, X-ray diffraction, and high-resolution dilatometry. Three main stages have been established, each of them characterized by a distinctive microstructure. Furthermore, the nanocrystalline structure generated by the bainite reaction confers the steel with an extraordinary tempering resistance.

Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

2012-01-01

We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

Penta-P2X (X=C, Si) monolayers as wide-bandgap semiconductors: A first principles prediction

NASA Astrophysics Data System (ADS)

Naseri, Mosayeb; Lin, Shiru; Jalilian, Jaafar; Gu, Jinxing; Chen, Zhongfang

2018-06-01

By means of density functional theory computations, we predicted two novel two-dimensional (2D) nanomaterials, namely P2X (X=C, Si) monolayers with pentagonal configurations. Their structures, stabilities, intrinsic electronic, and optical properties as well as the effect of external strain to the electronic properties have been systematically examined. Our computations showed that these P2C and P2Si monolayers have rather high thermodynamic, kinetic, and thermal stabilities, and are indirect semiconductors with wide bandgaps (2.76 eV and 2.69 eV, respectively) which can be tuned by an external strain. These monolayers exhibit high absorptions in the UV region, but behave as almost transparent layers for visible light in the electromagnetic spectrum. Their high stabilities and exceptional electronic and optical properties suggest them as promising candidates for future applications in UV-light shielding and antireflection layers in solar cells.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Synthesis and Structural Characterization of Silver Nanoparticles Stabilized with 3-Mercapto-1-Propansulfonate and 1-Thioglucose Mixed Thiols for Antibacterial Applications

PubMed Central

Porcaro, Francesco; Carlini, Laura; Ugolini, Andrea; Visaggio, Daniela; Visca, Paolo; Fratoddi, Ilaria; Venditti, Iole; Meneghini, Carlo; Simonelli, Laura; Marini, Carlo; Olszewski, Wojciech; Ramanan, Nitya; Luisetto, Igor; Battocchio, Chiara

2016-01-01

The synthesis, characterization and assessment of the antibacterial properties of hydrophilic silver nanoparticles (AgNPs) were investigated with the aim to probe their suitability for innovative applications in the field of nanobiotechnology. First, silver nanoparticles were synthetized and functionalized with two capping agents, namely 3-mercapto-1-propansulfonate (3MPS) and 1-β-thio-d-glucose (TG). The investigation of the structural and electronic properties of the nano-systems was carried out by means of X-ray Photoelectron Spectroscopy (XPS) and X-ray Absorption Spectroscopy (XAS). XPS data provided information about the system stability and the interactions between the metallic surface and the organic ligands. In addition, XPS data allowed us to achieve a deep understanding of the influence of the thiols stoichiometric ratio on the electronic properties and stability of AgNPs. In order to shed light on the structural and electronic local properties at Ag atoms sites, XAS at Ag K-Edge was successfully applied; furthermore, the combination of Dynamic Light Scattering (DLS) and XAS results allowed determining AgNPs sizes, ranging between 3 and 13 nm. Finally, preliminary studies on the antibacterial properties of AgNPs showed promising results on four of six multidrug-resistant bacteria belonging to the ESKAPE group (Enterococcus faecium, Staphylococcus aureus, Klebsiella pneumoniae, Acinetobacter baumannii, Pseudomonas aeruginosa, and Enterobacter sp.). PMID:28774148

Nanoparticles of CdI 2 with closed cage structures obtained via electron-beam irradiation

NASA Astrophysics Data System (ADS)

Sallacan, N.; Popovitz-Biro, R.; Tenne, R.

2003-06-01

Nanoparticles of various layered compounds were shown to form closed cage or nanotubular structures, which were designated as inorganic fullerene-like ( IF) materials. In particular, closed cage structures and nanotubes were synthesized from NiCl 2 and CdCl 2 in the past. In the present work IF-CdI 2 nanoparticles were synthesized by electron-beam irradiation of the source powder leading to evaporation and subsequent recrystallization into closed nanoparticles with a non-hollow core. This process created polyhedral nanoparticles with hexagonal or elongated rectangular characters. Consistent with previous observations, this study shows that the seamless structure of the IF materials can stabilize phases, which are otherwise unstable under the electron-beam irradiation.

3D structure of individual nanocrystals in solution by electron microscopy

NASA Astrophysics Data System (ADS)

Park, Jungwon; Elmlund, Hans; Ercius, Peter; Yuk, Jong Min; Limmer, David T.; Chen, Qian; Kim, Kwanpyo; Han, Sang Hoon; Weitz, David A.; Zettl, A.; Alivisatos, A. Paul

2015-07-01

Knowledge about the synthesis, growth mechanisms, and physical properties of colloidal nanoparticles has been limited by technical impediments. We introduce a method for determining three-dimensional (3D) structures of individual nanoparticles in solution. We combine a graphene liquid cell, high-resolution transmission electron microscopy, a direct electron detector, and an algorithm for single-particle 3D reconstruction originally developed for analysis of biological molecules. This method yielded two 3D structures of individual platinum nanocrystals at near-atomic resolution. Because our method derives the 3D structure from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unordered nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale.

Spectroscopic investigation of the electronic structure of yttria-stabilized zirconia

NASA Astrophysics Data System (ADS)

Götsch, Thomas; Bertel, Erminald; Menzel, Alexander; Stöger-Pollach, Michael; Penner, Simon

2018-03-01

The electronic structure and optical properties of yttria-stabilized zirconia are investigated as a function of the yttria content using multiple experimental and theoretical methods, including electron energy-loss spectroscopy, Kramers-Kronig analysis to obtain the optical parameters, photoelectron spectroscopy, and density functional theory. It is shown that many properties, including the band gaps, the crystal field splitting, the so-called defect gap between acceptor (YZr') and donor (VO••) states, as well as the index of refraction in the visible range exhibit the same "zig-zag-like" trend as the unit cell height does, showing the influence of an increased yttria content as well as of the tetragonal-cubic phase transition between 8 mol % and 20 mol %Y2O3 . Also, with Čerenkov spectroscopy (CS), a new technique is presented, providing information complementary to electron energy-loss spectroscopy. In CS, the Čerenkov radiation emitted inside the TEM is used to measure the onset of optical absorption. The apparent absorption edges in the Čerenkov spectra correspond to the energetic difference between the disorder states close to the valence band and the oxygen-vacancy-related electronic states within the band gap. Theoretical computations corroborate this assignment: they find both, the acceptor states and the donor states, at the expected energies in the band structures for diverse yttria concentrations. In the end, a schematic electronic structure diagram of the area around the band gap is constructed, including the chemical potential of the electrons obtained from photoelectron spectroscopy. The latter reveal that tetragonal YSZ corresponds to a p -type semiconductor, whereas the cubic samples exhibit n -type semiconductor properties.

Electronic structures of Al-Si clusters and the magic number structure Al8Si4

NASA Astrophysics Data System (ADS)

Du, Ning; Su, Mingzhi; Chen, Hongshan

2018-02-01

The low-energy structures of Al8Sim (m = 1-6) have been determined by using the genetic algorithm combined with density functional theory and the Second-order Moller-Plesset perturbation theory (MP2) models. The results show that the close-packed structures are preferable in energy for Al-Si clusters and in most cases there exist a few isomers with close energies. The valence molecular orbitals, the orbital level structures and the electron localisation function (ELF) consistently demonstrate that the electronic structures of Al-Si clusters can be described by the jellium model. Al8Si4 corresponds to a magic number structure with pronounced stability and large energy gap; the 40 valence electrons form closed 1S21P61D102S21F142P6 shells. The ELF attractors also suggest weak covalent Si-Si, Si-Al and Al-Al bonding, and doping Si in aluminium clusters promotes the covalent interaction between Al atoms.

Structural stability, electronic, magnetic and optical properties of zincblende Zn0.5V0.5Te under pressure

NASA Astrophysics Data System (ADS)

Yin, Zhu-Hua; Zhang, Jian-Min

2016-10-01

The structural stability, electronic, magnetic and optical properties of zincblende Zn0.5V0.5Te under pressures 0-5 GPa are investigated by the spin-polarized first-principles calculation. Under pressure, the Zn0.5V0.5Te is always half-metal with the total magnetic moment μtot of 3μB / cell mainly contributed by V2+ ion, but the spin-down channel opens a band gap. The Zn0.5V0.5Te also behaves in a ductile manner and is mechanical stable until 3.78 GPa pressure. The static dielectric function ε1 (0) and refractive index n (0) increase with pressure. The two absorption peaks located in energy regions 0-20 eV and 35-50 eV not only increase but also shift to the higher energy region (blue shift) with pressure. So the electronic and optical properties of Zn0.5V0.5Te could be tuned through external pressure, which is beneficial to the electronic and optical applications.

Electronic Structure and Stability of [B 12 X 12 ] 2– (X = F–At): A Combined Photoelectron Spectroscopic and Theoretical Study

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

Warneke, Jonas; Hou, Gao-Lei; Aprà, Edoardo

2017-10-09

The relative stability and electron loss process of Multiply Charged Anions have been traditionally explained in terms of the classical Coulomb interaction between spatially separated charges. In this study we report the surprising properties of [B12X12]2-, X = F – At, that are counterintuitive compared to the prevailing classical description and justify their classification into a new class of MCAs. In this new class of MCAs, comprising of a “Boron core” surrounded by a “Halogen shell”, the sign of the total charge in these two regions changes along the halogen series from F to At. With the aid of photoelectronmore » spectroscopy and electronic structure calculations we demonstrate that the behavior of these MCAs is largely determined by quantum effects rather than classical electrostatics. The second excess electron is always taken from the most positively charged region, viz. the “Boron core” for F – Br and the surrounding “Halogen shell” for I, At.« less

Fabrication of a biofuel cell improved by the π-conjugated electron pathway effect induced from a new enzyme catalyst employing terephthalaldehyde

NASA Astrophysics Data System (ADS)

Chung, Yongjin; Hyun, Kyu Hwan; Kwon, Yongchai

2015-12-01

A model explaining the π-conjugated electron pathway effect induced by a novel cross-linker adopted enzyme catalyst is suggested and the performance and stability of an enzymatic biofuel cell (EBC) adopting the new catalyst are evaluated. For this purpose, new terephthalaldehyde (TPA) and conventional glutaraldehyde (GA) cross-linkers are adopted on a glucose oxidase (GOx), polyethyleneimine (PEI) and carbon nanotube (CNT)(GOx/PEI/CNT) structure. GOx/PEI/CNT cross-linked by TPA (TPA/[GOx/PEI/CNT]) results in a superior EBC performance and stability to other catalysts. It is attributed to the π bonds conjugated between the aldehyde of TPA and amine of the GOx/PEI molecules. By π conjugation, electrons bonded with carbon and nitrogen are delocalized, promoting the electron transfer and catalytic activity with an excellent EBC performance. The maximum power density (MPD) of an EBC adopting TPA/[GOx/PEI/CNT] (0.66 mW cm-2) is far better than that of the other EBCs (the MPD of EBC adopting GOx/PEI/CNT is 0.40 mW cm-2). Regarding stability, the covalent bonding formed between TPA and GOx/PEI plays a critical role in preventing the denaturation of GOx molecules, leading to an excellent stability. By repeated measurements of the catalytic activity, TPA/[GOx/PEI/CNT] maintains its activity to 92% of its initial value even after five weeks.A model explaining the π-conjugated electron pathway effect induced by a novel cross-linker adopted enzyme catalyst is suggested and the performance and stability of an enzymatic biofuel cell (EBC) adopting the new catalyst are evaluated. For this purpose, new terephthalaldehyde (TPA) and conventional glutaraldehyde (GA) cross-linkers are adopted on a glucose oxidase (GOx), polyethyleneimine (PEI) and carbon nanotube (CNT)(GOx/PEI/CNT) structure. GOx/PEI/CNT cross-linked by TPA (TPA/[GOx/PEI/CNT]) results in a superior EBC performance and stability to other catalysts. It is attributed to the π bonds conjugated between the aldehyde of TPA and amine of the GOx/PEI molecules. By π conjugation, electrons bonded with carbon and nitrogen are delocalized, promoting the electron transfer and catalytic activity with an excellent EBC performance. The maximum power density (MPD) of an EBC adopting TPA/[GOx/PEI/CNT] (0.66 mW cm-2) is far better than that of the other EBCs (the MPD of EBC adopting GOx/PEI/CNT is 0.40 mW cm-2). Regarding stability, the covalent bonding formed between TPA and GOx/PEI plays a critical role in preventing the denaturation of GOx molecules, leading to an excellent stability. By repeated measurements of the catalytic activity, TPA/[GOx/PEI/CNT] maintains its activity to 92% of its initial value even after five weeks. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06703k

Photoemission analysis of chemically modified TlBr surfaces for improved radiation detectors

NASA Astrophysics Data System (ADS)

Nelson, A. J.; Lee, J.-S.; Stanford, J. A.; Grant, W. K.; Voss, L. F.; Beck, P. R.; Graff, R. T.; Swanberg, E. L.; Conway, A. M.; Nikolic, R. J.; Payne, S. A.; Kim, H.; Cirignano, L. J.; Shah, K.

2013-09-01

Device-grade TlBr was subjected to various chemical treatments used in room temperature radiation detector fabrication to determine the resulting surface composition and electronic structure. Samples of as polished TlBr were treated separately with 2%Br:MeOH, 10%HF, 10%HCl and 96%SOCl2 solutions. High-resolution photoemission measurements on the valence band electronic structure and Tl 4f, Br 3d, Cl 2p and S 2p core lines were used to evaluate surface chemistry. Results suggest anion substitution at the surface with subsequent shallow heterojunction formation. Surface chemistry and valence band electronic structure were further correlated with the goal of optimizing the long-term stability and radiation response.

Electronic structure and optical properties of the thiolate-protected Au28(SMe)20 cluster.

PubMed

Knoppe, Stefan; Malola, Sami; Lehtovaara, Lauri; Bürgi, Thomas; Häkkinen, Hannu

2013-10-10

The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: p-tert-butylbenzenethiolate) is analyzed with (time-dependent) density functional theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au14(6+) core and the ligand-protected cluster were analyzed, and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and circular dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.

Discovery of a superconducting high-entropy alloy.

PubMed

Koželj, P; Vrtnik, S; Jelen, A; Jazbec, S; Jagličić, Z; Maiti, S; Feuerbacher, M; Steurer, W; Dolinšek, J

2014-09-05

High-entropy alloys (HEAs) are multicomponent mixtures of elements in similar concentrations, where the high entropy of mixing can stabilize disordered solid-solution phases with simple structures like a body-centered cubic or a face-centered cubic, in competition with ordered crystalline intermetallic phases. We have synthesized an HEA with the composition Ta34Nb33Hf8Zr14Ti11 (in at. %), which possesses an average body-centered cubic structure of lattice parameter a=3.36  Å. The measurements of the electrical resistivity, the magnetization and magnetic susceptibility, and the specific heat revealed that the Ta34Nb33Hf8Zr14Ti11 HEA is a type II superconductor with a transition temperature Tc≈7.3  K, an upper critical field μ0H_c2≈8.2  T, a lower critical field μ0Hc1≈32  mT, and an energy gap in the electronic density of states (DOS) at the Fermi level of 2Δ≈2.2  meV. The investigated HEA is close to a BCS-type phonon-mediated superconductor in the weak electron-phonon coupling limit, classifying it as a "dirty" superconductor. We show that the lattice degrees of freedom obey Vegard's rule of mixtures, indicating completely random mixing of the elements on the HEA lattice, whereas the electronic degrees of freedom do not obey this rule even approximately so that the electronic properties of a HEA are not a "cocktail" of properties of the constituent elements. The formation of a superconducting gap contributes to the electronic stabilization of the HEA state at low temperatures, where the entropic stabilization is ineffective, but the electronic energy gain due to the superconducting transition is too small for the global stabilization of the disordered state, which remains metastable.

Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters

NASA Astrophysics Data System (ADS)

Guedes-Sobrinho, Diego; Chaves, Anderson S.; Piotrowski, Maurício J.; Da Silva, Juarez L. F.

2017-04-01

Although several studies have been reported for Pt55 and Au55 nanoclusters, our atomistic understanding of the interplay between the adsorbate-surface interactions and the mechanisms that lead to the formation of the distorted reduced core (DRC) structures, instead of the icosahedron (ICO) structure in gas phase, is still far from satisfactory. Here, we report a density functional theory (DFT) investigation of the role of the adsorption effects of PH3 (one lone pair of electrons) and SH2 (two lone pairs) on the relative stability of the Pt55 and Au55 nanoclusters. In gas phase, we found that the DRC structures with 7 and 9 atoms in the core region are about 5.34 eV (Pt55) and 2.20 eV (Au55) lower in energy than the ICO model with Ih symmetry and 13 atoms in the core region. However, the stability of the ICO structure increases by increasing the number of adsorbed molecules from 1 to 18, in which both DRC and ICO structures are nearly degenerate in energy at the limit of 18 ligands, which can be explained as follows. In gas phase, there is a strong compression of the cationic core region by the anionic surface atoms induced by the attractive Coulomb interactions (core+-surface-), and hence, the strain release is obtained by reducing the number of atoms in the cationic core region, which leads to the 55 atoms distorted reduced core structures. Thus, the Coulomb interactions between the core+ and surface- contribute to break the symmetry in the ICO55 structure. On the other hand, the addition of ligands on the anionic surface reduces the charge transfer between the core and surface, which contributes to decrease the Coulomb interactions and the strain on the core region of the ICO structure, and hence, it stabilizes a compact ICO structure. The same conclusion is obtained by adding van der Waals corrections to the plain DFT calculations. Similar results are obtained by the addition of steric effects, which are considered through the adsorption of triphenylphosphine (PPh3) molecules on Au55, in which the relative stability between ICO and DRC is the same as for PH3 and SH2. However, for Pt55, we found an inversion of stability due to the PPh3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

Density functional investigation of the adsorption effects of PH3 and SH2 on the structure stability of the Au55 and Pt55 nanoclusters.

PubMed

Guedes-Sobrinho, Diego; Chaves, Anderson S; Piotrowski, Maurício J; Da Silva, Juarez L F

2017-04-28

Although several studies have been reported for Pt 55 and Au 55 nanoclusters, our atomistic understanding of the interplay between the adsorbate-surface interactions and the mechanisms that lead to the formation of the distorted reduced core (DRC) structures, instead of the icosahedron (ICO) structure in gas phase, is still far from satisfactory. Here, we report a density functional theory (DFT) investigation of the role of the adsorption effects of PH 3 (one lone pair of electrons) and SH 2 (two lone pairs) on the relative stability of the Pt 55 and Au 55 nanoclusters. In gas phase, we found that the DRC structures with 7 and 9 atoms in the core region are about 5.34 eV (Pt 55 ) and 2.20 eV (Au 55 ) lower in energy than the ICO model with I h symmetry and 13 atoms in the core region. However, the stability of the ICO structure increases by increasing the number of adsorbed molecules from 1 to 18, in which both DRC and ICO structures are nearly degenerate in energy at the limit of 18 ligands, which can be explained as follows. In gas phase, there is a strong compression of the cationic core region by the anionic surface atoms induced by the attractive Coulomb interactions (core + -surface - ), and hence, the strain release is obtained by reducing the number of atoms in the cationic core region, which leads to the 55 atoms distorted reduced core structures. Thus, the Coulomb interactions between the core + and surface - contribute to break the symmetry in the ICO 55 structure. On the other hand, the addition of ligands on the anionic surface reduces the charge transfer between the core and surface, which contributes to decrease the Coulomb interactions and the strain on the core region of the ICO structure, and hence, it stabilizes a compact ICO structure. The same conclusion is obtained by adding van der Waals corrections to the plain DFT calculations. Similar results are obtained by the addition of steric effects, which are considered through the adsorption of triphenylphosphine (PPh 3 ) molecules on Au 55 , in which the relative stability between ICO and DRC is the same as for PH 3 and SH 2 . However, for Pt 55 , we found an inversion of stability due to the PPh 3 ligand effects, where ICO has higher stability than DRC by 2.40 eV. Our insights are supported by several structural, electronic, and energetic analyses.

Influence of emulsifiers on the characteristics of polyurethane structures used as drug carrier

PubMed Central

2013-01-01

Background Emulsifiers have a significant role in the emulsion polymerization by reducing the interfacial tension thus increasing the stability of colloidal dispersions of polymer nanostructures. This study evaluates the impact of four emulsifiers on the characteristics of polyurethane hollow structures used as drug delivery system. Results Polyurethane (PU) structures with high stability and sizes ranging from nano- to micro-scale were obtained by interfacial polyaddition combined with spontaneous emulsification. The pH of PU aqueous solutions (0.1% w/w) was slightly acidic, which is acceptable for products intended to be used on human skin. Agglomerated structures with irregular shapes were observed by scanning electron microscopy. The synthesized structures have melting points between 245-265°C and reveal promising results in different evaluations (TEWL, mexametry) on murine skin. Conclusions In this study hollow PU structures of reduced noxiousness were synthesized, their size and stability being influenced by emulsifiers. Such structures could be used in the pharmaceutical field as future drug delivery systems. PMID:23575277

Stabilization of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} through Si–Ti substitution

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

Xie, Weiwei, E-mail: weiweix@princeton.edu; Fuccillo, M.K.; Phelan, B.F.

2015-07-15

We report a route for designing and synthesizing Ti{sub 3}Co{sub 5}B{sub 2}-type compounds in the Ti–Ru–B system by using chemical substitution of Si for Ti to decrease the d-electron-based antibonding interactions that it is argued would otherwise drive an instability in this structure for unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2}. Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} with x=0.75, 1.00 and 1.25 nominal compositions crystalizes in the Ti{sub 3}Co{sub 5}B{sub 2} structure type using arc melting methods, whereas at lower doping levels (x=0.0, 0.25 and 0.50) the more complex Zn{sub 11}Rh{sub 18}B{sub 8}-type structure is stable. Electronic structure calculations show that in hypothetical,more » unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2} with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure, the antibonding interactions are strong around the Fermi level between the Ti and Ru in the structure that form tetragonal prisms. We propose that weakening these strong interactions through the partial substitution of isovalent Si for Ti leads to the observed stability of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} for x≈1. - Graphical abstract: We present the designing and synthesizing of Ti{sub 3}Co{sub 5}B{sub 2}-type compounds in the Ti–Ru–B system by using chemical substitution of Si for Ti to decrease the d-electron-based antibonding interactions that would otherwise drive an instability in this structure for unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2}. Electronic structure calculations show that in hypothetical, unsubstituted Ti{sub 3}Ru{sub 5}B{sub 2} with the Ti{sub 3}Co{sub 5}B{sub 2}-type structure, the antibonding interactions are strong around the Fermi level between the Ti and Ru in the structure that form tetragonal prisms. We propose that weakening these strong interactions through the partial substitution of isovalent Si for Ti leads to the observed stability of the Ti{sub 3}Co{sub 5}B{sub 2}-type structure for Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} for x≈1. - Highlights: • New quaternary phase Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} in Ti{sub 3}Co{sub 5}B{sub 2}-type structure is reported. • Chemical substitution of isovalent Si for Ti is used to stabilize the phase. • Decreasing the d-electron-based antibonding interactions is proved by calculation. • Physical properties of Ti{sub 3−x}Si{sub x}Ru{sub 5}B{sub 2} are presented down to 0.4 K.« less

An ab initio study on the structural, electronic and mechanical properties of quaternary full-Heusler alloys FeMnCrSn and FeMnCrSb

NASA Astrophysics Data System (ADS)

Erkişi, Aytaç

2018-06-01

The quaternary full Heusler alloys FeMnCrSn and FeMnCrSb, which have face-centred cubic (FCC) crystal structure and conform to ? space group with 216 space number, have been investigated using Generalised Gradient Approximation (GGA) in the Density Functional Theory (DFT) as implemented in VASP (Vienna Ab initio Simulation Package) software. These alloys are considered in ferromagnetic (FM) order. After the investigation of structural stability of these alloys, their mechanical and thermal properties and also electronic band structures have been examined. The calculated spin-polarised electronic band structures and total electronic density of states (DOS) within GGA approximation show that these alloys can exhibit both metallic and half-metallic characters in different structural phases. The calculated formation enthalpies and the plotted energy-volume graphs show that Type-III phase is most stable structural phase for these materials. Also, FeMnCrSb alloy in Type-I/Type-III phases and FeMnCrSn alloy in Type-III phase show half-metallic behaviour with integer total magnetic moments almost 2 and 1 μB per formula unit, respectively, since there are band gaps observed in spin-down states, whereas they have metallic behaviour in majority bands. Other structural phases of both systems are also metallic. Moreover, the calculated elastic constants and the estimated anisotropy shear factors indicate that these materials are stable mechanically in all of three phases except FeMnCrSn in Type-I phase that does not satisfy Born stability criteria in this phase and have high anisotropic behaviour.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

NASA Astrophysics Data System (ADS)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Electronic structure, elasticity, bonding features and mechanical behaviour of zinc intermetallics: A DFT study

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

Fatima, Bushra, E-mail: bushrafatima25@gmail.com; Acharya, Nikita; Sanyal, Sankar P.

2016-05-06

The structural stability, electronic structure, elastic and mechanical properties of TiZn and ZrZn intermetallics have been studied using ab-initio full potential linearized augmented plane wave (FP-LAPW) method within generalized gradient approximation for exchange and correlation potentials. The various structural parameters, such as lattice constant (a{sub 0}), bulk modulus (B), and its pressure derivative (B’) are analysed and compared. The investigation of elastic constants affirm that both TiZn and ZrZn are elastically stable in CsCl (B{sub 2} phase) structure. The electronic structures have been analysed quantitatively from the band structure which reveals the metallic nature of these compounds. To better illustratemore » the nature of bonding and charge transfer, we have also studied the Fermi surfaces. The three well known criterion of ductility namely Pugh’s rule, Cauchy’s pressure and Frantsevich rule elucidate the ductile nature of these compounds.« less

Computational predictions of the new Gallium nitride nanoporous structures

NASA Astrophysics Data System (ADS)

Lien, Le Thi Hong; Tuoc, Vu Ngoc; Duong, Do Thi; Thu Huyen, Nguyen

2018-05-01

Nanoporous structural prediction is emerging area of research because of their advantages for a wide range of materials science and technology applications in opto-electronics, environment, sensors, shape-selective and bio-catalysis, to name just a few. We propose a computationally and technically feasible approach for predicting Gallium nitride nanoporous structures with hollows at the nano scale. The designed porous structures are studied with computations using the density functional tight binding (DFTB) and conventional density functional theory methods, revealing a variety of promising mechanical and electronic properties, which can potentially find future realistic applications. Their stability is discussed by means of the free energy computed within the lattice-dynamics approach. Our calculations also indicate that all the reported hollow structures are wide band gap semiconductors in the same fashion with their parent’s bulk stable phase. The electronic band structures of these nanoporous structures are finally examined in detail.

Effects of electron doping on the stability of the metal hydride NaH

NASA Astrophysics Data System (ADS)

Olea-Amezcua, M. A.; Rivas-Silva, J. F.; de la Peña-Seaman, O.; Heid, R.; Bohnen, K. P.

2017-04-01

Alkali and alkali-earth metal hydrides have high volumetric and gravimetric hydrogen densities, but due to their high thermodynamic stability, they possess high dehydrogenation temperatures which may be reduced by transforming these compounds into less stable states/configurations. We present a systematic computational study of the electron doping effects on the stability of the alkali metal hydride NaH substituted with Mg, using the self-consistent version of the virtual crystal approximation to model the alloy Na1-x Mg x H. The phonon dispersions were studied paying special attention to the crystal stability and the correlations with the electronic structure taking into account the zero point energy contribution. We found that substitution of Na by Mg in the hydride invokes a reduction of the frequencies, leading to dynamical instabilities for Mg content of 25%. The microscopic origin of these instabilities could be related to the formation of ellipsoidal Fermi surfaces centered at the L point due to the metallization of the hydride by the Mg substitution. Applying the quasiharmonic approximation, thermodynamic properties like heat capacities, vibrational entropies and vibrational free energies as a function of temperature at zero pressure are obtained. These properties determine an upper temperature for the thermodynamic stability of the hydride, which decreases from 600 K for NaH to 300 K at 20% Mg concentration. This significant reduction of the stability range indicates that dehydrogenation could be favoured by electron doping of NaH.

Stabilizing subnanometer Ag(0) nanoclusters by thiolate and diphosphine ligands and their crystal structures

NASA Astrophysics Data System (ADS)

Yang, Huayan; Wang, Yu; Zheng, Nanfeng

2013-03-01

The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions.The combined use of thiolate and diphosphine as surface ligands helps to stabilize subnanometer Ag(0) nanoclusters, resulting in the successful crystallization of two Ag(0)-containing nanoclusters (Ag16 and Ag32) for X-ray single crystal analysis. Both clusters have core-shell structures with Ag86+ and Ag2212+ as their cores, which are not simply either fragments of face-centered cubic metals or their five-fold twinned counterparts. The clusters display UV-Vis absorption spectra consisting of molecule-like optical transitions. Electronic supplementary information (ESI) available: Experimental details, more pictures of the structure and XPS spectra of the clusters. CCDC 916463 and 916464. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c3nr34328f

Artificial photosynthetic systems: assemblies of slipped cofacial porphyrins and phthalocyanines showing strong electronic coupling.

PubMed

Satake, Akiharu; Kobuke, Yoshiaki

2007-06-07

This paper reviews selected types of structurally well defined assemblies of porphyrins and phthalocyanines with strong electronic coupling. Face-to-face, head-to-tail, slipped cofacial, and non-parallel dimeric motifs constructed by covalent and non-covalent bonds are compared in the earlier sections. Their molecular orientation, electronic overlap, and absorption and fluorescence properties are discussed with a view towards the development of artificial photosynthetic systems and molecular electronics. Complementary coordination dimers are fully satisfactory in terms of structural stability, orientation factor, pi-electronic overlap, and zero fluorescence quenching. In later sections, several polymeric and macrocyclic porphyrin assemblies constructed by a combination of covalent bonds and complementary coordination bonds are discussed from the viewpoint of light-harvesting antenna functions.

Synthesis and Characterization of Pure Copper Nanostructures Using Wood Inherent Architecture as a Natural Template

NASA Astrophysics Data System (ADS)

Dong, Youming; Wang, Kaili; Tan, Yi; Wang, Qingchun; Li, Jianzhang; Mark, Hughes; Zhang, Shifeng

2018-04-01

The inherent sophisticated structure of wood inspires researchers to use it as a natural template for synthesizing functional nanoparticles. In this study, pure copper nanoparticles were synthesized using poplar wood as a natural inexpensive and renewable template. The crystal structure and morphologies of the copper nanoparticles were characterized by X-ray diffraction and field emission scanning electron microscopy. The optical properties, antibacterial properties, and stability of the hybrid wood materials were also tested. Due to the hierarchical and anisotropic structure and electron-rich components of wood, pure copper nanoparticles with high stability were synthesized with fcc structure and uniform sizes and then assembled into corncob-like copper deposits along the wood cell lumina. The products of nanoparticles depended strongly on the initial OH- concentration. With an increase in OH- concentration, Cu2O gradually decreased and Cu remained. Due to the restrictions inherent in wood structure, the derived Cu nanoparticles showed similar grain size in spite of increased Cu2+ concentration. This combination of Cu nanostructures and wood exhibited remarkable optical and antibacterial properties.

Ceramic component for electrodes

DOEpatents

Marchant, David D.

1979-01-01

A ceramic component suitable for preparing MHD generator electrodes consists of HfO.sub.2 and sufficient Tb.sub.4 O.sub.7 to stabilize at least 60 volume percent of the HfO.sub.2 into the cubic structure. The ceramic component may also contain a small amount of PrO.sub.2, Yb.sub.2 O.sub.3 or a mixture of both to improve stability and electronic conductivity of the electrode. The component is highly resistant to corrosion by molten potassium seed and molten coal slag in the MHD fluid and exhibits both ionic and electronic conductivity.

Self-Standing Polypyrrole/Black Phosphorus Laminated Film: Promising Electrode for Flexible Supercapacitor with Enhanced Capacitance and Cycling Stability.

PubMed

Luo, Shaojuan; Zhao, Jinlai; Zou, Jifei; He, Zhiliang; Xu, Changwen; Liu, Fuwei; Huang, Yang; Dong, Lei; Wang, Lei; Zhang, Han

2018-01-31

With the rapid development of portable electronics, solid-state flexible supercapacitors (SCs) are considered as one of the promising energy devices in powering electronics because of their intrinsic advantages. Polypyrrole (PPy) is an ideal electrode material in constructing flexible SCs owing to its high electrochemical activity and inherent flexibility, although its relatively low capacitance and poor cycling stability are still worthy of improvement. Herein, through the innovative introduction of black phosphorus (BP) nanosheets, we developed a laminated PPy/BP self-standing film with enhanced capacitance and cycling stability via a facile one-step electrochemical deposition method. The film exhibits a high capacitance of 497.5 F g -1 (551.7 F cm -3 ) and outstanding cycling stability of 10 000 charging/discharging cycles, thanks to BP nanosheets inducing laminated assembly which hinder dense and disordered stacking of PPy during electrodeposition, consequently providing a precise pathway for ion diffusion and electron transport together with alleviation of the structural deterioration during charge/discharge. The flexible SC fabricated by laminated films delivers a high capacitance of 452.8 F g -1 (7.7 F cm -3 ) besides its remarkable mechanical flexibility and cycling stability. Our facile strategy paves the way to improve the electrochemical performance of PPy-based SC that could serve as promising flexible energy device for portable electronics.

Synthesis and characterization of an Fe(i) cage complex with high stability towards strong H-acids.

PubMed

Voloshin, Yan Z; Novikov, Valentin V; Nelyubina, Yulia V; Belov, Alexander S; Roitershtein, Dmitrii M; Savitsky, Anton; Mokhir, Andriy; Sutter, Jörg; Miehlich, Matthias E; Meyer, Karsten

2018-04-03

The first synthesized and X-ray structurally characterized "classical" iron(i) dioximate showed an unrivaled stability towards strong acids, thus calling for a reassessment of the origins of the electrocatalytic activity of similar low-valent cobalt and iron cage complexes with electron-withdrawing ribbed substituents, shown previously to be effective electrocatalysts of the HER.

Layered method of electrode for solid oxide electrochemical cells

DOEpatents

Jensen, Russell R.

1991-07-30

A process for fabricating a fuel electrode comprising: slurry dipping to form layers which are structurally graded from all or mostly all stabilized zirconia at a first layer, to an outer most layer of substantially all metal powder, such an nickel. Higher performaance fuel electrodes may be achieved if sinter active stabilized zirconia doped for electronic conductivity is used.

Structure and formation of highly luminescent protein-stabilized gold clusters† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc05086k

PubMed Central

Chevrier, D. M.; Thanthirige, V. D.; Luo, Z.; Driscoll, S.; Cho, P.; MacDonald, M. A.; Yao, Q.; Guda, R.; Xie, J.; Johnson, E. R.; Chatt, A.; Zheng, N.

2018-01-01

Highly luminescent gold clusters simultaneously synthesized and stabilized by protein molecules represent a remarkable category of nanoscale materials with promising applications in bionanotechnology as sensors. Nevertheless, the atomic structure and luminescence mechanism of these gold clusters are still unknown after several years of developments. Herein, we report findings on the structure, luminescence and biomolecular self-assembly of gold clusters stabilized by the large globular protein, bovine serum albumin. We highlight the surprising identification of interlocked gold-thiolate rings as the main gold structural unit. Importantly, such gold clusters are in a rigidified state within the protein scaffold, offering an explanation for their highly luminescent character. Combined free-standing cluster synthesis (without protecting protein scaffold) with rigidifying and un-rigidifying experiments, were designed to further verify the luminescence mechanism and gold atomic structure within the protein. Finally, the biomolecular self-assembly process of the protein-stabilized gold clusters was elucidated by time-dependent X-ray absorption spectroscopy measurements and density functional theory calculations. PMID:29732064

Rotationally resolved electronic spectroscopy study of the conformational space of 3-methoxyphenol

NASA Astrophysics Data System (ADS)

Wilke, Martin; Schneider, Michael; Wilke, Josefin; Ruiz-Santoyo, José Arturo; Campos-Amador, Jorge J.; González-Medina, M. Elena; Álvarez-Valtierra, Leonardo; Schmitt, Michael

2017-07-01

Conformational preferences are determined by (de-)stabilization effects like intramolecular hydrogen bonds or steric hindrance of adjacent substituents and thus, influence the stability and reactivity of the conformers. In the present contribution, we investigate the conformational landscape of 3-methoxyphenol using a combination of high resolution electronic spectroscopy and ab initio calculations. Three of the four possible conformational isomers were characterized in their electronic ground and lowest excited singlet states on the basis of their rotational constants and other molecular parameters. The absence of one conformer in molecular beam studies can be explained by its non-planar structure in the excited state, which leads to a vanishingly small Franck-Condon factor of the respective origin excitation.

Microstructural, thermal and antibacterial properties of electron beam irradiated Bombyx mori silk fibroin films

NASA Astrophysics Data System (ADS)

Asha, S.; Sangappa, Naik, Prashantha; Chandra, K. Sharat; Sanjeev, Ganesh

2014-04-01

The Bombyx mori silk fibroin (SF) films were prepared by solution casting method and the effects of electron beam on structural, thermal and antibacterial responses of the prepared films were studied. The electron irradiation for different doses was carried out using 8 MeV Microtron facility at Mangalore University. The changes in microstructural parameters and thermal stability of the films were investigated using Wide Angle X-ray Scattering (WAXS) and thermogravimetric analysis (TGA) respectively. Both microstructuralline parameters (crystallite size and lattice strain (g in %)) and thermal stability of the irradiated films have increased with radiation dosage. Agar diffusion method demonstrated the antibacterial activity of SF film which was increased after irradiation on both Gram-positive and Gram-negative species.

Structural and electronic stability of a volleyball-shaped B80 fullerene

NASA Astrophysics Data System (ADS)

Wang, Xiao-Qian

2010-10-01

We have studied the structural and electronic characteristics of a volleyball-shaped B80 cage using first-principles density-functional calculations. In contrast to the popularly ratified “magic” B80 buckyball with 20 hexagonal pyramids and 12 hollow pentagons, the volleyball-shaped B80 constitutes 12 pentagonal pyramids, 8 hexagonal pyramids, and 12 hollow hexagons. The B80 volleyball is markedly more stable than the previously assumed magic B80 buckyball, which is attributed to the improved aromaticity associated with the distinct configuration.

Flexible and weaveable capacitor wire based on a carbon nanocomposite fiber.

PubMed

Ren, Jing; Bai, Wenyu; Guan, Guozhen; Zhang, Ye; Peng, Huisheng

2013-11-06

A flexible and weaveable electric double-layer capacitor wire is developed by twisting two aligned carbon nanotube/ordered mesoporous carbon composite fibers with remarkable mechanical and electronic properties as electrodes. This capacitor wire exhibits high specific capacitance and long life stability. Compared with the conventional planar structure, the capacitor wire is also lightweight and can be integrated into various textile structures that are particularly promising for portable and wearable electronic devices. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3D structure of individual nanocrystals in solution by electron microscopy

DOE PAGES

Park, Jungwok; Elmlund, Hans; Ercius, Peter; ...

2015-07-17

Here, knowledge about the synthesis, growth mechanisms, and physical properties of colloidal nanoparticles has been limited by technical impediments. We introduce a method for determining three-dimensional (3D) structures of individual nanoparticles in solution. We combine a graphene liquid cell, high-resolution transmission electron microscopy, a direct electron detector, and an algorithm for single-particle 3D reconstruction originally developed for analysis of biological molecules. This method yielded two 3D structures of individual platinum nanocrystals at near-atomic resolution. Because our method derives the 3D structure from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unorderedmore » nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale.« less

Nanoparticle imaging. 3D structure of individual nanocrystals in solution by electron microscopy.

PubMed

Park, Jungwon; Elmlund, Hans; Ercius, Peter; Yuk, Jong Min; Limmer, David T; Chen, Qian; Kim, Kwanpyo; Han, Sang Hoon; Weitz, David A; Zettl, A; Alivisatos, A Paul

2015-07-17

Knowledge about the synthesis, growth mechanisms, and physical properties of colloidal nanoparticles has been limited by technical impediments. We introduce a method for determining three-dimensional (3D) structures of individual nanoparticles in solution. We combine a graphene liquid cell, high-resolution transmission electron microscopy, a direct electron detector, and an algorithm for single-particle 3D reconstruction originally developed for analysis of biological molecules. This method yielded two 3D structures of individual platinum nanocrystals at near-atomic resolution. Because our method derives the 3D structure from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unordered nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale. Copyright © 2015, American Association for the Advancement of Science.

3D structure of individual nanocrystals in solution by electron microscopy

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

Park, Jungwok; Elmlund, Hans; Ercius, Peter

Here, knowledge about the synthesis, growth mechanisms, and physical properties of colloidal nanoparticles has been limited by technical impediments. We introduce a method for determining three-dimensional (3D) structures of individual nanoparticles in solution. We combine a graphene liquid cell, high-resolution transmission electron microscopy, a direct electron detector, and an algorithm for single-particle 3D reconstruction originally developed for analysis of biological molecules. This method yielded two 3D structures of individual platinum nanocrystals at near-atomic resolution. Because our method derives the 3D structure from images of individual nanoparticles rotating freely in solution, it enables the analysis of heterogeneous populations of potentially unorderedmore » nanoparticles that are synthesized in solution, thereby providing a means to understand the structure and stability of defects at the nanoscale.« less

Gold-film coating assisted femtosecond laser fabrication of large-area, uniform periodic surface structures.

PubMed

Feng, Pin; Jiang, Lan; Li, Xin; Rong, Wenlong; Zhang, Kaihu; Cao, Qiang

2015-02-20

A simple, repeatable approach is proposed to fabricate large-area, uniform periodic surface structures by a femtosecond laser. 20 nm gold films are coated on semiconductor surfaces on which large-area, uniform structures are fabricated. In the case study of silicon, cross-links and broken structures of laser induced periodic surface structures (LIPSSs) are significantly reduced on Au-coated silicon. The good consistency between the scanning lines facilitates the formation of large-area, uniform LIPSSs. The diffusion of hot electrons in the Au films increases the interfacial carrier densities, which significantly enhances interfacial electron-phonon coupling. High and uniform electron density suppresses the influence of defects on the silicon and further makes the coupling field more uniform and thus reduces the impact of laser energy fluctuations, which homogenizes and stabilizes large-area LIPSSs.

Electronically conductive ceramics for high temperature oxidizing environments

DOEpatents

Kucera, Gene H.; Smith, James L.; Sim, James W.

1986-01-01

A high temperature, ceramic composition having electronic conductivity as measured by resistivity below about 500 ohm-cm, chemical stability particularly with respect to cathode conditions in a molten carbonate fuel cell, and composed of an alkali metal, transition metal oxide containing a dopant metal in the crystalline structure to replace a portion of the alkali metal or transition metal.

Single layers and multilayers of GaN and AlN in square-octagon structure: Stability, electronic properties, and functionalization

NASA Astrophysics Data System (ADS)

Gürbüz, E.; Cahangirov, S.; Durgun, E.; Ciraci, S.

2017-11-01

Further to planar single-layer hexagonal structures, GaN and AlN can also form free-standing, single-layer structures constructed from squares and octagons. We performed an extensive analysis of dynamical and thermal stability of these structures in terms of ab initio finite-temperature molecular dynamics and phonon calculations together with the analysis of Raman and infrared active modes. These single-layer square-octagon structures of GaN and AlN display directional mechanical properties and have wide, indirect fundamental band gaps, which are smaller than their hexagonal counterparts. These density functional theory band gaps, however, increase and become wider upon correction. Under uniaxial and biaxial tensile strain, the fundamental band gaps decrease and can be closed. The electronic and magnetic properties of these single-layer structures can be modified by adsorption of various adatoms, or by creating neutral cation-anion vacancies. The single-layer structures attain magnetic moment by selected adatoms and neutral vacancies. In particular, localized gap states are strongly dependent on the type of vacancy. The energetics, binding, and resulting electronic structure of bilayer, trilayer, and three-dimensional (3D) layered structures constructed by stacking the single layers are affected by vertical chemical bonds between adjacent layers. In addition to van der Waals interaction, these weak vertical bonds induce buckling in planar geometry and enhance their binding, leading to the formation of stable 3D layered structures. In this respect, these multilayers are intermediate between van der Waals solids and wurtzite crystals, offering a wide range of tunability.

Nanocarbon networks for advanced rechargeable lithium batteries.

PubMed

Xin, Sen; Guo, Yu-Guo; Wan, Li-Jun

2012-10-16

Carbon is one of the essential elements in energy storage. In rechargeable lithium batteries, researchers have considered many types of nanostructured carbons, such as carbon nanoparticles, carbon nanotubes, graphene, and nanoporous carbon, as anode materials and, especially, as key components for building advanced composite electrode materials. Nanocarbons can form efficient three-dimensional conducting networks that improve the performance of electrode materials suffering from the limited kinetics of lithium storage. Although the porous structure guarantees a fast migration of Li ions, the nanocarbon network can serve as an effective matrix for dispersing the active materials to prevent them from agglomerating. The nanocarbon network also affords an efficient electron pathway to provide better electrical contacts. Because of their structural stability and flexibility, nanocarbon networks can alleviate the stress and volume changes that occur in active materials during the Li insertion/extraction process. Through the elegant design of hierarchical electrode materials with nanocarbon networks, researchers can improve both the kinetic performance and the structural stability of the electrode material, which leads to optimal battery capacity, cycling stability, and rate capability. This Account summarizes recent progress in the structural design, chemical synthesis, and characterization of the electrochemical properties of nanocarbon networks for Li-ion batteries. In such systems, storage occurs primarily in the non-carbon components, while carbon acts as the conductor and as the structural buffer. We emphasize representative nanocarbon networks including those that use carbon nanotubes and graphene. We discuss the role of carbon in enhancing the performance of various electrode materials in areas such as Li storage, Li ion and electron transport, and structural stability during cycling. We especially highlight the use of graphene to construct the carbon conducting network for alloy anodes, such as Si and Ge, to accelerate electron transport, alleviate volume change, and prevent the agglomeration of active nanoparticles. Finally, we describe the power of nanocarbon networks for the next generation rechargeable lithium batteries, including Li-S, Li-O(2), and Li-organic batteries, and provide insights into the design of ideal nanocarbon networks for these devices. In addition, we address the ways in which nanocarbon networks can expand the applications of rechargeable lithium batteries into the emerging fields of stationary energy storage and transportation.

Structure, reactivity and electronic properties of Mn doped Ni13 clusters

NASA Astrophysics Data System (ADS)

Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

2013-06-01

In this work we have studied the structural and magnetic properties of Ni13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni12Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni12MnH2. Our analysis of the stability and HOMO-LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H2 absorption in the doped NiMnm alloy clusters. This has been reported earlier for smaller Nin clusters [1].

Massive Interfacial Reconstruction at Misfit Dislocations in Metal/Oxide Interfaces

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

Choudhury, Samrat; Morgan, Dane; Uberuaga, Blas P.

Electronic structure calculations were performed to study the role of misfit dislocations on the structure and chemistry of a metal/oxide interface. We found that a chemical imbalance exists at the misfit dislocation which leads to dramatic changes in the point defect content at the interface – stabilizing the structure requires removing as much as 50% of the metal atoms and insertion of a large number of oxygen interstitials. The exact defect composition that stabilizes the interface is sensitive to the external oxygen partial pressure. We relate the preferred defect structure at the interface to a competition between chemical and strainmore » energies as defects are introduced.« less

Massive Interfacial Reconstruction at Misfit Dislocations in Metal/Oxide Interfaces

DOE PAGES

Choudhury, Samrat; Morgan, Dane; Uberuaga, Blas P.

2014-10-17

Electronic structure calculations were performed to study the role of misfit dislocations on the structure and chemistry of a metal/oxide interface. We found that a chemical imbalance exists at the misfit dislocation which leads to dramatic changes in the point defect content at the interface – stabilizing the structure requires removing as much as 50% of the metal atoms and insertion of a large number of oxygen interstitials. The exact defect composition that stabilizes the interface is sensitive to the external oxygen partial pressure. We relate the preferred defect structure at the interface to a competition between chemical and strainmore » energies as defects are introduced.« less

Robust diamond-like Fe-Si network in the zero-strain Na xFeSiO 4 cathode

DOE PAGES

Ye, Zhuo; Zhao, Xin; Li, Shouding; ...

2016-07-14

Sodium orthosilicates Na 2 MSiO 4 ( M denotes transition metals) have attracted much attention due to the possibility of exchanging two electrons per formula unit. In this work, we report a group of sodium iron orthosilicates Na 2FeSiO 4. Their crystal structures are characterized by a diamond-like Fe-Si network. The Fe-Si network is quite robust against the charge/discharge process, which explains the high structural stability observed in experiment. Furthermore, using the density functional theory within the GGA + U framework and X-ray diffraction studies, the crystal structures and structural stabilities during the sodium extraction/re-insertion process are systematically investigated.

Aging effects on vertical graphene nanosheets and their thermal stability

NASA Astrophysics Data System (ADS)

Ghosh, S.; Polaki, S. R.; Ajikumar, P. K.; Krishna, N. G.; Kamruddin, M.

2018-03-01

The present study investigates environmental aging effects and thermal stability of vertical graphene nanosheets (VGN). Self-organized VGN is synthesized by plasma enhanced chemical vapor deposition and exposed to ambient conditions over 6-month period to examine its aging behavior. A systematic inspection is carried out on morphology, chemical structure, wettability and electrical property by scanning electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, water contact angle and four-probe resistivity measurements at regular intervals, respectively. Detailed microscopic and spectroscopic analysis substantiated the retention of graphitic quality and surface chemistry of VGN over the test period. An unchanged sheet resistance and hydrophobicity reveals its electrical and wetting stability over the time, respectively. Thermogravimetric analysis ensures an excellent thermal stability of VGN up to 575 °C in ambient atmosphere. These findings of long-term morphological, structural, wetting, electrical and thermal stability of VGN validate their potential utilization for the next-generation device applications.

First-principles phase stability at high temperatures and pressure in Nb 90Zr 10 alloy

DOE PAGES

Landa, A.; Soderlind, P.

2016-08-18

The phase stability of Nb 90Zr 10 alloy at high temperatures and compression is explored by means of first-principles electronic-structure calculations. Utilizing the self-consistent ab initio lattice dynamics (SCAILD) approach in conjunction with density-functional theory, we show that pressure-induced mechanical instability of the body-centered cubic phase, which results in formation of a rhombohedral phase at around 50 GPa, will prevail significant heating. As a result, the body-centered cubic structure will recover before melting at ~1800 K.

Electronic structure, stability and magnetic properties of small M1-4(M = Fe, Co, Ni) clusters encapsulated inside a (BN)48 cage

NASA Astrophysics Data System (ADS)

Liang, Wenjuan; Jia, Jianfeng; Lv, Jin; Wu, Haishun

2015-02-01

The geometrical structure and magnetic properties of M1-4(M = Fe, Co and Ni) clusters within a (BN)48 cage were calculated at the BPW91/LanL2DZ level. The small M1-4 clusters generally prefer an off-centered position near the hexagonal rings in the (BN)48 cages. The (BN)48 cages can increase the stability of these small magnetic clusters while protecting the magnetic nature of M and M2 clusters.

Sc20C60: a volleyballene

NASA Astrophysics Data System (ADS)

Wang, Jing; Ma, Hong-Man; Liu, Ying

2016-06-01

An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable.An exceptionally stable hollow cage containing 20 scandium atoms and 60 carbon atoms has been identified. This Sc20C60 molecular cluster has a Th point group symmetry and a volleyball-like shape that we refer to below as ``Volleyballene''. Electronic structure analysis shows that the formation of delocalized π bonds between Sc atoms and the neighboring pentagonal rings made of carbon atoms is crucial for stabilizing the cage structure. A relatively large HOMO-LUMO gap (~1.4 eV) was found. The results of vibrational frequency analysis and molecular dynamics simulations both demonstrate that this Volleyballene molecule is exceptionally stable. Electronic supplementary information (ESI) available: Sc20C60: a Volleyballene_SI. See DOI: 10.1039/c5nr07784b

Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality.

PubMed

Sergeeva, Alina P; Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Romanescu, Constantin; Wang, Lai-Sheng; Boldyrev, Alexander I

2014-04-15

Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron's electron deficiency and leads to fluxional behavior, which has been observed in B13(+) and B19(-). A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B(-), formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B(-)/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors' laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.

Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

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

Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.

Conspectus Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center–two-electron (2c–2e) σ bonds on the periphery and delocalized multicenter–two-electron (nc–2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron’s electron deficiency and leads to fluxional behavior, which has been observed in B13+ and B19–. A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiationmore » has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B–, formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B–/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors’ laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.« less

Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam

DOE PAGES

Lin, Feng; Markus, Isaac M.; Doeff, Marca M.; ...

2014-07-16

Our investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. But, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi 0.4Mn 0.4Co 0.18Ti 0.02O 2 particles, repeated electron beam irradiation induced a phase transition from an Rmore » $$\\bar{3}$$m layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from R$$\\bar{3}$$m 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, in using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results.« less

Density-functional tight-binding investigation of the structure, stability and material properties of nickel hydroxide nanotubes

NASA Astrophysics Data System (ADS)

Jahangiri, Soran; Mosey, Nicholas J.

2018-01-01

Nickel hydroxide is a material composed of two-dimensional layers that can be rolled up to form cylindrical nanotubes belonging to a class of inorganic metal hydroxide nanotubes that are candidates for applications in catalysis, energy storage, and microelectronics. The stabilities and other properties of this class of inorganic nanotubes have not yet been investigated in detail. The present study uses self-consistent-charge density-functional tight-binding calculations to examine the stabilities, mechanical properties, and electronic properties of nickel hydroxide nanotubes along with the energetics associated with the adsorption of water by these systems. The tight-binding model was parametrized for this system based on the results of first-principles calculations. The stabilities of the nanotubes were examined by calculating strain energies and performing molecular dynamics simulations. The results indicate that single-walled nickel hydroxide nanotubes are stable at room temperature, which is consistent with experimental investigations. The nanotubes possess size-dependent mechanical properties that are similar in magnitude to those of other inorganic nanotubes. The electronic properties of the nanotubes were also found to be size-dependent and small nickel oxyhydroxide nanotubes are predicted to be semiconductors. Despite this size-dependence, both the mechanical and electronic properties were found to be almost independent of the helical structure of the nanotubes. The calculations also show that water molecules have higher adsorption energies when binding to the interior of the nickel hydroxide nanotubes when compared to adsorption in nanotubes formed from other two-dimensional materials such as graphene. The increased adsorption energy is due to the hydrophilic nature of nickel hydroxide. Due to the broad applications of nickel hydroxide, the nanotubes investigated here are also expected to be used in catalysis, electronics, and clean energy production.

Silacyanogen

NASA Astrophysics Data System (ADS)

Ignatyev, Igor S.; Schaefer, Henry F., III

1997-10-01

Structures of all possible linear isomers of the Si-substituted cyanogen were optimized at the SCF, B3LYP, MP2, and CCSD levels of theory. At all levels of theory the most stable isomer was found to be SiNCN, while for cyanogen the most stable structure is well known to be NCCN. The theoretical ordering of the stability of the acyclic structures is SiNCN>SiNNO>NSiCN>NSiNC. The difference in the order of stability of silacyanogen and cyanogen isomers is rationalized, taking into account the position of the unpaired electron on carbon in the CN radical and that on nitrogen in the SiN radical.

Electronic and structural properties of B i2S e3:Cu

NASA Astrophysics Data System (ADS)

Sobczak, Kamil; Strak, Pawel; Kempisty, Pawel; Wolos, Agnieszka; Hruban, Andrzej; Materna, Andrzej; Borysiuk, Jolanta

2018-04-01

Electronic and structural properties of B i2S e3 and its extension to copper doped B i2S e3:Cu were studied using combined ab initio simulations and transmission electron microscopy based techniques, including electron energy loss spectroscopy, energy filtered transmission electron microscopy, and energy dispersive x-ray spectroscopy. The stability of the mixed phases was investigated for substitutional and intercalation changes of basic B i2S e3 structure. Four systems were compared: B i2S e3 , structures obtaining by Cu intercalation of the van der Waals gap, by substitution of Bi by Cu in quintuple layers, and C u2Se . The structures were identified and their electronic properties were obtained. Transmission electron microscopy measurements of B i2S e3 and the B i2S e3:Cu system identified the first structure as uniform and the second as composite, consisting of a nonuniform lower-Cu-content matrix and randomly distributed high-Cu-concentration precipitates. Critical comparison of the ab initio and experimental data identified the matrix as having a B i2S e3 dominant part with randomly distributed Cu-intercalated regions having 1Cu-B i2S e3 structure. The precipitates were determined to have 3Cu-B i2S e3 structure.

Mesh-structured N-doped graphene@Sb2Se3 hybrids as an anode for large capacity sodium-ion batteries.

PubMed

Zhao, Wenxi; Li, Chang Ming

2017-02-15

A mesh-structured N-doped graphene@Sb 2 Se 3 (NGS) hybrid was one-pot prepared to realize N-doping, nanostructuring and hybridization for a sodium-ion battery anode to deliver much larger reversible specific capacity, faster interfacial electron transfer rate, better ionic and electronic transport, higher rate performance and longer cycle life stability in comparison to the plain Sb 2 Se 3 one. The better performance is ascribed to the unique intertwined porous mash-like structure associated with a strong synergistic effect of N-doped graphene for dramatic improvement of electronic and ionic conductivity by the unique porous structure, the specific capacity of graphene from N doping and fast interfacial electron transfer rate by N-doping induced surface effect and the structure-shortening insertion/desertion pathway of Na + . The detail electrochemical process on the NGS electrode is proposed and analyzed in terms of the experimental results. Copyright © 2016 Elsevier Inc. All rights reserved.

Crystal structure stability and electronic properties of the layered nickelate La4Ni3O10

NASA Astrophysics Data System (ADS)

Puggioni, Danilo; Rondinelli, James M.

2018-03-01

We investigate the crystal structure and the electronic properties of the trilayer nickelate La4Ni3O10 by means of quantum-mechanical calculations in the framework of the density-functional theory. We find that, at low temperature, La4Ni3O10 undergoes a hitherto unreported structural phase transition and transforms to a new monoclinic P 21/a phase. This phase exhibits electronic properties in agreement with recent angle-resolved photoemission spectroscopy data reported in H. Li et al., [Nat. Commun. 8, 704 (2017), 10.1038/s41467-017-00777-0] and should be considered in models focused on explaining the observed ˜140 K metal-to-metal phase transition.

Exploration of multi-fold symmetry element-loaded superconducting radio frequency structure for reliable acceleration of low- & medium-beta ion species

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

Huang, Shichun; Geng, Rongli

2015-09-01

Reliable acceleration of low- to medium-beta proton or heavy ion species is needed for future high-current superconducting radio frequency (SRF) accelerators. Due to the high-Q nature of an SRF resonator, it is sensitive to many factors such as electron loading (from either the accelerated beam or from parasitic field emitted electrons), mechanical vibration, and liquid helium bath pressure fluctuation etc. To increase the stability against those factors, a mechanically strong and stable RF structure is desirable. Guided by this consideration, multi-fold symmetry element-loaded SRF structures (MFSEL), cylindrical tanks with multiple (n>=3) rod-shaped radial elements, are being explored. The top goalmore » of its optimization is to improve mechanical stability. A natural consequence of this structure is a lowered ratio of the peak surface electromagnetic field to the acceleration gradient as compared to the traditional spoke cavity. A disadvantage of this new structure is an increased size for a fixed resonant frequency and optimal beta. This paper describes the optimization of the electro-magnetic (EM) design and preliminary mechanical analysis for such structures.« less

First-principles calculations of structural, elastic, electronic, and optical properties of perovskite-type KMgH3 crystals: novel hydrogen storage material.

PubMed

Reshak, Ali H; Shalaginov, Mikhail Y; Saeed, Yasir; Kityk, I V; Auluck, S

2011-03-31

We report a first-principles study of structural and phase stability in three different structures of perovskite-types KMgH(3) according to H position. While electronic and optical properties were measured only for stable perovskite-type KMgH(3), our calculated structural parameters are found in good agreement with experiment and other theoretical results. We also study the electronic charge density space distribution contours in the (200), (101), and (100) crystallographic planes, which gives better insight picture of chemical bonding between K-H, K-Mg-H, and Mg-H. Moreover, we have calculated the electronic band structure dispersion, total, and partial density of electron states to study the band gap origin and the contribution of s-band of H, s and p-band of Mg in the valence band, and d-band of K in the conduction band. Furthermore, optical features such as dielectric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients, optical conductivities, and loss functions of stable KMgH(3) were calculated for photon energies up to 40 eV.

Bilayered graphene/h-BN with folded holes as new nanoelectronic materials: modeling of structures and electronic properties

PubMed Central

Chernozatonskii, Leonid A.; Demin, Viсtor A.; Bellucci, Stefano

2016-01-01

The latest achievements in 2-dimensional (2D) material research have shown the perspective use of sandwich structures in nanodevices. We demonstrate the following generation of bilayer materials for electronics and optoelectronics. The atomic structures, the stability and electronic properties of Moiré graphene (G)/h-BN bilayers with folded nanoholes have been investigated theoretically by ab-initio DFT method. These perforated bilayers with folded hole edges may present electronic properties different from the properties of both graphene and monolayer nanomesh structures. The closing of the edges is realized by C-B(N) bonds that form after folding the borders of the holes. Stable ≪round≫ and ≪triangle≫ holes organization are studied and compared with similar hole forms in single layer graphene. The electronic band structures of the considered G/BN nanomeshes reveal semiconducting or metallic characteristics depending on the sizes and edge terminations of the created holes. This investigation of the new types of G/BN nanostructures with folded edges might provide a directional guide for the future of this emerging area. PMID:27897237

Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole

NASA Astrophysics Data System (ADS)

Arjunan, V.; Raj, Arushma; Santhanam, R.; Marchewka, M. K.; Mohan, S.

2013-02-01

Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. 1H and 13C NMR chemical shifts and the electronic transitions of the molecule are also discussed.

The Calculation Study of Electronic Properties of Doped RE (Eu, Er and Tm)-GaN using Density Functional Theory

NASA Astrophysics Data System (ADS)

Zaharo, Aflah; Purqon, Acep

2017-07-01

The calculation of the structure and electronic properties of Rare Earth (RE) at the wurtzite Gallium Nitride (GaN) based on DFT has completed. GGA approximation used for exchange correlation and Ultra soft pseudo potential too. The stability structure of GaN is seen that difference lattice parameter 11% lower than another calculation and experiment result. It is shown the stability structure GaN have direct band gap energy on Gamma point hexagonal lattice Brillouin zone. The width Eg is 2.6 eV. When one atom Ga is substituted with one atom RE, the bond length is change 12 % longest. An in good agreement with theoretical doping RE concentration increases, the edge of energy level shifted towards to make the band gap narrow which is allow the optical transitions and help to improve the optical performance of GaN. The RE doped GaN is potentially applicable for various color of LED with lower energy consumption and potentially energy saving application

Zirconia and its allotropes; A Quantum Monte Carlo study

NASA Astrophysics Data System (ADS)

Jokisaari, Andrea; Benali, Anouar; Shin, Hyeondeok; Luo, Ye; Lopez Bezanilla, Alejandro; Ratcliff, Laura; Littlewood, Peter; Heinonen, Olle

With a high strength and stability at elevated temperatures, Zirconia (zirconium dioxide) is one of the best corrosion-resistant and refractive materials used in metallurgy, and is used in structural ceramics, catalytic converters, oxygen sensors, nuclear industry, and in chemically passivating surfaces. The wide range of applications of ZrO2 has motivated a large number of electronic structures studies of its known allotropes (monoclinic, tetragonal and cubic). Density Functional Theory has been successful at reproducing some of the fundamental properties of some of the allotropes, but these results remain dependent on the specific combination of exchange-correlation functional and type of pseudopotentials, making any type of structural prediction or defect analysis uncertain. Quantum Monte Carlo (QMC) is a many-body quantum theory solving explicitly the electronic correlations, allowing reproducing and predicting materials properties with a limited number of controlled approximations. In this study, we use QMC to revisit the energetic stability of Zirconia's allotropes and compare our results with those obtained from density functional theory.

Electrochemical performance of a thermally rearranged polybenzoxazole nanocomposite membrane as a separator for lithium-ion batteries at elevated temperature

NASA Astrophysics Data System (ADS)

Lee, Moon Joo; Hwang, Jun-Ki; Kim, Ji Hoon; Lim, Hyung-Seok; Sun, Yang-Kook; Suh, Kyung-Do; Lee, Young Moo

2016-02-01

Shape-tunable hydroxyl copolyimide (HPI) nanoparticles are fabricated by a re-precipitation method and are coated onto electrospun HPI membranes, followed by heat treatment to prepare thermally rearranged polybenzoxazole (TR-PBO) composite membranes. The morphology of HPI nanoparticles consisted of sphere and sea-squirt structures, which is controlled by changing the concentration of the stabilizer. The morphological characteristics of TR-PBO nanoparticles convert from HPI nanoparticles by heat treatment and their composite membranes is confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), infrared spectroscopy (ATR-IR), thermogravimetric analysis (TGA) analysis, and contact angle measurements. TGA and DSC measurements confirm the excellent thermal stability compared to Celgard, a commercial PP separator for lithium-ion batteries (LIBs). Further, TR-PBO nano-composite membranes used in coin-cell type LIBs as a separator show excellent high power density performance as compared to Celgard. This is due to the fact that sea-squirt structured nanoparticles have better electrochemical properties than sphere structured nanoparticles at high temperature.

The stability of aluminium oxide monolayer and its interface with two-dimensional materials

NASA Astrophysics Data System (ADS)

Song, Ting Ting; Yang, Ming; Chai, Jian Wei; Callsen, Martin; Zhou, Jun; Yang, Tong; Zhang, Zheng; Pan, Ji Sheng; Chi, Dong Zhi; Feng, Yuan Ping; Wang, Shi Jie

2016-07-01

The miniaturization of future electronic devices requires the knowledge of interfacial properties between two-dimensional channel materials and high-κ dielectrics in the limit of one atomic layer thickness. In this report, by combining particle-swarm optimization method with first-principles calculations, we present a detailed study of structural, electronic, mechanical, and dielectric properties of Al2O3 monolayer. We predict that planar Al2O3 monolayer is globally stable with a direct band gap of 5.99 eV and thermal stability up to 1100 K. The stability of this high-κ oxide monolayer can be enhanced by substrates such as graphene, for which the interfacial interaction is found to be weak. The band offsets between the Al2O3 monolayer and graphene are large enough for electronic applications. Our results not only predict a stable high-κ oxide monolayer, but also improve the understanding of interfacial properties between a high-κ dielectric monolayer and two-dimensional material.

Dendronic trimaltoside amphiphiles (DTMs) for membrane protein study† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03700g

PubMed Central

Sadaf, Aiman; Du, Yang; Santillan, Claudia; Mortensen, Jonas S.; Molist, Iago; Seven, Alpay B.; Hariharan, Parameswaran; Skiniotis, Georgios; Loland, Claus J.; Kobilka, Brian K.; Guan, Lan; Byrne, Bernadette

2017-01-01

The critical contribution of membrane proteins in normal cellular function makes their detailed structure and functional analysis essential. Detergents, amphipathic agents with the ability to maintain membrane proteins in a soluble state in aqueous solution, have key roles in membrane protein manipulation. Structural and functional stability is a prerequisite for biophysical characterization. However, many conventional detergents are limited in their ability to stabilize membrane proteins, making development of novel detergents for membrane protein manipulation an important research area. The architecture of a detergent hydrophobic group, that directly interacts with the hydrophobic segment of membrane proteins, is a key factor in dictating their efficacy for both membrane protein solubilization and stabilization. In the current study, we developed two sets of maltoside-based detergents with four alkyl chains by introducing dendronic hydrophobic groups connected to a trimaltoside head group, designated dendronic trimaltosides (DTMs). Representative DTMs conferred enhanced stabilization to multiple membrane proteins compared to the benchmark conventional detergent, DDM. One DTM (i.e., DTM-A6) clearly outperformed DDM in stabilizing human β2 adrenergic receptor (β2AR) and its complex with Gs protein. A further evaluation of this DTM led to a clear visualization of β2AR-Gs complex via electron microscopic analysis. Thus, the current study not only provides novel detergent tools useful for membrane protein study, but also suggests that the dendronic architecture has a role in governing detergent efficacy for membrane protein stabilization. PMID:29619178

Analysis of the electron density features of small boron clusters and the effects of doping with C, P, Al, Si, and Zn: Magic B7P and B8Si clusters

NASA Astrophysics Data System (ADS)

Saha, P.; Rahane, A. B.; Kumar, V.; Sukumar, N.

2016-05-01

Boron atomic clusters show several interesting and unusual size-dependent features due to the small covalent radius, electron deficiency, and higher coordination number of boron as compared to carbon. These include aromaticity and a diverse array of structures such as quasi-planar, ring or tubular shaped, and fullerene-like. In the present work, we have analyzed features of the computed electron density distributions of small boron clusters having up to 11 boron atoms, and investigated the effect of doping with C, P, Al, Si, and Zn atoms on their structural and physical properties, in order to understand the bonding characteristics and discern trends in bonding and stability. We find that in general there are covalent bonds as well as delocalized charge distribution in these clusters. We associate the strong stability of some of these planar/quasiplanar disc-type clusters with the electronic shell closing with effectively twelve delocalized valence electrons using a disc-shaped jellium model. {{{{B}}}9}-, B10, B7P, and B8Si, in particular, are found to be exceptional with very large gaps between the highest occupied molecular orbital and the lowest unoccupied molecular orbital, and these are suggested to be magic clusters.

Structure and Magnetic Properties of Rare Earth Doped Transparent Alumina

NASA Astrophysics Data System (ADS)

Limmer, Krista; Neupane, Mahesh; Chantawansri, Tanya

Recent experimental studies of rare earth (RE) doped alumina suggest that the RE induced novel phase-dependent structural and magnetic properties. Motivated by these efforts, the effects of RE doping of alpha and theta alumina on the local structure, magnetic properties, and phase stability have been examined in this first principles study. Although a direct correlation between the magnetic field dependent materials properties observed experimentally and calculated from first principles is not feasible because of the applied field and the scale, the internal magnetic properties and other properties of the doped materials are evaluated. The RE dopants are shown to increase the substitutional site volume as well as increasingly distort the site structure as a function of ionic radii. Doping both the alpha (stable) and theta (metastable) phases enhanced the relative stability of the theta phase. The energetic doping cost and internal magnetic moment were shown to be a function of the electronic configuration of the RE-dopant, with magnetic moment directly proportional to the number of unpaired electrons and doping cost being inversely related.

Cargo–shell and cargo–cargo couplings govern the mechanics of artificially loaded virus-derived cages†

PubMed Central

Llauró, Aida; Luque, Daniel; Edwards, Ethan; Trus, Benes L.; Avera, John; Reguera, David; Douglas, Trevor

2016-01-01

Nucleic acids are the natural cargo of viruses and key determinants that affect viral shell stability. In some cases the genome structurally reinforces the shell, whereas in others genome packaging causes internal pressure that can induce destabilization. Although it is possible to pack heterologous cargoes inside virus-derived shells, little is known about the physical determinants of these artificial nanocontainers’ stability. Atomic force and three-dimensional cryo-electron microscopy provided mechanical and structural information about the physical mechanisms of viral cage stabilization beyond the mere presence/absence of cargos. We analyzed the effects of cargo–shell and cargo–cargo interactions on shell stability after encapsulating two types of proteinaceous payloads. While bound cargo to the inner capsid surface mechanically reinforced the capsid in a structural manner, unbound cargo diffusing freely within the shell cavity pressurized the cages up to ~30 atm due to steric effects. Strong cargo–cargo coupling reduces the resilience of these nanocompartments in ~20% when bound to the shell. Understanding the stability of artificially loaded nanocages will help to design more robust and durable molecular nanocontainers. PMID:27091107

Site occupancy, composition and magnetic structure dependencies of martensitic transformation in Mn2Ni1 + x Sn1-x.

PubMed

Kundu, Ashis; Ghosh, Subhradip

2017-11-29

A delicate balance between various factors such as site occupancy, composition and magnetic ordering seems to affect the stability of the martensitic phase in [Formula: see text] [Formula: see text] [Formula: see text]. Using first-principles DFT calculations, we explore the impacts of each one of these factors on the martensitic stability of this system. Our results on total energies, magnetic moments and electronic structures upon changes in the composition, the magnetic configurations and the site occupancies show that the occupancies at the 4d sites in the inverse Heusler crystal structure play the most crucial role. The presence of Mn at the 4d sites originally occupied by Sn and its interaction with the Mn atoms at other sites decide the stability of the martensitic phases. This explains the discrepancy between the experiments and earlier DFT calculations regarding phase stability in [Formula: see text]NiSn. Our results qualitatively explain the trends observed experimentally with regard to martensitic phase stability and the magnetisations in Ni-excess, Sn-deficient [Formula: see text]NiSn system.

Electronically conductive ceramics for high temperature oxidizing environments

DOEpatents

Kucera, G.H.; Smith, J.L.; Sim, J.W.

1983-11-10

This invention pertains to a high temperature, ceramic composition having electronic conductivity as measured by resistivity below about 500 ohm-cm, chemical stability particularly with respect to cathode conditions in a molten carbonate fuel cell, and composed of an alkali metal, transition metal oxide containing a dopant metal in the crystalline structure to replace a portion of the alkali metal or transition metal.

Unconditionally marginal stability of harmonic electron hole equilibria in current-driven plasmas

NASA Astrophysics Data System (ADS)

Schamel, Hans

2018-06-01

Two forms of the linearized eigenvalue problem with respect to linear perturbations of a privileged cnoidal electron hole as a structural nonlinear equilibrium element are established. Whereas its integral form involves integrations along the characteristics or unperturbed particle orbits, the differential form has to cope with a differential operator of infinite order. Both are hence faced with difficulties to obtain a solution. A first successful attempt is, however, made by addressing a single harmonic wave as a nonlinear equilibrium structure. By this microscopic nonlinear approach, its marginal stability against linear perturbations in both linear stability regimes, the sub- and super-critical one, is shown independent of the mobility of ions and in favor with recent observations. Responsible for vanishing damping (growth) is the microscopic distortion of the resonant distribution function. The macroscopic form of the trapping nonlinearity—the 3/2 power term of the electrostatic potential in the density—which disappears in the monochromatic harmonic wave limit is consequently necessary for the occurrence of a nonlinear plasma instability in the sub-critical regime.

Excited state electron transfer in systems with a well-defined geometry. [cyclophane

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

Kaufmann, K.J.

1980-12-01

The effect of temperature, dielectric strength and ligand on the structure of the mesopyropheophorbide cyclophanes will be studied. ESR, NMR, emission and absorption spectroscopy, as well as circular dichroism will be used. The changes in structure will be correlated with changes in the photochemical activity. Electron acceptors such as benzoquinone will be utilized to stabilize the charge separation. Charge separation in porphyrin quinone dimers will also be studied. It was found that electron transfer in the cyclophane system is relatively slow. This is presumably due to an orientation requirement for fast electron transfer. Solvent dielectric also is important in producingmore » a charge separation. Decreasing the temperature effects the yield of charge transfer, but not the kinetics.« less

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

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

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimatesmore » or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.« less

Structural and optical properties of electron beam evaporated yttria stabilized zirconia thin films

NASA Astrophysics Data System (ADS)

Kirubaharan, A. Kamalan; Kuppusami, P.; Singh, Akash; Dharini, T.; Ramachandran, D.; Mohandas, E.

2015-06-01

Yttria stabilized zirconia (10 mole % Y2O3) thin films were deposited on quartz substrates using electron beam physical vapor deposition at the substrate temperatures in the range 300 - 973 K. XRD analysis showed cubic crystalline phase of YSZ films with preferred orientation along (111). The surface roughness was found to increase with the increase of deposition temperatures. The optical band gap of ˜5.7 eV was calculated from transmittance curves. The variation in the optical properties is correlated with the changes in the microstructural features of the films prepared as a function of substrate temperature.

Investigations of mechanical, electronic, and magnetic properties of non-magnetic MgTe and ferro-magnetic Mg0.75 TM 0.25Te (TM = Fe, Co, Ni): An ab-initio calculation

NASA Astrophysics Data System (ADS)

Q, Mahmood; S, M. Alay-e.-Abbas; I, Mahmood; Mahmood, Asif; N, A. Noor

2016-04-01

The mechanical, electronic and magnetic properties of non-magnetic MgTe and ferro-magnetic (FM) Mg0.75 TM 0.25Te (TM = Fe, Co, Ni) in the zinc-blende phase are studied by ab-initio calculations for the first time. We use the generalized gradient approximation functional for computing the structural stability, and mechanical properties, while the modified Becke and Johnson local (spin) density approximation (mBJLDA) is utilized for determining the electronic and magnetic properties. By comparing the energies of non-magnetic and FM calculations, we find that the compounds are stable in the FM phase, which is confirmed by their structural stabilities in terms of enthalpy of formation. Detailed descriptions of elastic properties of Mg0.75 TM 0.25Te alloys in the FM phase are also presented. For electronic properties, the spin-polarized electronic band structures and density of states are computed, showing that these compounds are direct bandgap materials with strong hybridizations of TM 3d states and Te p states. Further, the ferromagnetism is discussed in terms of the Zener free electron model, RKKY model and double exchange model. The charge density contours in the (110) plane are calculated to study bonding properties. The spin exchange splitting and crystal field splitting energies are also calculated. The distribution of electron spin density is employed in computing the magnetic moments appearing at the magnetic sites (Fe, Co, Ni), as well as at the non-magnetic sites (Mg, Te). It is found that the p-d hybridization causes not only magnetic moments on the magnetic sites but also induces negligibly small magnetic moments at the non-magnetic sites.

A Chemical Approach to Understanding Oxide Surface Structure and Reactivity

NASA Astrophysics Data System (ADS)

Enterkin, James Andrew

Transmission electron microscopy and diffraction are powerful tools for solving complex structural problems. They complement other analytical techniques, such as x-ray diffraction, elucidating problems which cannot be solved by other techniques. One area where they are of particularly great value is in the determination of surface structures. The research presented herein uses electron microscopy and diffraction as the primary experimental techniques in the development of a chemistry of surface structures. High-resolution electron microscopy revealed that the La4Cu 3MoO12 structure has turbostratic disorder and a lower symmetry space group (Pm) than was previously found. The refinement of the x-ray data was significantly improved by using a disordered model and the Pm space group. A bond valence analysis confirmed that the disordered structure is the superior model. Strontium titanate, SrTiO3, single crystal surfaces were examined principally via transmission electron diffraction. A homologous series with intergrowths was discovered on the (110) surface of strontium titanate, marking the first time that these important concepts of solid state chemistry have been found at the surface. Atmospheric adsorbates, such as H2O and CO2, were found to help to stabilize undercoordinated surface structures on the (100) surface. It was shown that chemical bonding, bond valence, atomic coordination, and stoichiometry greatly influence the development of surface structures. Additionally, such chemistry based analysis was demonstrated to be able to predict surface structure stability and reactivity. Application of a modified Wulff construction to the observed shape of strontium titanate nanocuboids revealed that the surface structure and particle stoichiometry are interlinked, with control over one allowing equally precise control over the other. Platinum nanoparticles on the strontium titanate nanocuboids were shown via high resolution electron microscopy to have cube-on-cube epitaxy, with the shape of the platinum nanoparticles governed by the Winterbottom construction. Precise modification of the support surface will therefore allow engineering of supported metal particles with precise control over which facets are exposed. These results suggest that control over the support surface chemistry can be used to engineer thermodynamically stable, face selective catalysts.

Importance of asparagine on the conformational stability and chemical reactivity of selected anti-inflammatory peptides

NASA Astrophysics Data System (ADS)

Soriano-Correa, Catalina; Barrientos-Salcedo, Carolina; Campos-Fernández, Linda; Alvarado-Salazar, Andres; Esquivel, Rodolfo O.

2015-08-01

Inflammatory response events are initiated by a complex series of molecular reactions that generate chemical intermediaries. The structure and properties of peptides and proteins are determined by the charge distribution of their side chains, which play an essential role in its electronic structure and physicochemical properties, hence on its biological functionality. The aim of this study was to analyze the effect of changing one central amino acid, such as substituting asparagine for aspartic acid, from Cys-Asn-Ser in aqueous solution, by assessing the conformational stability, physicochemical properties, chemical reactivity and their relationship with anti-inflammatory activity; employing quantum-chemical descriptors at the M06-2X/6-311+G(d,p) level. Our results suggest that asparagine plays a more critical role than aspartic acid in the structural stability, physicochemical features, and chemical reactivity of these tripeptides. Substituent groups in the side chain cause significant changes on the conformational stability and chemical reactivity, and consequently on their anti-inflammatory activity.

Microstructural, thermal and antibacterial properties of electron beam irradiated Bombyx mori silk fibroin films

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

Asha, S.; Sanjeev, Ganesh, E-mail: ganeshsanjeev@rediffmail.com; Sangappa

The Bombyx mori silk fibroin (SF) films were prepared by solution casting method and the effects of electron beam on structural, thermal and antibacterial responses of the prepared films were studied. The electron irradiation for different doses was carried out using 8 MeV Microtron facility at Mangalore University. The changes in microstructural parameters and thermal stability of the films were investigated using Wide Angle X-ray Scattering (WAXS) and thermogravimetric analysis (TGA) respectively. Both microstructuralline parameters (crystallite size and lattice strain (g in %)) and thermal stability of the irradiated films have increased with radiation dosage. Agar diffusion method demonstrated themore » antibacterial activity of SF film which was increased after irradiation on both Gram-positive and Gram-negative species.« less

Surface mediated assembly of small, metastable gold nanoclusters

NASA Astrophysics Data System (ADS)

Pettibone, John M.; Osborn, William A.; Rykaczewski, Konrad; Talin, A. Alec; Bonevich, John E.; Hudgens, Jeffrey W.; Allendorf, Mark D.

2013-06-01

The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities.The unique properties of metallic nanoclusters are attractive for numerous commercial and industrial applications but are generally less stable than nanocrystals. Thus, developing methodologies for stabilizing nanoclusters and retaining their enhanced functionality is of great interest. We report the assembly of PPh3-protected Au9 clusters from a heterogeneous mixture into films consisting of sub 3 nm nanocluster assemblies. The depositing nanoclusters are metastable in solution, but the resulting nanocluster assemblies are stabilized indefinitely in air or fresh solvent. The films exhibit distinct structure from Au nanoparticles observed by X-ray diffraction, and film dissolution data support the preservation of small nanoclusters. UV-Vis spectroscopy, electrospray ionization mass spectrometry, X-ray photoelectron spectroscopy and electron microscopy are used to elucidate information regarding the nanocluster formation and assembly mechanism. Preferential deposition of nanocluster assemblies can be achieved on multiple substrates, including polymer, Cr, Si, SiO2, SiNx, and metal-organic frameworks (MOFs). Unlike other vapor phase coating processes, nanocluster assembly on the MIL-68(In) MOF crystal is capable of preferentially coating the external surface and stabilizing the crystal structure in hydrothermal conditions, which should enhance their storage, separation and delivery capabilities. Electronic supplementary information (ESI) available: Further details on stored plating solution preparation, film characterization, solution processing, MOF crystal FIB reconstruction and stability are available. See DOI: 10.1039/c3nr01708g

Ab Initio Study of Electronic Excitation Effects on SrTiO 3

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

Zhao, Shijun; Zhang, Yanwen; Weber, William J.

Interaction of energetic ions or lasers with solids often induces electronic excitations that may modify material properties significantly. In this study, effects of electronic excitations on strontium titanate SrTiO 3 (STO) are investigated based on first-principles calculations. The lattice structure, electronic properties, lattice vibrational frequencies, and dynamical stabilities are studied in detail. The results suggest that electronic excitation induces charge redistribution that is mainly observed in Ti–O bonds. The electronic band gap increases with increasing electronic excitation, as excitation mainly induces depopulation of Ti 3d states. Phonon analysis indicates that there is a large phonon band gap induced by electronicmore » excitation because of the changes in the vibrational properties of Ti and O atoms. In addition, a new peak appears in the phonon density of states with imaginary frequencies, an indication of lattice instability. Further dynamics simulations confirm that STO undergoes transition to an amorphous structure under strong electronic excitations. In conclusion, the optical properties of STO under electronic excitation are consistent with the evolution of atomic and electronic structures, which suggests a possibility to probe the properties of STO in nonequilibrium state using optical measurement.« less

Ab Initio Study of Electronic Excitation Effects on SrTiO 3

DOE PAGES

Zhao, Shijun; Zhang, Yanwen; Weber, William J.

2017-11-14

Interaction of energetic ions or lasers with solids often induces electronic excitations that may modify material properties significantly. In this study, effects of electronic excitations on strontium titanate SrTiO 3 (STO) are investigated based on first-principles calculations. The lattice structure, electronic properties, lattice vibrational frequencies, and dynamical stabilities are studied in detail. The results suggest that electronic excitation induces charge redistribution that is mainly observed in Ti–O bonds. The electronic band gap increases with increasing electronic excitation, as excitation mainly induces depopulation of Ti 3d states. Phonon analysis indicates that there is a large phonon band gap induced by electronicmore » excitation because of the changes in the vibrational properties of Ti and O atoms. In addition, a new peak appears in the phonon density of states with imaginary frequencies, an indication of lattice instability. Further dynamics simulations confirm that STO undergoes transition to an amorphous structure under strong electronic excitations. In conclusion, the optical properties of STO under electronic excitation are consistent with the evolution of atomic and electronic structures, which suggests a possibility to probe the properties of STO in nonequilibrium state using optical measurement.« less

Structure Stabilization by Mixed Anions in Oxyfluoride Cathodes for High-Energy Lithium Batteries

DOE PAGES

Kim, Sung-Wook; Pereira, Nathalie; Chernova, Natasha A.; ...

2015-08-24

Mixed-anion oxyfluorides (i.e., FeO xF 2-x) are an appealing alternative to pure fluorides as high-capacity cathodes in lithium batteries, with enhanced cyclability via oxygen substitution. Yet, it is still unclear how the mixed anions impact the local phase transformation and structural stability of oxyfluorides during cycling due to the complexity of electrochemical reactions, involving both lithium intercalation and conversion. Herein, we investigated the local chemical and structural ordering in FeO 0.7F 1.3 at length scales spanning from single particles to the bulk electrode, via a combination of electron spectrum-imaging, magnetization, electrochemistry, and synchrotron X-ray measurements. The FeO 0.7F 1.3more » nanoparticles retain a FeF 2-like rutile structure but chemically heterogeneous, with an F-rich core covered by thin O-rich shell. Upon lithiation the O-rich rutile phase is transformed into Li—Fe—O(—F) rocksalt that has high lattice coherency with converted metallic Fe, a feature that may facilitate the local electron and ion transport. The O-rich rocksalt is highly stable over lithiation/delithiation and thus advantageous to maintain the integrity of the particle, and due to its predominant distribution on the surface, it is expected to prevent the catalytic interaction of Fe with electrolyte. Our findings of the structural origin of cycling stability in oxyfluorides may provide insights into developing viable high-energy electrodes for lithium batteries.« less

Structural, electronic and magnetic properties of chevron-type graphene, BN and BC2N nanoribbons

NASA Astrophysics Data System (ADS)

Guerra, T.; Azevedo, S.; Kaschny, J. R.

2017-04-01

Graphene nanoribbons are predicted to be essential components in future nanoelectronics. The size, edge type, arrangement of atoms and width of nanoribbons drastically change their properties. Boronnitrogencarbon nanoribbons properties are not fully understood so far. In the present contribution it was investigated the structural, electronic and magnetic properties of chevron-type carbon, boron nitride and BC2N nanoribbons, using first-principles calculations. The results indicate that the structural stability is closely related to the discrepancies in the bond lengths, which can induce structural deformations and stress. Such nanoribbons present a wide range of electronic behaviors, depending on their composition and particularities of the atomic arrangement. A net magnetic moment is found for structures that present carbon atoms at the nanoribbon borders. Nevertheless, the calculated magnetic moment depends on the peculiarities of the symmetric arrangement of atoms and imbalance of carbon atoms between different sublattices. It was found that all structures which have a significant energy gap do not present magnetic moment, and vice-versa. Such result indicates the strong correlation between the electronic and magnetic properties of the chevron-type nanoribbons.

Persistent order due to transiently enhanced nesting in an electronically excited charge density wave

DOE PAGES

Rettig, L.; Cortés, R.; Chu, J. -H.; ...

2016-01-25

Non-equilibrium conditions may lead to novel properties of materials with broken symmetry ground states not accessible in equilibrium as vividly demonstrated by non-linearly driven mid-infrared active phonon excitation. Potential energy surfaces of electronically excited states also allow to direct nuclear motion, but relaxation of the excess energy typically excites fluctuations leading to a reduced or even vanishing order parameter as characterized by an electronic energy gap. Here, using femtosecond time-and angle-resolved photoemission spectroscopy, we demonstrate a tendency towards transient stabilization of a charge density wave after near-infrared excitation, counteracting the suppression of order in the non-equilibrium state. Analysis of themore » dynamic electronic structure reveals a remaining energy gap in a highly excited transient state. In conclusion, our observation can be explained by a competition between fluctuations in the electronically excited state, which tend to reduce order, and transiently enhanced Fermi surface nesting stabilizing the order.« less

Tuning of electronic properties and dynamical stability of graphene oxide with different functional groups

NASA Astrophysics Data System (ADS)

Dabhi, Shweta D.; Jha, Prafulla K.

2017-09-01

The structural, electronic and vibrational properties of graphene oxide (GO) with varying proportion of epoxy and hydroxyl functional groups have been studied using density functional theory. The functional groups and oxygen density have an obvious influence on the electronic and vibrational properties. The dependence of band gap on associated functional groups and oxygen density shows a possibility of tuning the band gap of graphene by varying the functional groups as well as oxidation level. The absorption of high oxygen content in graphene leads to the gap opening and resulting in a transition from semimetal to semiconductor. Phonon dispersion curves show no imaginary frequency or no softening of any phonon mode throughout the Brillouin zone which confirms the dynamical stability of all considered GO models. Different groups and different oxygen density result into the varying characteristics of phonon modes. The computed results show good agreement with the experimental observations. Our results present interesting possibilities for engineering the electronic properties of graphene and GO and impact the fabrication of new electronics.

A simple photoionization scheme for characterizing electron and ion spectrometers

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

Wituschek, A.; Vangerow, J. von; Grzesiak, J.

We present a simple diode laser-based photoionization scheme for generating electrons and ions with well-defined spatial and energetic (≲2 eV) structures. This scheme can easily be implemented in ion or electron imaging spectrometers for the purpose of off-line characterization and calibration. The low laser power ∼1 mW needed from a passively stabilized diode laser and the low flux of potassium atoms in an effusive beam make our scheme a versatile source of ions and electrons for applications in research and education.

High pressure structural investigation on alluaudites Na{sub 2}Fe{sub 3}(PO{sub 4}){sub 3}-Na{sub 2}FeMn{sub 2}(PO{sub 4}){sub 3} system

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

Gao, Jing; Huang, Weifeng; Qin, Shan

Alluaudites are promising electrochemical materials benefited from the open structure. Structural variations of alluaudites Na{sub 2}M{sub 3}(PO{sub 4}){sub 3} (M{sub 3}=Fe{sub 3}, Fe{sub 2}Mn and FeMn{sub 2}) system have been studied by synchrotron radiation X-ray diffraction combined with diamond anvil cell technique up to ~10 GPa at room temperature. No phase transition is observed. The excellent structural stability is mainly due to the flexible framework plus strong covalent P-O bond. Mn{sup 2+} instead of Fe can be described as Na{sup +}+2Fe{sup 2+}→Mn{sup 2+}+Fe{sup 3+}+□ where □ represents a lattice vacancy. The replacement of Fe with larger Mn{sup 2+} is equivalentmore » to applying negative chemical pressure to the material. And it causes a more compressible b-axis, lattice expansion, structural compressibility and intensifies the core/electron-electron interactions of Fe. External pressure effect produces anisotropic lattice shrinkage. Structural considerations related to these variations and promising application prospects are discussed. - Graphical abstract: Figure 1 The crystal structure of alluaudites Na{sub 2}M{sub 3}(PO{sub 4}){sub 3} (M{sub 3}=Fe{sub 3}, Fe{sub 2}Mn and FeMn{sub 2}) projected along the c-axis. Alluaudites adopt a flexible framework plus strong covalent P-O bond, which contribute to excellent structural stability up to ~10 GPa. Mn{sup 2+} instead of Fe can be described as Na{sup ++}2Fe{sup 2+}→Mn{sup 2+}+Fe{sup 3+}+□ where □ represents a lattice vacancy, and it is equivalent to applying negative chemical pressure to the host. The substitution causes a more compressible b-axis, lattice expansion, structural compressibility and intensifies the core/electron-electron interactions of Fe.« less

Effect of substitutions and defects in half-Heusler FeVSb studied by electron transport measurements and KKR-CPA electronic structure calculations

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

Jodin, L.; Tobola, J.; Pecheur, P.

2004-11-01

The structural and electron transport properties of the pure and Co-, Ti-, and Zr-substituted FeVSb half-Heusler phases have been investigated using x-ray diffraction, Moessbauer spectroscopy, and Electron Probe Microscopy Analysis as well as resistivity, thermopower, and Hall effect measurements in the 80-900 K temperature range. In a parallel study, the electronic structures of FeVSb and the aforementioned alloys were calculated using the Korringa-Kohn-Rostoker method with the coherent potential approximation (KKR-CPA) in the LDA framework. The electronic densities of states and dispersion curves were obtained. The crystal structure stability and site preference analysis were addressed using total energy computations. Most ofmore » these experimental results correspond to electronic structure computations only if they take into account extra crystal defects such as antisite defects or vacancies present to various extents in the samples. Indeed a remarkable variation of KKR-CPA density of states occurring both in FeVSb and FeV{sub 1-x}Zr{sub x}Sb including defects may explain why FeVSb is not fully semiconducting as well as why there is a change of the thermopower sign in the FeV{sub 1-x}Zr{sub x}Sb versus x content.« less

Insights into the Distinct Mechanisms of Action of Taxane and Non-Taxane Microtubule Stabilizers from Cryo-EM Structures.

PubMed

Kellogg, Elizabeth H; Hejab, Nisreen M A; Howes, Stuart; Northcote, Peter; Miller, John H; Díaz, J Fernando; Downing, Kenneth H; Nogales, Eva

2017-03-10

A number of microtubule (MT)-stabilizing agents (MSAs) have demonstrated or predicted potential as anticancer agents, but a detailed structural basis for their mechanism of action is still lacking. We have obtained high-resolution (3.9-4.2Å) cryo-electron microscopy (cryo-EM) reconstructions of MTs stabilized by the taxane-site binders Taxol and zampanolide, and by peloruside, which targets a distinct, non-taxoid pocket on β-tubulin. We find that each molecule has unique distinct structural effects on the MT lattice structure. Peloruside acts primarily at lateral contacts and has an effect on the "seam" of heterologous interactions, enforcing a conformation more similar to that of homologous (i.e., non-seam) contacts by which it regularizes the MT lattice. In contrast, binding of either Taxol or zampanolide induces MT heterogeneity. In doubly bound MTs, peloruside overrides the heterogeneity induced by Taxol binding. Our structural analysis illustrates distinct mechanisms of these drugs for stabilizing the MT lattice and is of relevance to the possible use of combinations of MSAs to regulate MT activity and improve therapeutic potential. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Insights into the Distinct Mechanisms of Action of Taxane and Non-Taxane Microtubule Stabilizers from Cryo-EM Structures

DOE PAGES

Kellogg, Elizabeth H.; Hejab, Nisreen M. A.; Howes, Stuart; ...

2017-01-17

A number of microtubule (MT)-stabilizing agents (MSAs) have demonstrated or predicted potential as anticancer agents, but a detailed structural basis for their mechanism of action is still lacking. We have obtained high-resolution (3.9–4.2 Å) cryo-electron microscopy (cryo-EM) reconstructions of MTs stabilized by the taxane-site binders Taxol and zampanolide, and by peloruside, which targets a distinct, non-taxoid pocket on β-tubulin. We find that each molecule has unique distinct structural effects on the MT lattice structure. Peloruside acts primarily at lateral contacts and has an effect on the “seam” of heterologous interactions, enforcing a conformation more similar to that of homologous (i.e., non-seam)more » contacts by which it regularizes the MT lattice. In contrast, binding of either Taxol or zampanolide induces MT heterogeneity. In doubly bound MTs, peloruside overrides the heterogeneity induced by Taxol binding. Our structural analysis illustrates distinct mechanisms of these drugs for stabilizing the MT lattice and is of relevance to the possible use of combinations of MSAs to regulate MT activity and improve therapeutic potential.« less

Insights into the Distinct Mechanisms of Action of Taxane and Non-Taxane Microtubule Stabilizers from Cryo-EM Structures

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

Kellogg, Elizabeth H.; Hejab, Nisreen M. A.; Howes, Stuart

A number of microtubule (MT)-stabilizing agents (MSAs) have demonstrated or predicted potential as anticancer agents, but a detailed structural basis for their mechanism of action is still lacking. We have obtained high-resolution (3.9–4.2 Å) cryo-electron microscopy (cryo-EM) reconstructions of MTs stabilized by the taxane-site binders Taxol and zampanolide, and by peloruside, which targets a distinct, non-taxoid pocket on β-tubulin. We find that each molecule has unique distinct structural effects on the MT lattice structure. Peloruside acts primarily at lateral contacts and has an effect on the “seam” of heterologous interactions, enforcing a conformation more similar to that of homologous (i.e., non-seam)more » contacts by which it regularizes the MT lattice. In contrast, binding of either Taxol or zampanolide induces MT heterogeneity. In doubly bound MTs, peloruside overrides the heterogeneity induced by Taxol binding. Our structural analysis illustrates distinct mechanisms of these drugs for stabilizing the MT lattice and is of relevance to the possible use of combinations of MSAs to regulate MT activity and improve therapeutic potential.« less

Determination of the size and phase composition of silver nanoparticles in a gel film of bacterial cellulose by small-angle X-ray scattering, electron diffraction, and electron microscopy

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

Volkov, V. V.; Klechkovskaya, V. V., E-mail: klechvv@ns.crys.ras.ru; Shtykova, E. V.

2009-03-15

The nanoscale structural features in a composite (gel film of Acetobacter Xylinum cellulose with adsorbed silver nanoparticles, stabilized by N-polyvinylpyrrolidone) have been investigated by small-angle X-ray scattering. The size distributions of inhomogeneities in the porous structure of the cellulose matrix and the size distributions of silver nanoparticles in the composite have been determined. It is shown that the sizes of synthesized nanoparticles correlate with the sizes of inhomogeneities in the gel film. Particles of larger size (with radii up to 100 nm) have also been found. Electron microscopy of thin cross sections of a dried composite layer showed that largemore » particles are located on the cellulose layer surface. Electron diffraction revealed a crystal structure of silver nanoparticles in the composite.« less

Pressure-stabilized binary compounds of magnesium and silicon on Materials Project

DOE Data Explorer

Kristin Persson; Huan Tran

2018-04-13

Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

Electronic Structure, Mechanical and Dynamical Stability of Hexagonal Subcarbides M2C (M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt): Ab Initio Calculations

NASA Astrophysics Data System (ADS)

Suetin, D. V.; Shein, I. R.

2018-02-01

Ab initio calculations were used to study the properties of a series of hexagonal (Fe2N-like) subcarbides M2C, where M = Tc, Ru, Rh, Pd, Re, Os, Ir, and Pt, and to calculate their equilibrium structural parameters, electronic properties, phase stability, elastic constants, compression modulus, shear modulus, Young's modulus, compressibility, Pugh's indicator, Poisson ratio, elastic anisotropy indices, and also hardness, Debye temperature, sound velocity, and low-temperature heat capacity. It is found based on these results that all the subcarbides are mechanically stable; however, their formation energies E form are positive with respect to a mixture of d-metal and graphite. In addition, the calculation of the phonon spectra of these subcarbides shows the existence of negative modes, which indicates their dynamical instability. Thus, a successful synthesis of these subcarbides at normal conditions is highly improbable.

Body-centered orthorhombic C 16 : A novel topological node-line semimetal

DOE PAGES

Wang, Jian -Tao; Weng, Hongming; Nie, Simin; ...

2016-05-11

We identify by ab initio calculations a novel topological semimetal carbon phase in all-sp 2 bonding networks with a 16-atom body-centered orthorhombic unit cell, termed bco-C 16. Total-energy calculations show that bco-C 16 is comparable to solid fcc-C 60 in energetic stability, and phonon and molecular dynamics simulations confirm its dynamical stability. This all-sp 2 carbon allotrope can be regarded as a three-dimensional modification of graphite, and its simulated x-ray diffraction (XRD) pattern matches well a previously unexplained diffraction peak in measured XRD spectra of detonation and chimney soot, indicating its presence in the specimen. Electronic band structure calculations revealmore » that bco-C 16 is a topological node-line semimetal with a single nodal ring. Lastly, these findings establish a novel carbon phase with intriguing structural and electronic properties of fundamental significance and practical interest.« less

Amorphous Red Phosphorus Embedded in Sandwiched Porous Carbon Enabling Superior Sodium Storage Performances.

PubMed

Wu, Ying; Liu, Zheng; Zhong, Xiongwu; Cheng, Xiaolong; Fan, Zhuangjun; Yu, Yan

2018-03-01

The red P anode for sodium ion batteries has attracted great attention recently due to the high theoretical capacity, but the poor intrinsic electronic conductivity and large volume expansion restrain its widespread applications. Herein, the red P is successfully encapsulated into the cube shaped sandwich-like interconnected porous carbon building (denoted as P@C-GO/MOF-5) via the vaporization-condensation method. Superior cycling stability (high capacity retention of about 93% at 2 A g -1 after 100 cycles) and excellent rate performance (502 mAh g -1 at 10 A g -1 ) can be obtained for the P@C-GO/MOF-5 electrode. The superior electrochemical performance can be ascribed to the successful incorporation of red P into the unique carbon matrix with large surface area and pore volume, interconnected porous structure, excellent electronic conductivity and superior structural stability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optical properties of boron-group (V) hexagonal nanowires: DFT investigation

NASA Astrophysics Data System (ADS)

Santhibhushan, B.; Soni, Mahesh; Srivastava, Anurag

2017-07-01

The paper presents structural, electronic and optical properties of boron-group V hexagonal nanowires (h-NW) within the framework of density functional theory. The h-NW of boron-group V compounds with an analogous diameter of 12 Å have been designed in (1 1 1) plane. Stability analysis performed through formation energies reveal that, the stability of these structures decreases with increasing atomic number of the group V element. The band nature predicts that these nanowires are good electrical conductors. Optical behaviour of the nanowires has been analysed through absorption coefficient, reflectivity, refractive index, optical conductivity and electron energy loss spectrum (EELS), that are computed from the frequency-dependent complex dielectric function. The analysis reveals high reactivity of BP and BAs h-NWs to the incident light especially in the IR and visible ranges, and the optical transparency of BN h-NW in the visible and UV ranges.

Theoretical Study of Decomposition Pathways for HArF and HKrF

NASA Technical Reports Server (NTRS)

Chaban, Galina M.; Lundell, Jan; Gerber, R. Benny; Kwak, Donchan (Technical Monitor)

2002-01-01

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Conducting linear chains of sulphur inside carbon nanotubes

PubMed Central

Fujimori, Toshihiko; Morelos-Gómez, Aarón; Zhu, Zhen; Muramatsu, Hiroyuki; Futamura, Ryusuke; Urita, Koki; Terrones, Mauricio; Hayashi, Takuya; Endo, Morinobu; Young Hong, Sang; Chul Choi, Young; Tománek, David; Kaneko, Katsumi

2013-01-01

Despite extensive research for more than 200 years, the experimental isolation of monatomic sulphur chains, which are believed to exhibit a conducting character, has eluded scientists. Here we report the synthesis of a previously unobserved composite material of elemental sulphur, consisting of monatomic chains stabilized in the constraining volume of a carbon nanotube. This one-dimensional phase is confirmed by high-resolution transmission electron microscopy and synchrotron X-ray diffraction. Interestingly, these one-dimensional sulphur chains exhibit long domain sizes of up to 160 nm and high thermal stability (~800 K). Synchrotron X-ray diffraction shows a sharp structural transition of the one-dimensional sulphur occurring at ~450–650 K. Our observations, and corresponding electronic structure and quantum transport calculations, indicate the conducting character of the one-dimensional sulphur chains under ambient pressure. This is in stark contrast to bulk sulphur that needs ultrahigh pressures exceeding ~90 GPa to become metallic. PMID:23851903

Two-dimensional titanium carbonitrides and their hydroxylated derivatives: Structural, electronic properties and stability of MXenes Ti3C2-xNx(OH)2 from DFTB calculations

NASA Astrophysics Data System (ADS)

Enyashin, A. N.; Ivanovskii, A. L.

2013-11-01

The structural, electronic properties and stability of the new MXene compounds—two-dimensional pristine carbonitrides Ti3C2-xNx and their hydroxylated derivatives Ti3C2-xNx(OH)2 are studied by means of DFTB calculations. The genesis of the properties is discussed in the sequence: binary MXenes Ti3C2 (Ti3N2)→hydroxylated forms Ti3C2(OH)2 (Ti3N2(OH)2)→pristine MXene Ti3C2-xNx→hydroxylated Ti3C2-xNx(OH)2. All examined materials are metallic-like. The most favorable type of OH-covering is presented by the occupation of the hollow sites between three neighboring carbon (nitrogen) atoms. Two-dimensional MXene carbonitrides with random distribution of C and N atoms are found to be thermodynamically more favorable.

Dynamic performance of the beam position monitor support at the SSRF.

PubMed

Wang, Xiao; Cao, Yun; Du, Hanwen; Yin, Lixin

2009-01-01

Electron beam stability is very important for third-generation light sources, especially for the Shanghai Synchrotron Radiation Facility whose ground vibrations are much larger than those for other light sources. Beam position monitors (BPMs), used to monitor the position of the electron beam, require a greater stability than other mechanical structures. This paper concentrates on an investigation of the dynamic performance of the BPM support prototype. Modal and response analyses have been carried out by finite-element (FE) calculations and vibration measurements. Inconsistent results between calculation and measurement have motivated a change in the soft connections between the support and the ground from a ground bolt in the initial design to full grout. As a result the mechanical stability of the BPM support is greatly improved, showing an increase in the first eigenfrequency from 20.2 Hz to 50.2 Hz and a decrease in the ratio of the root-mean-square displacement (4-50 Hz) between the ground and the top of the support from 4.36 to 1.23 in the lateral direction. An example is given to show how FE analysis can guide the mechanical design and dynamic measurements (i.e. it is not just used as a verification method). Similar ideas can be applied to improve the stability of other mechanical structures.

Assigning crystallographic electron densities with free energy calculations—The case of the fluoride channel Fluc

PubMed Central

2018-01-01

Approximately 90% of the structures in the Protein Data Bank (PDB) were obtained by X-ray crystallography or electron microscopy. Whereas the overall quality of structure is considered high, thanks to a wide range of tools for structure validation, uncertainties may arise from density maps of small molecules, such as organic ligands, ions or water, which are non-covalently bound to the biomolecules. Even with some experience and chemical intuition, the assignment of such disconnected electron densities is often far from obvious. In this study, we suggest the use of molecular dynamics (MD) simulations and free energy calculations, which are well-established computational methods, to aid in the assignment of ambiguous disconnected electron densities. Specifically, estimates of (i) relative binding affinities, for instance between an ion and water, (ii) absolute binding free energies, i.e., free energies for transferring a solute from bulk solvent to a binding site, and (iii) stability assessments during equilibrium simulations may reveal the most plausible assignments. We illustrate this strategy using the crystal structure of the fluoride specific channel (Fluc), which contains five disconnected electron densities previously interpreted as four fluoride and one sodium ion. The simulations support the assignment of the sodium ion. In contrast, calculations of relative and absolute binding free energies as well as stability assessments during free MD simulations suggest that four of the densities represent water molecules instead of fluoride. The assignment of water is compatible with the loss of these densities in the non-conductive F82I/F85I mutant of Fluc. We critically discuss the role of the ion force fields for the calculations presented here. Overall, these findings indicate that MD simulations and free energy calculations are helpful tools for modeling water and ions into crystallographic density maps. PMID:29771936

X-ray source assembly having enhanced output stability, and fluid stream analysis applications thereof

DOEpatents

Radley, Ian [Glenmont, NY; Bievenue, Thomas J [Delmar, NY; Burdett, John H [Charlton, NY; Gallagher, Brian W [Guilderland, NY; Shakshober, Stuart M [Hudson, NY; Chen, Zewu [Schenectady, NY; Moore, Michael D [Alplaus, NY

2008-06-08

An x-ray source assembly and method of operation are provided having enhanced output stability. The assembly includes an anode having a source spot upon which electrons impinge and a control system for controlling position of the anode source spot relative to an output structure. The control system can maintain the anode source spot location relative to the output structure notwithstanding a change in one or more operating conditions of the x-ray source assembly. One aspect of the disclosed invention is most amenable to the analysis of sulfur in petroleum-based fuels.

The impact of electron correlations on the energetics and stability of silicon nanoclusters

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

Matsko, N. L.; Baturin, V. S.; Lepeshkin, S. V.

2016-08-21

The first-principles prediction of stable nanocluster structure is often hampered by the existence of many isomer configurations with energies close to the ground state. This fact attaches additional importance to many-electron effects beyond density functional theory (DFT), because their contributions can change a subtle energy order of competitive structures. To analyze this problem, we consider, as an example, the energetics of silicon nanoclusters passivated by hydrogen Si{sub 10}H{sub 2n} (0 ≤ n ≤ 11), where passivation changes the structure from compact to loosely packed and branched. Our calculations performed with DFT, hybrid functionals, and Hartree-Fock methods, as well as bymore » the GW approximation, confirm a considerable sensitivity of isomer energy ordering to many-electron effects.« less

Structural, electronic, magnetic and thermodynamic properties of Ni1-xTixO alloys an ab initio calculation and Monte Carlo study

NASA Astrophysics Data System (ADS)

Klaa, K.; Labidi, S.; Masrour, R.; Jabar, A.; Labidi, M.; Amara, A.; Drici, A.; Hlil, E. K.; Ellouze, M.

2018-06-01

Structural, electronic, magnetic and thermodynamic main features for Ni1-xTixO ternary alloys in rock-salt structure with Ti content in the range ? were studied using the full potential Linearized augmented plane wave (FP-LAPW) method within density functional theory. The exchange-correlation potential was calculated by the generalized gradient approximation. The analysis of the electronic density of states curves allowed the computation of the magnetic moments which are considered to lie along (010) axes. The thermodynamic stability of this alloy was investigated by calculating the excess enthalpy of mixing ? as well as the phase diagram. In addition, the Monte Carlo simulations have been exploited to calculate the transition temperature and magnetic coercive field in the alloy.

Electronic structural studies on the improved thermal stability of Li(Ni0.8Co0.15Al0.05)O2 by ZrO2 coating for lithium ion batteries

DOE PAGES

Kim, Ji-Young; Kim, Sang Hoon; Kim, Dong Hyun; ...

2017-03-21

The electronic structures of bare and ZrO 2-coated Li(Ni 0.8Co 0.15Al 0.05)O 2 electrode systems were investigated using a combination of time-resolved X-ray diffraction and soft X-ray absorption spectroscopy (XAS) techniques. The ZrO 2 coating on the surface of Li(Ni 0.8Co 0.15Al 0.05)O 2 was effective in elevating the onset temperature of the dissociation of charged Li 0.33(Ni 0.8Co 0.15Al 0.05)O 2, which will enhance the safety of Li-ion cells. Lastly, soft XAS spectra of the Ni LII,III-edge in the partial electron yield mode were obtained, which showed that the enhanced electrochemical properties and thermal stability of the cathode materialsmore » by ZrO 2 coating can be attributed to the suppression of unwanted Ni oxidation state changes at the surface.« less

Size-Dependent Grain-Boundary Structure with Improved Conductive and Mechanical Stabilities in Sub-10-nm Gold Crystals

NASA Astrophysics Data System (ADS)

Wang, Chunyang; Du, Kui; Song, Kepeng; Ye, Xinglong; Qi, Lu; He, Suyun; Tang, Daiming; Lu, Ning; Jin, Haijun; Li, Feng; Ye, Hengqiang

2018-05-01

Low-angle grain boundaries generally exist in the form of dislocation arrays, while high-angle grain boundaries (misorientation angle >15 ° ) exist in the form of structural units in bulk metals. Here, through in situ atomic resolution aberration corrected electron microscopy observations, we report size-dependent grain-boundary structures improving both stabilities of electrical conductivity and mechanical properties in sub-10-nm-sized gold crystals. With the diameter of a nanocrystal decreasing below 10 nm, the high-angle grain boundary in the crystal exists as an array of dislocations. This size effect may be of importance to a new generation of interconnects applications.

Inner reorganization limiting electron transfer controlled hydrogen bonding: intra- vs. intermolecular effects.

PubMed

Martínez-González, Eduardo; Frontana, Carlos

2014-05-07

In this work, experimental evidence of the influence of the electron transfer kinetics during electron transfer controlled hydrogen bonding between anion radicals of metronidazole and ornidazole, derivatives of 5-nitro-imidazole, and 1,3-diethylurea as the hydrogen bond donor, is presented. Analysis of the variations of voltammetric EpIcvs. log KB[DH], where KB is the binding constant, allowed us to determine the values of the binding constant and also the electron transfer rate k, confirmed by experiments obtained at different scan rates. Electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level for metronidazole, including the solvent effect by the Cramer/Truhlar model, suggested that the minimum energy conformer is stabilized by intramolecular hydrogen bonding. In this structure, the inner reorganization energy, λi,j, contributes significantly (0.5 eV) to the total reorganization energy of electron transfer, thus leading to a diminishment of the experimental k.

Dynamical and electronic properties of rare-earth aluminides

NASA Astrophysics Data System (ADS)

Sharma, Ramesh; Sharma, Yamini

2018-04-01

Rare-earth dialuminides belong to a large family of compounds that stabilize in cubic MgCu2 structure. A large number of these compounds are superconducting, amongst these YAl2, LaAl2 and LuAl2 have been chosen as reference materials for studying 4f-electron systems. In order to understand the role of the RE atoms, we have applied the FPLAPW and PAW methods within the density functional theory (DFT). Our results show that the contribution of RE atoms is dominant in both electronic structure and phonon dispersion. The anomalous behavior of superconducting LaAl2 is well explained from an analysis of the electron localization function (ELF), Bader charge analysis, density of electronic states as well as the dynamical phonon vibrational modes. The interaction of phonon modes contributed by low frequency vibrations of La atoms with the high density La 5d-states at EF in LaAl2 lead to strong electron-phonon coupling.

Investigation of the plasma shaping effects on the H-mode pedestal structure using coupled kinetic neoclassical/MHD stability simulations

NASA Astrophysics Data System (ADS)

Pankin, A. Y.; Rafiq, T.; Kritz, A. H.; Park, G. Y.; Snyder, P. B.; Chang, C. S.

2017-06-01

The effects of plasma shaping on the H-mode pedestal structure are investigated. High fidelity kinetic simulations of the neoclassical pedestal dynamics are combined with the magnetohydrodynamic (MHD) stability conditions for triggering edge localized mode (ELM) instabilities that limit the pedestal width and height in H-mode plasmas. The neoclassical kinetic XGC0 code [Chang et al., Phys. Plasmas 11, 2649 (2004)] is used in carrying out a scan over plasma elongation and triangularity. As plasma profiles evolve, the MHD stability limits of these profiles are analyzed with the ideal MHD ELITE code [Snyder et al., Phys. Plasmas 9, 2037 (2002)]. Simulations with the XGC0 code, which includes coupled ion-electron dynamics, yield predictions for both ion and electron pedestal profiles. The differences in the predicted H-mode pedestal width and height for the DIII-D discharges with different elongation and triangularities are discussed. For the discharges with higher elongation, it is found that the gradients of the plasma profiles in the H-mode pedestal reach semi-steady states. In these simulations, the pedestal slowly continues to evolve to higher pedestal pressures and bootstrap currents until the peeling-ballooning stability conditions are satisfied. The discharges with lower elongation do not reach the semi-steady state, and ELM crashes are triggered at earlier times. The plasma elongation is found to have a stronger stabilizing effect than the plasma triangularity. For the discharges with lower elongation and lower triangularity, the ELM frequency is large, and the H-mode pedestal evolves rapidly. It is found that the temperature of neutrals in the scrape-off-layer (SOL) region can affect the dynamics of the H-mode pedestal buildup. However, the final pedestal profiles are nearly independent of the neutral temperature. The elongation and triangularity affect the pedestal widths of plasma density and electron temperature profiles differently. This provides a new mechanism of controlling the pedestal bootstrap current and the pedestal stability.

Investigation of the plasma shaping effects on the H-mode pedestal structure using coupled kinetic neoclassical/MHD stability simulations

DOE PAGES

Pankin, A. Y.; Rafiq, T.; Kritz, A. H.; ...

2017-06-08

The effects of plasma shaping on the H-mode pedestal structure are investigated. High fidelity kinetic simulations of the neoclassical pedestal dynamics are combined with the magnetohydrodynamic (MHD) stability conditions for triggering edge localized mode (ELM) instabilities that limit the pedestal width and height in H-mode plasmas. We use the neoclassical kinetic XGC0 code [Chang et al., Phys. Plasmas 11, 2649 (2004)] to carry out a scan over plasma elongation and triangularity. As plasma profiles evolve, the MHD stability limits of these profiles are analyzed with the ideal MHD ELITE code [Snyder et al., Phys. Plasmas 9, 2037 (2002)]. In simulationsmore » with the XGC0 code, which includes coupled ion-electron dynamics, yield predictions for both ion and electron pedestal profiles. The differences in the predicted H-mode pedestal width and height for the DIII-D discharges with different elongation and triangularities are discussed. For the discharges with higher elongation, it is found that the gradients of the plasma profiles in the H-mode pedestal reach semi-steady states. In these simulations, the pedestal slowly continues to evolve to higher pedestal pressures and bootstrap currents until the peeling-ballooning stability conditions are satisfied. The discharges with lower elongation do not reach the semi-steady state, and ELM crashes are triggered at earlier times. The plasma elongation is found to have a stronger stabilizing effect than the plasma triangularity. For the discharges with lower elongation and lower triangularity, the ELM frequency is large, and the H-mode pedestal evolves rapidly. It is found that the temperature of neutrals in the scrape-off-layer (SOL) region can affect the dynamics of the H-mode pedestal buildup. But the final pedestal profiles are nearly independent of the neutral temperature. The elongation and triangularity affect the pedestal widths of plasma density and electron temperature profiles differently. This provides a new mechanism of controlling the pedestal bootstrap current and the pedestal stability.« less

Investigation of the plasma shaping effects on the H-mode pedestal structure using coupled kinetic neoclassical/MHD stability simulations

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

Pankin, A. Y.; Rafiq, T.; Kritz, A. H.

The effects of plasma shaping on the H-mode pedestal structure are investigated. High fidelity kinetic simulations of the neoclassical pedestal dynamics are combined with the magnetohydrodynamic (MHD) stability conditions for triggering edge localized mode (ELM) instabilities that limit the pedestal width and height in H-mode plasmas. We use the neoclassical kinetic XGC0 code [Chang et al., Phys. Plasmas 11, 2649 (2004)] to carry out a scan over plasma elongation and triangularity. As plasma profiles evolve, the MHD stability limits of these profiles are analyzed with the ideal MHD ELITE code [Snyder et al., Phys. Plasmas 9, 2037 (2002)]. In simulationsmore » with the XGC0 code, which includes coupled ion-electron dynamics, yield predictions for both ion and electron pedestal profiles. The differences in the predicted H-mode pedestal width and height for the DIII-D discharges with different elongation and triangularities are discussed. For the discharges with higher elongation, it is found that the gradients of the plasma profiles in the H-mode pedestal reach semi-steady states. In these simulations, the pedestal slowly continues to evolve to higher pedestal pressures and bootstrap currents until the peeling-ballooning stability conditions are satisfied. The discharges with lower elongation do not reach the semi-steady state, and ELM crashes are triggered at earlier times. The plasma elongation is found to have a stronger stabilizing effect than the plasma triangularity. For the discharges with lower elongation and lower triangularity, the ELM frequency is large, and the H-mode pedestal evolves rapidly. It is found that the temperature of neutrals in the scrape-off-layer (SOL) region can affect the dynamics of the H-mode pedestal buildup. But the final pedestal profiles are nearly independent of the neutral temperature. The elongation and triangularity affect the pedestal widths of plasma density and electron temperature profiles differently. This provides a new mechanism of controlling the pedestal bootstrap current and the pedestal stability.« less

Structural phase transition and 5f-electrons localization of PuSe explored by ab initio calculations

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

Cui Shouxin, E-mail: shouxincui@yahoo.co; Feng Wenxia; Hu Haiquan

2010-04-15

An investigation into the structural phase transformation, electronic and optical properties of PuSe under high pressure was conducted by using the full potential linearized augmented plane wave plus local orbitals (FP-LAPW+lo) method, in the presence and in the absence of spin-orbit coupling (SOC). Our results demonstrate that there exists a structural phase transition from rocksalt (B 1) structure to CsCl-type (B 2) structure at the transition pressure of 36.3 GPa (without SOC) and 51.3 GPa (with SOC). The electronic density of states (DOS) for PuSe show that the f-electrons of Pu are more localized and concentrated in a narrow peakmore » near the Fermi level, which is consistent with the experimental studies. The band structure shows that B 1-PuSe is metallic. A pseudogap appears around the Fermi level of the total density of states of B 1 phase PuSe, which may contribute to its stability. The calculated reflectivity R(omega) shows agreement with the available experimental results. Furthermore, the absorption spectrum, refractive index, extinction coefficient, energy-loss spectrum and dielectric function were calculated. The origin of the spectral peaks was interpreted based on the electronic structures. - Abstract: Graphical Abstract Legend (TOC Figure): 5f-electrons are more localized by the analysis of the density of states (SOC). The origin spectra peaks was interpreted based on electronic structures.« less

Effects of radial envelope modulations on the collisionless trapped-electron mode in tokamak plasmas

NASA Astrophysics Data System (ADS)

Chen, Hao-Tian; Chen, Liu

2018-05-01

Adopting the ballooning-mode representation and including the effects of radial envelope modulations, we have derived the corresponding linear eigenmode equation for the collisionless trapped-electron mode in tokamak plasmas. Numerical solutions of the eigenmode equation indicate that finite radial envelope modulations can affect the linear stability properties both quantitatively and qualitatively via the significant modifications in the corresponding eigenmode structures.

Structure and stability of small Li2 +(X2Σ+ g )-Xen (n = 1-6) clusters

NASA Astrophysics Data System (ADS)

Saidi, Sameh; Ghanmi, Chedli; Berriche, Hamid

2014-04-01

We have studied the structure and stability of the Li2 +(X2Σ+ g )Xe n ( n = 1-6) clusters for special symmetry groups. The potential energy surfaces of these clusters, are described using an accurate ab initio approach based on non-empirical pseudopotential, parameterized l-dependent polarization potential and analytic potential forms for the Li+Xe and Xe-Xe interactions. The pseudopotential technique has reduced the number of active electrons of Li2 +(X2Σ+ g )-Xe n ( n = 1-6) clusters to only one electron, the Li valence electron. The core-core interactions for Li+Xe are included using accurate CCSD(T) potential fitted using the analytical form of Tang and Toennies. For the Xe-Xe potential interactions we have used the analytical form of Lennard Jones (LJ6 - 12). The potential energy surfaces of the Li2 +(X2Σ+ g )Xe n ( n = 1-6) clusters are performed for a fixed distance of the Li2 +(X2Σ+ g ) alkali dimer, its equilibrium distance. They are used to extract information on the stability of the Li2 +(X2Σ+ g Xe n ( n = 1-6) clusters. For each n, the stability of the different isomers is examined by comparing their potential energy surfaces. Moreover, we have determined the quantum energies ( D 0), the zero-point-energies (ZPE) and the ZPE%. To our best knowledge, there are neither experimental nor theoretical works realized for the Li2 +(X2Σ+ g Xe n ( n = 1-6) clusters, our results are presented for the first time.

High yield production of long branched Au nanoparticles characterized by atomic resolution transmission electron microscopy

PubMed Central

Mayoral, Alvaro; Magen, Cesar; Jose-Yacaman, Miguel

2011-01-01

Long multi-branched gold nanoparticles have been synthesized in a very high yield through a facile synthesis combining two different capping agents. The stability of these materials with the time has been tested and their characterization have been performed by diverse advanced electron microscopy techniques, paying special attention to aberration corrected transmission electron microscopy in order to unambiguously analyze the surface structure of the branches and provide insights for the formation of stellated gold nanoparticles. PMID:22125420

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

NASA Astrophysics Data System (ADS)

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-01

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands.

PubMed

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-07

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5](-) clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN(-1) were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Structure, Electronic Properties, and Electrochemical Behavior of a Boron-Doped Diamond/Quartz Optically Transparent Electrode.

PubMed

Wächter, Naihara; Munson, Catherine; Jarošová, Romana; Berkun, Isil; Hogan, Timothy; Rocha-Filho, Romeu C; Swain, Greg M

2016-10-26

The morphology, microstructure, chemistry, electronic properties, and electrochemical behavior of a boron-doped nanocrystalline diamond (BDD) thin film grown on quartz were evaluated. Diamond optically transparent electrodes (OTEs) are useful for transmission spectroelectrochemical measurements, offering excellent stability during anodic and cathodic polarization and exposure to a variety of chemical environments. We report on the characterization of a BDD OTE by atomic force microscopy, optical spectroscopy, Raman spectroscopic mapping, alternating-current Hall effect measurements, X-ray photoelectron spectroscopy, and electrochemical methods. The results reported herein provide the first comprehensive study of the relationship between the physical and chemical structure and electronic properties of a diamond OTE and the electrode's electrochemical activity.

Hierarchical meso/macro-porous carbon fabricated from dual MgO templates for direct electron transfer enzymatic electrodes.

PubMed

Funabashi, Hiroto; Takeuchi, Satoshi; Tsujimura, Seiya

2017-03-23

We designed a three-dimensional (3D) hierarchical pore structure to improve the current production efficiency and stability of direct electron transfer-type biocathodes. The 3D hierarchical electrode structure was fabricated using a MgO-templated porous carbon framework produced from two MgO templates with sizes of 40 and 150 nm. The results revealed that the optimal pore composition for a bilirubin oxidase-catalysed oxygen reduction cathode was a mixture of 33% macropores and 67% mesopores (MgOC 33 ). The macropores improve mass transfer inside the carbon material, and the mesopores improve the electron transfer efficiency of the enzyme by surrounding the enzyme with carbon.

Hierarchical meso/macro-porous carbon fabricated from dual MgO templates for direct electron transfer enzymatic electrodes

NASA Astrophysics Data System (ADS)

Funabashi, Hiroto; Takeuchi, Satoshi; Tsujimura, Seiya

2017-03-01

We designed a three-dimensional (3D) hierarchical pore structure to improve the current production efficiency and stability of direct electron transfer-type biocathodes. The 3D hierarchical electrode structure was fabricated using a MgO-templated porous carbon framework produced from two MgO templates with sizes of 40 and 150 nm. The results revealed that the optimal pore composition for a bilirubin oxidase-catalysed oxygen reduction cathode was a mixture of 33% macropores and 67% mesopores (MgOC33). The macropores improve mass transfer inside the carbon material, and the mesopores improve the electron transfer efficiency of the enzyme by surrounding the enzyme with carbon.

Aerodynamic Simulation Analysis of Unmanned Airborne Electronic Bomb

NASA Astrophysics Data System (ADS)

Yang, Jiaoying; Guo, Yachao

2017-10-01

For microelectronic bombs for UAVs, on the basis of the use of rotors to lift the insurance on the basis of ammunition, increased tail to increase stability. The aerodynamic simulation of the outer structure of the ammunition was carried out by FLUENT software. The resistance coefficient, the lift coefficient and the pitch moment coefficient under different angle of attack and Mach number were obtained, and the aerodynamic characteristics of the electronic bomb were studied. The pressure line diagram and the velocity line diagram of the flow around the bomb are further analyzed, and the rationality of the external structure is verified, which provides a reference for the subsequent design of the electronic bomb.

Near-atomic model of microtubule-tau interactions.

PubMed

Kellogg, Elizabeth H; Hejab, Nisreen M A; Poepsel, Simon; Downing, Kenneth H; DiMaio, Frank; Nogales, Eva

2018-06-15

Tau is a developmentally regulated axonal protein that stabilizes and bundles microtubules (MTs). Its hyperphosphorylation is thought to cause detachment from MTs and subsequent aggregation into fibrils implicated in Alzheimer's disease. It is unclear which tau residues are crucial for tau-MT interactions, where tau binds on MTs, and how it stabilizes them. We used cryo-electron microscopy to visualize different tau constructs on MTs and computational approaches to generate atomic models of tau-tubulin interactions. The conserved tubulin-binding repeats within tau adopt similar extended structures along the crest of the protofilament, stabilizing the interface between tubulin dimers. Our structures explain the effect of phosphorylation on MT affinity and lead to a model of tau repeats binding in tandem along protofilaments, tethering together tubulin dimers and stabilizing polymerization interfaces. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

The rational design of a Au(I) precursor for focused electron beam induced deposition

PubMed Central

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au–Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe3, they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe3 and MeAuPMe3 shows that Au–Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au–Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au. PMID:29354346

The rational design of a Au(I) precursor for focused electron beam induced deposition.

PubMed

Marashdeh, Ali; Tiesma, Thiadrik; van Velzen, Niels J C; Harder, Sjoerd; Havenith, Remco W A; De Hosson, Jeff T M; van Dorp, Willem F

2017-01-01

Au(I) complexes are studied as precursors for focused electron beam induced processing (FEBIP). FEBIP is an advanced direct-write technique for nanometer-scale chemical synthesis. The stability and volatility of the complexes are characterized to design an improved precursor for pure Au deposition. Aurophilic interactions are found to play a key role. The short lifetime of ClAuCO in vacuum is explained by strong, destabilizing Au-Au interactions in the solid phase. While aurophilic interactions do not affect the stability of ClAuPMe 3 , they leave the complex non-volatile. Comparison of crystal structures of ClAuPMe 3 and MeAuPMe 3 shows that Au-Au interactions are much weaker or partially even absent for the latter structure. This explains its high volatility. However, MeAuPMe 3 dissociates unfavorably during FEBIP, making it an unsuitable precursor. The study shows that Me groups reduce aurophilic interactions, compared to Cl groups, which we attribute to electronic rather than steric effects. Therefore we propose MeAuCO as a potential FEBIP precursor. It is expected to have weak Au-Au interactions, making it volatile. It is stable enough to act as a volatile source for Au deposition, being stabilized by 6.5 kcal/mol. Finally, MeAuCO is likely to dissociate in a single step to pure Au.

Effects of alloying element on stabilities, electronic structures, and mechanical properties of Pd-based superalloys

NASA Astrophysics Data System (ADS)

Yan, Pei; Chong, Xiao-Yu; Jiang, Ye-Hua; Feng, Jing

2017-12-01

Not Available Project supported by the Young-Talent Support Programs of Kunming University of Science and Technology, China (Grant No. 11504146) and the National Natural Science Foundation of China (Grant No. 51762028).

Magnetic ground state and electronic structure of CeRu(2)Al(10).

PubMed

Goraus, Jerzy; Ślebarski, Andrzej

2012-03-07

We present a combined theoretical and experimental study of the electronic structure for CeRu(2)Al(10) based on ab initio band structure calculations and x-ray photoemission spectroscopy (XPS) data. Our calculations were performed for the base unit cell and for the hypothetical unit cell which enables antiferromagnetic ordering. The stability of the magnetic phase was investigated within fixed spin moment calculations. When additional 4f correlations are not included in the LSDA C U approach, CeRu(2)Al(10) exhibits an unstable magnetic configuration with the difference in total energy per unit cell between the weakly magnetic state and the non-magnetic one of the order ~0.3 meV. We found that Coulomb correlations among 4f electrons, when they are included in the LSDA C U approach, stabilize the magnetic structure. In the weakly correlated system (small U) an antiferromagnetic (AFM) ground state with the lowest total energy is preferred. The situation is, however, the opposite when the 4f correlations are strong. In this case the ferromagnetic (FM) ground state is preferred. By comparing our calculations with the experimental data we conclude that the 4f correlations in CeRu(2)Al(10) are weak. We also carried out a structural relaxation of atomic positions within the Cmcm unit cell and we found that the Al atoms exhibit noticeable displacement from their positions known from x-ray diffraction (XRD) analysis.

Stability of rhombohedral phases in vanadium at high-pressure and high-temperature: first-principles investigations

NASA Astrophysics Data System (ADS)

Wang, Yi X.; Wu, Q.; Chen, Xiang R.; Geng, Hua Y.

2016-09-01

The pressure-induced transition of vanadium from BCC to rhombohedral structures is unique and intriguing among transition metals. In this work, the stability of these phases is revisited by using density functional theory. At finite temperatures, a novel transition of rhombohedral phases back to BCC phase induced by thermal electrons is discovered. This reentrant transition is found not driven by phonons, instead it is the electronic entropy that stabilizes the latter phase, which is totally out of expectation. Parallel to this transition, we find a peculiar and strong increase of the shear modulus C44 with increasing temperature. It is counter-intuitive in the sense that it suggests an unusual harding mechanism of vanadium by temperature. With these stability analyses, the high-pressure and finite-temperature phase diagram of vanadium is proposed. Furthermore, the dependence of the stability of RH phases on the Fermi energy and chemical environment is investigated. The results demonstrate that the position of the Fermi level has a significant impact on the phase stability, and follows the band-filling argument. Besides the Fermi surface nesting, we find that the localization/delocalization of the d orbitals also contributes to the instability of rhombohedral distortions in vanadium.

Electronic structure and mechanical properties of osmium borides, carbides and nitrides from first principles

NASA Astrophysics Data System (ADS)

Liang, Yongcheng; Zhao, Jianzhi; Zhang, Bin

2008-06-01

The stabilities, mechanical properties and electronic structures of osmium boride (OsB), carbide (OsC) and nitride (OsN), in the tungsten carbide (WC), rocksalt (NaCl), cesium chloride (CsCl) and zinc blende (ZnS) structures respectively, are systematically predicted by calculations from first-principles. Only four phases, namely, OsB(WC), OsB(CsCl), OsC(WC), and OsC(ZnS), are mechanically stable, and none is a superhard compound, contrary to previous speculation. Most importantly, we find that the changing trends of bulk modulus and shear modulus are completely different for OsB, OsC and OsN in same hexagonal WC structure, which indicates that the underlying sources of hardness and incompressibility are fundamentally different: the former is determined by bonding nature while the latter is closely associated with valence electron density.

Heptagraphene: Tunable dirac cones in a graphitic structure

DOE PAGES

Lopez-Bezanilla, Alejandro; Martin, Ivar; Littlewood, Peter B.

2016-09-13

Here, we predict the existence and dynamical stability of heptagraphene, a new graphitic structure formed of rings of 10 carbon atoms bridged by carbene groups yielding seven-membered rings. Despite the rectangular unit cell, the band structure is topologically equivalent to that of strongly distorted graphene. Density-functional-theory calculations demonstrate that heptagraphene has Dirac cones on symmetry lines that are robust against biaxial strain but which open a gap under shear. At high deformation values bond reconstructions lead to different electronic band arrangements in dynamically stable configurations. Within a tight-binding framework this richness of the electronic behavior is identified as a directmore » consequence of the symmetry breaking within the cell which, unlike other graphitic structures, leads to band gap opening. A combined approach of chemical and physical modification of graphene unit cell unfurls the opportunity to design carbon-based systems in which one aims to tune an electronic band gap.« less

First-principles study of structural stability, electronic, optical and elastic properties of binary intermetallic: PtZr

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

Pagare, Gitanjali, E-mail: gita-pagare@yahoo.co.in; Jain, Ekta, E-mail: jainekta05@gmail.com; Sanyal, S. P., E-mail: sps.physicsbu@gmail.com

2016-05-06

Structural, electronic, optical and elastic properties of PtZr have been studied using the full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT). The energy against volume and enthalpy vs. pressure variation in three different structures i.e. B{sub 1}, B{sub 2} and B{sub 3} for PtZr has been presented. The equilibrium lattice parameter, bulk modulus and its pressure derivative have been obtained using optimization method for all the three phases. Furthermore, electronic structure was discussed to reveal the metallic character of the present compound. The linear optical properties are also studied under zero pressure for the first time.more » Results on elastic properties are obtained using generalized gradient approximation (GGA) for exchange correlation potentials. Ductile nature of PtZr compound is predicted in accordance with Pugh’s criteria.« less

The Pressure Dependence of Structural, Electronic, Mechanical, Vibrational, and Thermodynamic Properties of Palladium-Based Heusler Alloys

NASA Astrophysics Data System (ADS)

Çoban, Cansu

2017-08-01

The pressure dependent behaviour of the structural, electronic, mechanical, vibrational, and thermodynamic properties of Pd2TiX (X=Ga, In) Heusler alloys was investigated by ab initio calculations. The lattice constant, the bulk modulus and its first pressure derivative, the electronic band structure and the density of states (DOS), mechanical properties such as elastic constants, anisotropy factor, Young's modulus, etc., the phonon dispersion curves and phonon DOS, entropy, heat capacity, and free energy were obtained under pressure. It was determined that the calculated lattice parameters are in good agreement with the literature, the elastic constants obey the stability criterion, and the phonon dispersion curves have no negative frequency which shows that the compounds are stable. The band structures at 0, 50, and 70 GPa showed valence instability at the L point which explains the superconductivity in Pd2TiX (X=Ga, In).

First-principles predictions of structural, mechanical and electronic properties of βTiNb under high pressure

NASA Astrophysics Data System (ADS)

Wang, Z. P.; Fang, Q. H.; Li, J.; Liu, B.

2018-04-01

Structural, mechanical and electronic properties of βTiNb alloy under high pressure have been investigated based on the density functional theory (DFT). The dependences of dimensionless volume ratio, elastic constants, bulk modulus, Young's modulus, shear modulus, ductile/brittle, anisotropy and Poisson's ratio on applied pressure are all calculated successfully. The results reveal that βTiNb alloy is mechanically stable under pressure below 23.45 GPa, and the pressure-induced phase transformation could occur beyond this critical value. Meanwhile, the applied pressure can effectively promote the mechanical properties of βTiNb alloy, including the resistances to volume change, elastic deformation and shear deformation, as well as the material ductility and metallicity. Furthermore, the calculated electronic structures testify that βTiNb alloy performs the metallicity and the higher pressure reduces the structural stability of unit cell.

Behavior of magnesium at high pressures and high temperatures

NASA Astrophysics Data System (ADS)

Cynn, H.; Evans, W.; Yoo, C. S.; Ohishi, Y.; Sata, N.; Shimomura, O.

2004-03-01

Structural stability relationship manifested by 3-, 4-, 5d-electron transition metals also appears in so-called nearly free electron metal, magnesium as exampled by HCP to BCC structure change at high pressures. This transition has been examined by theory and confirmed by experiment. Recently, HCP to DHCP crystal structure change has been reported at high temperatures below 20 GPa. However, this type of structure change is rather common in 4f-electron lanthanides. In this study, we used synchrotron x-ray diffraction to find out the relationship between BCC and DHCP employing a diamond anvil cell technique coupled with external and laser heating methods. We also examined pressure gradient effects in relation with the existence of DHCP. This work has been supported by PDRP program at the Lawrence Livermore National Laboratory, University of California under the auspices of the U.S. Department of Energy under Contract No. W-7405-ENG-48

Electronic structure and acid-base properties of Kojic acid and its dimers. A DFT and quantum topology study

NASA Astrophysics Data System (ADS)

Aziz, Saadullah G.; Alyoubi, Abdulrahman O.; Elroby, Shaaban A.; Hilal, Rifaat H.

2017-10-01

Kojic acid is a polyfunctional heterocyclic compound, with several important reaction centres; it has a wide range of applications in the cosmetic, medicine, food, agriculture and chemical industries. The present study aims at better insight into its electronic structure and bonding characteristics. Thus, density functional theory at the M06-2x /6-311++G** level of theory is used to investigate its ground state electronic and acid-base properties. Protonation and deprotonation enthalpies are computed and analysed. The ability of Kojic acid to form both water complexes and dimers is explored. Several different complexes and dimer structures were examined. Natural bond order and quantum topology features of the charge density were analysed. The origin of the stability of the studied complexes and dimer structures can be traced to hydrogen bonding, π-conjugative and non-covalent dispersive interactions.

Electronic structure of binuclear acetylacetonates of boron difluoride

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Svistunova, Irina V.; Samoilov, Ilya S.; Osmushko, Ivan S.; Borisenko, Aleksandr V.; Vovna, Vitaliy I.

2018-05-01

The electronic structure of boron difluoride acetylacetonate and its three derivatives was studied using photoelectron and absorption spectroscopy, as well as the density functional theory. In a series of binuclear acetylacetonate complexes containing bridge-moieties of sulfur and selenium atoms, it was found an appreciable mixing of the π3-orbital of the chelate cycle with atomic orbitals S 3p and Se 4p resulting in destabilization of the HOMO levels by 0.4-0.6 eV, in comparison with the monomer. The positively charged fragment C(CH3)-CX-C(CH3) causes the field effect, which leads to stabilization of the LUMO levels by 0.3-0.4 eV and C 1s-levels by 0.5-1.2 eV. An analysis of the research results on the electronic structure made it possible to determine the effect of substituents in the γ position on the absorption spectra, which is mainly determined by the electron density transfer from the chalcogen atoms to the chelate cycles. It is shown that the calculated energy intervals between electron levels correlate well with the structure of the photoelectron spectra of valence and core electrons.

Investigations on the electronic, structural, magnetic properties related to shape-memory behavior in Ti{sub 2}CoX (X=Al, Ga, In)

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

Wei, Xiao-Ping, E-mail: weixp2008@gmail.com; Chu, Yan-Dong; Sun, Xiao-Wei

2015-02-15

Highlights: • The analysis of phase stability trend is studied for Ti{sub 2}CoX(X = Al, Ga, In). • Ti{sub 2}CoGa is more suitable as shape memory alloy. • Total magnetic moments disappear with a increase of c/a ratio for all systems. • Density of states at the Fermi level are also shown. - Abstract: Using the full-potential local orbital minimum-basis method, we have performed a systematic investigations on the electronic, structural, and magnetic properties related to shape memory applications for Ti{sub 2}CoX (X=Al, Ga, In) alloys. Our results confirm that these alloys are half-metallic ferromagnets with total magnetic moment ofmore » 2μ{sub B} per formula unit in austenite phase, and undergo a martensitic transformation at low temperatures. The relative stabilities of the martensitic phases differ considerably between Ti{sub 2}CoX (X=Al, Ga, In). Details of the electronic structures suggest that the differences in hybridizations between the magnetic components are responsible for trends of phase. Quantitative estimates for the energetics and the magnetizations indicate that Ti{sub 2}CoGa is a promising candidate for shape memory applications.« less

Probing the structural and electronic properties of cationic rubidium-gold clusters: [AunRb]+ (n = 1-10)

NASA Astrophysics Data System (ADS)

Zhao, Ya-Ru; Zhang, Hai-Rong; Qian, Yu; Duan, Xu-Chao; Hu, Yan-Fei

2016-03-01

Density functional theory has been applied to study the geometric structures, relative stabilities, and electronic properties of cationic [AunRb]+ and Aun + 1+ (n = 1-10) clusters. For the lowest energy structures of [AunRb]+ clusters, the planar to three-dimensional transformation is found to occur at cluster size n = 4 and the Rb atoms prefer being located at the most highly coordinated position. The trends of the averaged atomic binding energies, fragmentation energies, second-order difference of energies, and energy gaps show pronounced even-odd alternations. It indicated that the clusters containing odd number of atoms maintain greater stability than the clusters in the vicinity. In particular, the [Au6Rb]+ clusters are the most stable isomer for [AunRb]+ clusters in the region of n = 1-10. The charges in [AunRb]+ clusters transfer from the Rb atoms to Aun host. Density of states revealed that the Au-5d, Au-5p, and Rb-4p orbitals hardly participated in bonding. In addition, it is found that the most favourable channel of the [AunRb]+ clusters is Rb+ cation ejection. The electronic localisation function (ELF) analysis of the [AunRb]+ clusters shown that strong interactions are not revealed in this study.

Features of the electronic structure of FeTe compounds

NASA Astrophysics Data System (ADS)

Grechnev, G. E.; Lyogenkaya, A. A.; Panfilov, A. S.; Logosha, A. V.; Kotlyar, O. V.; Gnezdilov, V. P.; Makarova, I. P.; Chareev, D. A.; Mitrofanova, E. S.

2015-12-01

A theoretical and experimental study of the electronic structure and nature of the chemical bonds in FeTe compounds in antiferromagnetic (AFM) and paramagnetic phases was carried out. It is established that the nature of the chemical bonds is mainly metallic, and the presence of covalent bonds Fe-Te and Te-Te helps to stabilize the structural distortions of the tetragonal phase of FeTe in the low-temperature region. It is found that the bicollinear AFM structure corresponds to the ground state of the FeTe compound and the calculated value of the magnetic moment MFe = -2.4μB is in good agreement with the data from neutron diffraction measurements. At the same time, the Fermi surface (FS) of the low-temperature AFM phase is radically different from the FS of the paramagnetic FeTe. Reconstructing the FS can lead to a sign change of the Hall coefficient observed in FeTe. The calculation results serve as evidence of the fact that the electronic structures and magnetic properties of FeTe are well-described by the model of itinerant d-electrons and the density functional theory (DFT-GGA).

Flash Nanoprecipitation: Particle Structure and Stability

PubMed Central

Pustulka, Kevin M.; Wohl, Adam R.; Lee, Han Seung; Michel, Andrew R.; Han, Jing; Hoye, Thomas R.; McCormick, Alon V.; Panyam, Jayanth; Macosko, Christopher W.

2013-01-01

Flash nanoprecipitation (FNP) is a process that, through rapid mixing, stabilizes an insoluble low molecular weight compound in a nano-sized, polymer-stabilized delivery vehicle. The polymeric components are typically amphiphilic diblock copolymers (BCPs). In order to fully exploit the potential of FNP, factors affecting particle structure, size, and stability must be understood. Here we show that polymer type, hydrophobicity and crystallinity of the small molecule, and small molecule loading levels all affect particle size and stability. Of the four block copolymers (BCP) that we have studied here, poly(ethylene glycol)-b-poly(lactic-co-glycolic acid) (PEG-b-PLGA) was most suitable for potential drug delivery applications due to its ability to give rise to stable nanoparticles, its biocompatibility, and its degradability. We found little difference in particle size when using PLGA block sizes over the range of 5 to 15kDa. The choice of hydrophobic small molecule was important, as molecules with a calculated water-octanol partition coefficient (clogP) below 6 gave rise to particles that were unstable and underwent rapid Ostwald ripening. Studies probing the internal structure of nanoparticles were also performed. Analysis of differential scanning calorimetry (DSC), cryogenic transmission electron microscopy (cryo-TEM), and 1H-NMR experiments support a three-layer core-shell-corona nanoparticle structure. PMID:24053447

Probing the Structures and Electronic Properties of Dual-Phosphorus-Doped Gold Cluster Anions (AunP-2, n = 1–8): A Density functional Theory Investigation

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

Xu, Kang-Ming; Huang, Teng; Liu, Yi-Rong

2015-07-29

The geometries of gold clusters doped with two phosphorus atoms, (AunP-2, n = 1–8) were investigated using density functional theory (DFT) methods. Various two-dimensional (2D) and three-dimensional (3D) structures of the doped clusters were studied. The results indicate that the structures of dual-phosphorus-doped gold clusters exhibit large differences from those of pure gold clusters with small cluster sizes. In our study, as for Au6P-2, two cis–trans isomers were found. The global minimum of Au8P-2 presents a similar configuration to that of Au-20, a pyramid-shaped unit, and the potential novel optical and catalytic properties of this structure warrant further attention. Themore » higher stability of AunP-2 clusters relative to Au-n+2 (n = 1–8) clusters was verified based on various energy parameters, and the results indicate that the phosphorus atom can improve the stabilities of the gold clusters. We then explored the evolutionary path of (n = 1–8) clusters. We found that AunP-2 clusters exhibit the 2D–3D structural transition at n = 6, which is much clearer and faster than that of pure gold clusters and single-phosphorus-doped clusters. The electronic properties of AunP-2 (n = 1–8) were then investigated. The photoelectron spectra provide additional fundamental information on the structures and molecular orbitals shed light on the evolution of AunP-2 (n = 1–8). Natural bond orbital (NBO) described the charge distribution in stabilizing structures and revealed the strong relativistic effects of the gold atoms.« less

Stabilities of nitrogen containing heterocyclic radicals and geometrical influences on non-radiative processes in organic molecules

NASA Technical Reports Server (NTRS)

Evleth, E. M.

1972-01-01

Stabilities of nitrogen containing heterocyclic radicals were studied to detect radicals of the type R-N-R, and to theoretically rationalize their electronic structure. The computation of simple potential energy surfaces for ground and excited states is discussed along with the photophysical properties of indolizine. Methods of calculation and problems associated with the calculations are presented. Results, tables, diagrams, discussions, and references are included.

D3h [A-CE3-A]- (E = Al and Ga, A = Si, Ge, Sn, and Pb): A new class of hexatomic mono-anionic species with trigonal bipyramidal carbon

NASA Astrophysics Data System (ADS)

Wu, Yan-Bo; Li, Yan-Qin; Bai, Hui; Lu, Hai-Gang; Li, Si-Dian; Zhai, Hua-Jin; Wang, Zhi-Xiang

2014-03-01

The non-classical trigonal bipyramidal carbon (TBPC) arrangement generally exists as transition states (TSs) in nucleophilic bimolecular substitution (SN2) reactions. Nevertheless, chemists have been curious about whether such a carbon bonding could be stable in equilibrium structures for decades. As the TBPC arrangement was normally realized as cationic species theoretically and experimentally, only one anionic example ([At-C(CN)3-At]-) was computationally devised. Herein, we report the design of a new class of anionic TBPC species by using the strategy similar to that for stabilizing the non-classical planar hypercoordinate carbon. When electron deficient Al and Ga were used as the equatorial ligands, eight D3h [A-CE3-A]- (E = Al and Ga, A = Si, Ge, Sn, and Pb) TBPC structures were found to be the energy minima rather than TSs at both the B3LYP and MP2 levels. Remarkably, the energetic results at the CCSD(T) optimization level further identify [Ge-CAl3-Ge]- and [Sn-CGa3-Sn]- even to be the global minima and [Si-CAl3-Si]- and [Ge-CGa3-Ge]- to be the local minima, only slightly higher than their global minima. The electronic structure analyses reveal that the substantial ionic C-E bonding, the peripheral E-A covalent bonding, and the axial mc-2e (multi center-two electrons) bonding play roles in stabilizing these TBPC structures. The structural simplicity and the high thermodynamic stability suggest that some of these species may be generated and captured in the gas phase. Furthermore, as mono-anionic species, their first vertical detachment energies are differentiable from those of their nearest isomers, which would facilitate their characterization via experiments such as the negative ion photoelectron spectroscopy.

Modification of electronic structure, magnetic structure, and topological phase of bismuthene by point defects

NASA Astrophysics Data System (ADS)

Kadioglu, Yelda; Kilic, Sevket Berkay; Demirci, Salih; Aktürk, O. Üzengi; Aktürk, Ethem; Ciraci, Salim

2017-12-01

This paper reveals how the electronic structure, magnetic structure, and topological phase of two-dimensional (2D), single-layer structures of bismuth are modified by point defects. We first showed that a free-standing, single-layer, hexagonal structure of bismuth, named h-bismuthene, exhibits nontrivial band topology. We then investigated interactions between single foreign adatoms and bismuthene structures, which comprise stability, bonding, electronic structure, and magnetic structures. Localized states in diverse locations of the band gap and resonant states in band continua of bismuthene are induced upon the adsorption of different adatoms, which modify electronic and magnetic properties. Specific adatoms result in reconstruction around the adsorption site. Single vacancies and divacancies can form readily in bismuthene structures and remain stable at high temperatures. Through rebondings, Stone-Whales-type defects are constructed by divacancies, which transform into a large hole at high temperature. Like adsorbed adatoms, vacancies induce also localized gap states, which can be eliminated through rebondings in divacancies. We also showed that not only the optical and magnetic properties, but also the topological features of pristine h-bismuthene can be modified by point defects. The modification of the topological features depends on the energies of localized states and also on the strength of coupling between point defects.

Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole.

PubMed

Arjunan, V; Raj, Arushma; Santhanam, R; Marchewka, M K; Mohan, S

2013-02-01

Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. (1)H and (13)C NMR chemical shifts and the electronic transitions of the molecule are also discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Theoretical prediction of a novel inorganic fullerene-like family of silicon-carbon materials

NASA Astrophysics Data System (ADS)

Wang, Ruoxi; Zhang, Dongju; Liu, Chengbu

2005-08-01

In an effort to search for new inorganic fullerene-like structures, we designed a series of novel silicon-carbon cages, (SiC) n ( n = 6-36), based on the uniformly hybrid Si-C four- and six-membered-rings, and researched their geometrical and electronic structures, as well as their relative stabilities using the density function theory. Among these cages, the structures for n = 12, 16, and 36 were found to been energetically more favorable. The calculated disproportionation energy and binding energy per SiC unit show that the (SiC) 12 cage is the most stable one among these designed structures. The present calculations not only indicate that silicon-carbon fullerenes are promised to be synthesized in future, but also provide a new way for stabilizing silicon cages by uniformly doping carbon atoms into silicon structures.

Stabilization of fullerene-like boron cages by transition metal encapsulation

NASA Astrophysics Data System (ADS)

Lv, Jian; Wang, Yanchao; Zhang, Lijun; Lin, Haiqing; Zhao, Jijun; Ma, Yanming

2015-06-01

The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ~38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials.The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ~38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01659b

Using real-time electron microscopy to explore the effects of transition-metal composition on the local thermal stability in charged Li xNi yMn zCo 1-y-zO 2 cathode materials

DOE PAGES

Hwang, Sooyeon; Kim, Seung Min; Bak, Seong -Min; ...

2015-05-08

In this study, we use in-situ transmission electron microcopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged Li xNi yMn zCo 1-y-zO 2 (NMC) cathode materials of different composition (with y, z=0.8, 0.1 and 0.6, 0.2 and 0.4, 0.3), after they have been charged to their practical upper limit voltage (4.3V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z =more » 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositions – this is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100°C. Electron energy loss spectroscopy indicates that the thermally induced reduction of Ni ions drives these changes, and that this is exacerbated by the presence of an additional redox reaction that occurs at 4.2V in the y, z = 0.8, 0.1 material. Exploration of individual particles shows that there are substantial variations in the onset temperatures and overall extent of these changes. Of the compositions studied, the composition of y, z = 0.6, 0.2 has the optimal combination of high energy density and reasonable thermal stability. The observations herein demonstrate that real time electron microscopy provide direct insight into the changes that occur in cathode materials with temperature, allowing optimization of different alloy concentrations to maximize overall performance.« less

Designing a porous-crystalline structure of β-Ga2O3: a potential approach to tune its opto-electronic properties.

PubMed

Banerjee, Swastika; Jiang, Xiangwei; Wang, Lin-Wang

2018-04-04

β-Ga2O3 has drawn recent attention as a state-of-the-art electronic material due to its stability, optical transparency and appealing performance in power devices. However, it has also found a wider range of opto-electronic applications including photocatalysis, especially in its porous form. For such applications, a lower band gap must be obtained and an electron-hole spatial separation would be beneficial. Like many other metal oxides (e.g. Al2O3), Ga2O3 can also form various types of porous structure. In the present study, we investigate how its optical and electronic properties can be changed in a particular porous structure with stoichiometrically balanced and extended vacancy channels. We apply a set of first principles computational methods to investigate the formation and the structural, dynamic, and opto-electronic properties. We find that such an extended vacancy channel is mechanically stable and has relatively low formation energy. We also find that this results in a spatial separation of the electron and hole, forming a long-lived charge transfer state that has desirable characteristics for a photocatalyst. In addition, the electronic band gap reduces to the vis-region unlike the transparency in the pure β-Ga2O3 crystal. Thus, our systematic study is promising for the application of such a porous structure of β-Ga2O3 as a versatile electronic material.

Chlorine adsorption on the InAs (001) surface

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

Bakulin, A. V.; Eremeev, S. V.; Tereshchenko, O. E.

2011-01-15

Chlorine adsorption on the In-stabilized InAs(001) surface with {zeta}-(4 Multiplication-Sign 2) and {beta}3 Prime -(4 Multiplication-Sign 2) reconstructions and on the Ga-stabilized GaAs (001)-{zeta}-(4 Multiplication-Sign 2) surface has been studied within the electron density functional theory. The equilibrium structural parameters of these reconstructions, surface atom positions, bond lengths in dimers, and their changes upon chlorine adsorption are determined. The electronic characteristics of the clean surface and the surface with adsorbed chlorine are calculated. It is shown that the most energetically favorable positions for chlorine adsorption are top positions over dimerized indium or gallium atoms. The mechanism of chlorine binding withmore » In(Ga)-stabilized surface is explained. The interaction of chlorine atoms with dimerized surface atoms weakens surface atom bonds and controls the initial stage of surface etching.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

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

McSkimming, Alex; Su, Jing; Cheisson, Thibault

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

Coordination Chemistry of a Strongly-Donating Hydroxylamine with Early Actinides: An Investigation of Redox Properties and Electronic Structure

DOE PAGES

McSkimming, Alex; Su, Jing; Cheisson, Thibault; ...

2018-03-23

Separations of f-block elements are a critical aspect of nuclear waste processing. Redox-based separations offer promise, but challenges remain in stabilizing and differentiating actinides in high oxidation states. The investigation of new ligand types that provide thermodynamic stabilization to high-valent actinides is essential for expanding their fundamental chemistry and to elaborate new separation techniques and storage methods. We report herein the preparation and characterization of Th and U complexes of the pyridyl-hydroxylamine ligand, N-tert-butyl-N-(pyridin-2-yl)hydroxylamine (pyNO–). Electrochemical studies performed on the homoleptic complexes [M(pyNO) 4] (M = Th, U) revealed significant stabilization of the U complex upon one-electron oxidation. The saltmore » [U(pyNO) 4] + was isolated by chemical oxidation of [U(pyNO) 4]; spectroscopic and computational data support assignment as a U V cation.« less

On the effect of Ti on the stability of amorphous indium zinc oxide used in thin film transistor applications

NASA Astrophysics Data System (ADS)

Lee, Sunghwan; Paine, David C.

2011-06-01

In2O3-based amorphous oxide channel materials are of increasing interest for thin film transisitor applications due, in part, to the remarkable stability of this class of materials amorphous structure and electronic properties. We report that this stability is degraded in the presence of Ti, which is widely used as a contact and/or adhesion layer. A cross-sectional transmission electron microscopy analysis, supported by glancing incident angle x-ray and selected area diffraction examination, shows that amorphous indium zinc oxide in contact with Ti undergoes crystallization to the bixbyite phase and reacts to form the rutile phase of TiO2 at a temperature of 200 °C. A basic thermodynamic analysis is presented and forms the basis of a model that describes both the crystallization and the resistivity decrease.

Biopolymer stabilized water dispersible polyaniline for supercapacitor electrodes

NASA Astrophysics Data System (ADS)

Anbalagan, Amarnath Chellachamy; Sawant, Shilpa Nandkishor

2018-04-01

Polyaniline colloidal nanoparticles (PANI CNs) were synthesized, employing biopolymer pectin (Pec) as a stabilizer along with hydrochloric acid dopant and ammonium persulfate oxidant. Chemical nature and electronic structure was studied by FT-IR and UV-visible spectroscopy respectively. FE-SEM revealed spindle like morphology of PANI CNs and displayed the nearly discrete particles without aggregation, showing stabilizing capacity of the Pec. Cyclic voltammetry and galvanostatic charge-discharge measurements demonstrated the electroactivity and supercapacitive property of the PANI CNs in 1 M HCl. The specific capacitance of PANI CNs in 1 M HCl at 1.5 A/g was found to be 197 F/g, where 70% of specific capacitance was retained even after 1000 cycles. These findings establish the feasibility of using the PANI CNs as a potential material for energy storage in aqueous acidic medium. Furthermore, this colloidal dispersion can find potential application in electrodes of flexible supercapacitor device and printable electronics.

Electronic and magnetic properties of SnS2 monolayer doped with 4d transition metals

NASA Astrophysics Data System (ADS)

Xiao, Wen-Zhi; Xiao, Gang; Rong, Qing-Yan; Chen, Qiao; Wang, Ling-Ling

2017-09-01

We investigate the electronic structures and magnetic properties of SnS2 monolayers substitutionally doped with 4-d transition-metal through systematic first principles calculations. The doped complexes exhibit interesting electronic and magnetic behaviors, depending on the interplay between crystal field splitting, Hund's rule, and 4d levels. The system doped with Y is nonmagnetic metal. Both the Zr- and Pd-doped systems remain nonmagnetic semiconductors. Doping results in half-metallic states for Nb-, Ru-, Rh-, Ag, and Cd doped cases, and magnetic semiconductors for systems with Mo and Tc dopants. In particular, the Nb- and Mo-doped systems display long-ranged ferromagnetic ordering with Curie temperature above room temperature, which are primarily attributable to the double-exchange mechanism, and the p-d/p-p hybridizations, respectively. Moreover, The Mo-doped system has excellent energetic stability and flexible mechanical stability, and also possesses remarkable dynamic and thermal (500 K) stability. Our studies demonstrate that Nb- and Mo-doped SnS2 monolayers are promising candidates for preparing 2D diluted magnetic semiconductors, and hence will be a helpful clue for experimentalists.

Analytic model of a laser-accelerated composite plasma target and its stability

NASA Astrophysics Data System (ADS)

Khudik, Vladimir; Shvets, Gennady

2013-10-01

A self-consistent analytical model of monoenergetic acceleration of a one and two-species ultrathin target irradiated by a circularly polarized laser pulse is developed. In the accelerated reference frame, the bulk plasma in the target is neutral and its parameters are assumed to be stationary. It is found that the structure of the target depends strongly on the temperatures of electrons and ions, which are both strongly influenced by the laser pulse pedestal. When the electron temperature is large, the hot electrons bounce back and forth inside the potential well formed by ponderomotive and electrostatic potentials while the heavy and light ions are forced-balanced by the electrostatic and non-inertial fields forming two separated layers. In the opposite limiting case when the ion temperature is large, the hot ions are trapped in the potential well formed by the ion-sheath's electric and non-inertial potentials while the cold electrons are forced-balanced by the electrostatic and ponderomotive fields. Using PIC simulations we have determined which scenario is realized in practice depending on the initial target structure and laser intensity. Target stability with respect to Rayleigh-Taylor instability will also be discussed. This work is supported by the US DOE grants DE-FG02-04ER41321 and DE-FG02-07ER54945.

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

Structural and electronic properties of Ga2O3-Al2O3 alloys

NASA Astrophysics Data System (ADS)

Peelaers, Hartwin; Varley, Joel B.; Speck, James S.; Van de Walle, Chris G.

2018-06-01

Ga2O3 is emerging as an important electronic material. Alloying with Al2O3 is a viable method to achieve carrier confinement, to increase the bandgap, or to modify the lattice parameters. However, the two materials have very different ground-state crystal structures (monoclinic β-gallia for Ga2O3 and corundum for Al2O3). Here, we use hybrid density functional theory calculations to assess the alloy stabilities and electronic properties of the alloys. We find that the monoclinic phase is the preferred structure for up to 71% Al incorporation, in close agreement with experimental phase diagrams, and that the ordered monoclinic AlGaO3 alloy is exceptionally stable. We also discuss bandgap bowing, lattice constants, and band offsets that can guide future synthesis and device design efforts.

Kinetic stability analysis on electromagnetic filamentary structure

NASA Astrophysics Data System (ADS)

Lee, Wonjae; Krasheninnikov, Sergei

2014-10-01

A coherent radial transport of filamentary structures in SOL region is important for its characteristics that can increase unwanted high fluxes to plasma facing components. In the course of propagation in radial direction, the coherency of the filaments is significantly limited by electrostatic resistive drift instability (Angus et al., 2012). Considering higher plasma pressure, which would have more large impact in heat fluxes, electromagnetic effects will reduce the growth rate of the drift wave instability and increase the instabilities from electron inertial effects. According to a linear stability analysis on equations with fluid approximation, the maximum growth rate of the instability from the electron inertia is higher than that of drift-Alfvén wave instability in high beta filaments such as ELMs. However, the analysis on the high beta filaments requires kinetic approach, since the decreased collisionality will make the fluid approximation broken. Therefore, the kinetic analysis will be presented for the electromagnetic effects on the dynamics of filamentary structures. This work was supported by the USDOE Grants DE-FG02-04ER54739 and DE-SC0010413 at UCSD and also by the Kwanjeong Educational Foundation.

Thermoelectric and transport properties of sintered n-type K{sub 8}Ba{sub 16}Ga{sub 40}Sn{sub 96} with type-II clathrate structure

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

Koda, Shota; Kishimoto, Kengo, E-mail: kkishi@yamaguchi-u.ac.jp; Asada, Hironori

This clathrate had a maximum dimensionless figure-of-merit, ZT, of 0.93 at 637 K, which was slightly higher than that of 0.83 for the sintered type-VIII clathrate Ba{sub 8}Ga{sub 16}Sn{sub 30}. We investigated the high-temperature thermoelectric properties, transport properties, electronic structures, and thermal stabilities of the clathrates. The type-II clathrate was found to be superior to the type-VIII clathrate as a thermoelectric material; it had a high thermal stability and melting point, 859 K, high mobility, 141 cm{sup 2}V{sup −1}s{sup −1} at 300 K, because of its low inertial mass, and low high-temperature lattice thermal conductivity, approximately 4 mW cm{sup −1}K{sup −1}, resulting frommore » a larger unit cell and weaker bipolar thermal conduction. We discuss these properties in terms of the electronic structure and the differences between the two types of clathrate.« less

Role of organic cations on hybrid halide perovskite CH3NH3PbI3 surfaces

NASA Astrophysics Data System (ADS)

Teng, Qiang; Shi, Ting-Ting; Tian, Ren-Yu; Yang, Xiao-Bao; Zhao, Yu-Jun

2018-02-01

Organic-inorganic hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has received rapid progress in power conversion efficiency as promising photovoltaic materials, yet the surface structures and the role of MA cations are not well understood. In this work, we investigated the structural stability and electronic properties of (001) surface of cubic, (001) and (110) surfaces of tetragonal and orthorhombic phases of MAPbI3 with considering the orientation of MA cations, by density functional theory calculations. We demonstrate that the orientation of MA cations has profound consequences on the structural stability and the electronic properties of the surfaces, in contrast to the bulk phases. Compared with the MA-I terminated surfaces, the Pb-I2 terminated ones generally have smaller band gaps and the advantage to enable the photo-excited holes to transfer to the hole-transport materials in both tetragonal and orthorhombic phases. Overall, we suggest that the films with Pb-I2 terminated surfaces would prevail in high performance solar energy absorbers.

Effects of ionizing radiation and temperature on uranyl silicates: soddyite (UO2)2(SiO4)(H2O)2 and Uranophane Ca(UO2)2(SiO3OH)2·5H2O.

PubMed

Sureda, R; Casas, I; Giménez, J; de Pablo, J; Quiñones, J; Zhang, J; Ewing, R C

2011-03-15

The stability of soddyite under electron irradiation has been studied over the temperature range of 25-300 °C. At room temperature, soddyite undergoes a crystalline-to-amorphous transformation (amorphization) at a total dose of 6.38 × 10(8) Gy. The electron beam irradiation results suggest that the soddyite structure is susceptible to radiation-induced nanocrystallization of UO(2). The temperature dependence of amorphization dose increases linearly up to 300 °C. A thermogravimetric and calorimetric analysis (TGA-DSC) combined with X-ray diffraction (XRD) indicates that soddyite retains its water groups up to 400 °C, followed by the collapse of the structure. Based on thermal analysis of uranophane, the removal of some water groups at relatively low temperatures provokes the collapse of the uranophane structure. This structural change appears to be the reason for the increase of amorphization dose at 140 °C. According to the results obtained, radiation field of a nuclear waste repository, rather than temperature effects, may cause changes in the crystallinity of soddyite and affect its stability during long-term storage.

Synthesis and thermal stability of W/WS{sub 2} inorganic fullerene-like nanoparticles with core-shell structure

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

Chang Lianxia; Yang Haibin; Fu Wuyou

W/WS{sub 2} inorganic fullerene-like (IF) nanoparticles with core-shell structure are synthesized by the reaction of tungsten nanospheres and sulfur at relatively low temperatures (380-600 deg. C) under hydrogen atmosphere, in which tungsten nanospheres were prepared by wire electrical explosion method. Images of transmission electron microscopy and high-resolution transmission electron microscopy show that the composite particles are of core-shell structure with spherical shape and the shell thickness is about 10 nm. X-ray powder diffraction results indicate that the interlayer spacing of IF-WS{sub 2} shell decreases and approaches that of 2H-WS{sub 2} with increasing annealing temperatures, representing an expansion of 3.3-1.6%. Amore » mechanism of IF-WS{sub 2} formation via sulfur diffusion into fullerene nanoparticles is discussed. Thermal analysis shows that the nanoparticles obtained at different temperatures exhibit similar thermal stability and the onset temperature of oxidization is about 410 deg. C. Encapsulating hard tungsten core into IF-WS{sub 2} and the spherical shape of the core-shell structures may enhance their performance in tribological applications.« less

Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra [On the Thermal Stability of Metal Nanocrystals: An Investigation of the Surface and Bulk Reconstructions of Pd Concave Icosahedra

DOE PAGES

Gilroy, Kyle D.; Elnabawy, Ahmed O.; Yang, Tung -Han; ...

2017-04-27

Despite the remarkable success in controlling the synthesis of metal nanocrystals, it still remains a grand challenge to stabilize and preserve the shapes or internal structures of metastable kinetic products. In this work, we address this issue by systematically investigating the surface and bulk reconstructions experienced by a Pd concave icosahedron when subjected to heating up to 600 °C in vacuum. We used in situ high-resolution transmission electron microscopy to identify the equilibration pathways of this far-from-equilibrium structure. We were able to capture key structural transformations occurring during the thermal annealing process, which were mechanistically rationalized by implementing self-consistent plane-wavemore » density functional theory (DFT) calculations. Specifically, the concave icosahedron was found to evolve into a regular icosahedron via surface reconstruction in the range of 200–400 °C, and then transform into a pseudospherical crystalline structure through bulk reconstruction when further heated to 600 °C. As a result, the mechanistic understanding may lead to the development of strategies for enhancing the thermal stability of metal nanocrystals.« less

Benchmarking the stability of human detergent-solubilised voltage-gated sodium channels for structural studies using eel as a reference

PubMed Central

Slowik, Daria; Henderson, Richard

2015-01-01

With the ultimate goal of detailed structural analysis of mammalian and particularly human voltage-gated sodium channels (VGSCs), we have investigated the relative stability of human and rat VGSCs and compared them with electric eel VGSC. We found that NaV1.3 from rat was the most stable after detergent solubilisation. The order of stability was rNaV1.3 > hNaV1.2 > hNaV1.1 > hNaV1.6 > hNaV1.3 > hNaV1.4. However, a comparison with the VGSC from Electrophorus electricus, which is most similar to NaV1.4, shows that the eel VGSC is considerably more stable in detergent than the human VGSCs examined. We conclude that current methods of structural analysis, such as single particle electron cryomicroscopy (cryoEM), may be most usefully targeted to eel VGSC or rNaV1.3, but that structural analysis on the full spectrum of VGSCs, by methods that require greater stability such as crystallisation and X-ray crystallography, will require further stabilisation of the channel. PMID:25838126

Substrate Effects for Atomic Chain Electronics

NASA Technical Reports Server (NTRS)

Yamada, Toshishige; Saini, Subhash (Technical Monitor)

1998-01-01

A substrate for future atomic chain electronics, where adatoms are placed at designated positions and form atomically precise device components, is studied theoretically. The substrate has to serve as a two-dimensional template for adatom mounting with a reasonable confinement barrier and also provide electronic isolation, preventing unwanted coupling between independent adatom structures. For excellent structural stability, we demand chemical bonding between the adatoms and substrate atoms, but then good electronic isolation may not be guaranteed. Conditions are clarified for good isolation. Because of the chemical bonding, fundamental adatom properties are strongly influenced: a chain with group IV adatoms having two chemical bonds, or a chain with group III adatoms having one chemical bond is semiconducting. Charge transfer from or to the substrate atoms brings about unintentional doping, and the electronic properties have to be considered for the entire combination of the adatom and substrate systems even if the adatom modes are well localized at the surface.

Electron-doping by hydrogen in transition-metal dichalcogenides

NASA Astrophysics Data System (ADS)

Oh, Sehoon; Im, Seongil; Choi, Hyoung Joon

Using first-principles calculations, we investigate the atomic and electronic structures of 2H-phase transition-metal dichalcogenides (TMDC), 2H-MX2, with and without defects, where M is Mo or W and X is S, Se or Te. We find that doping of atomic hydrogen on 2H-MX2 induces electron doping in the conduction band. To understand the mechanism of this electron doping, we analyze the electronic structures with and without impurities. We also calculate the diffusion energy barrier to discuss the spatial stability of the doping. Based on these results, we suggest a possible way to fabricate elaborately-patterned circuits by modulating the carrier type of 2H-MoTe2. We also discuss possible applications of this doping in designing nano-devices. This work was supported by NRF of Korea (Grant No. 2011-0018306) and KISTI supercomputing center (Project No. KSC-2016-C3-0052).

Electronic structure and chemical bonding of the electron-poor II-V semiconductors ZnSb and ZnAs

NASA Astrophysics Data System (ADS)

Benson, Daryn; Sankey, Otto F.; Häussermann, Ulrich

2011-09-01

The binary compounds ZnSb and ZnAs with the CdSb structure are semiconductors (II-V), although the average electron concentration (3.5 per atom) is lower than that of the tetrahedrally bonded III-V and II-VI archetype systems (four per atom). We report a detailed electronic structure and chemical bonding analysis for ZnSb and ZnAs based on first-principles calculations. ZnSb and ZnAs are compared to the zinc blende-type semiconductors GaSb, ZnTe, GaAs, and ZnSe, as well as the more ionic, hypothetical, II-V systems MgSb and MgAs. We establish a clearly covalent bonding scenario for ZnSb and ZnAs where multicenter bonded structural entities (rhomboid rings Zn2Sb2 and Zn2As2) are connected to each other by classical two-center, two-electron bonds. This bonding scenario is only compatible with a weak ionicity in II-V semiconductor systems, and weak ionicity appears as a necessary condition for the stability of the CdSb structure type. It is argued that a chemical bonding scenario with mixed multicenter and two-center bonding resembles that of boron and boron-rich compounds and is typical of electron-poor sp-bonded semiconductors with average valence electron concentrations below four per atom.

Quantum-chemical study of the effect of ligands on the structure and properties of gold clusters

NASA Astrophysics Data System (ADS)

Golosnaya, M. N.; Pichugina, D. A.; Oleinichenko, A. V.; Kuz'menko, N. E.

2017-02-01

The structures of [Au4(dpmp)2X2]2+clusters, where X =-C≡CH,-CH3,-SCH3,-F,-Cl,-Br,-I, dpmp is bis((diphenylphosphino)methyl)(phenyl)phosphine, are calculated at the level of density functional theory with the PBE functional and a modified Dirac-Coulomb-Breit Hamiltonian in an all-electron basis set (Λ). Using the example of [Au4(dpmp)2(C≡CC6H5)2]2+, the interatomic distances and bond angles calculated by means of PBE0/LANL2DZ, TPSS/LANL2DZ, TPSSh/LANL2DZ, and PBE/Λ are compared to X-ray crystallography data. It is shown that PBE/Λ yields the most accurate calculation of the geometrical parameters of this cluster. The ligand effect on the electronic stability of a cluster and the stability in reactions of decomposition into different fragments is studied, along with the capability of ligand exchange. Stability is predicted for [Au4(dpmp)2F2]2+ and [Au4(dpmp)2(SCH3)2]2+, while [Au4(dpmp)2I2]2+ cluster is unstable and its decomposes into two identical fragments is supposed.

Optimization of the structural characteristics of CaO and its effective stabilization yield high-capacity CO2 sorbents.

PubMed

Naeem, Muhammad Awais; Armutlulu, Andac; Imtiaz, Qasim; Donat, Felix; Schäublin, Robin; Kierzkowska, Agnieszka; Müller, Christoph R

2018-06-19

Calcium looping, a CO 2 capture technique, may offer a mid-term if not near-term solution to mitigate climate change, triggered by the yet increasing anthropogenic CO 2 emissions. A key requirement for the economic operation of calcium looping is the availability of highly effective CaO-based CO 2 sorbents. Here we report a facile synthesis route that yields hollow, MgO-stabilized, CaO microspheres featuring highly porous multishelled morphologies. As a thermal stabilizer, MgO minimized the sintering-induced decay of the sorbents' CO 2 capacity and ensured a stable CO 2 uptake over multiple operation cycles. Detailed electron microscopy-based analyses confirm a compositional homogeneity which is identified, together with the characteristics of its porous structure, as an essential feature to yield a high-performance sorbent. After 30 cycles of repeated CO 2 capture and sorbent regeneration, the best performing material requires as little as 11 wt.% MgO for structural stabilization and exceeds the CO 2 uptake of the limestone-derived reference material by ~500%.

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

PubMed Central

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; Wang, Shibing; Lin, Yu; Zeng, Qiaoshi; Xu, Gang; Liu, Zhenxian; Solanki, G. K.; Patel, K. D.; Cui, Yi; Hwang, Harold Y.; Mao, Wendy L.

2015-01-01

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe2 up to ∼60 GPa using multiple experimental techniques and ab-initio calculations. MoSe2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSe2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides. PMID:26088416

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

DOE PAGES

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; ...

2015-06-19

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe 2 up to ~60 GPa using multiple experimental techniques and ab-initio calculations. MoSe 2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS 2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSemore » 2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides.« less

Ordered structure of FeGe2 formed during solid-phase epitaxy

NASA Astrophysics Data System (ADS)

Jenichen, B.; Hanke, M.; Gaucher, S.; Trampert, A.; Herfort, J.; Kirmse, H.; Haas, B.; Willinger, E.; Huang, X.; Erwin, S. C.

2018-05-01

Fe3Si /Ge (Fe ,Si ) /Fe3Si thin-film stacks were grown by a combination of molecular beam epitaxy and solid-phase epitaxy (Ge on Fe3Si ). The stacks were analyzed using electron microscopy, electron diffraction, and synchrotron x-ray diffraction. The Ge(Fe,Si) films crystallize in the well-oriented, layered tetragonal structure FeGe2 with space group P 4 m m . This kind of structure does not exist as a bulk material and is stabilized by the solid-phase epitaxy of Ge on Fe3Si . We interpret this as an ordering phenomenon induced by minimization of the elastic energy of the epitaxial film.

Probing the Complexities of Structural Changes in Layered Oxide Cathode Materials for Li-Ion Batteries during Fast Charge-Discharge Cycling and Heating.

PubMed

Hu, Enyuan; Wang, Xuelong; Yu, Xiqian; Yang, Xiao-Qing

2018-02-20

The rechargeable lithium-ion battery (LIB) is the most promising energy storage system to power electric vehicles with high energy density and long cycling life. However, in order to meet customers' demands for fast charging, the power performances of current LIBs need to be improved. From the cathode aspect, layer-structured cathode materials are widely used in today's market and will continue to play important roles in the near future. The high rate capability of layered cathode materials during charging and discharging is critical to the power performance of the whole cell and the thermal stability is closely related to the safety issues. Therefore, the in-depth understanding of structural changes of layered cathode materials during high rate charging/discharging and the thermal stability during heating are essential in developing new materials and improving current materials. Since structural changes take place from the atomic level to the whole electrode level, combination of characterization techniques covering multilength scales is quite important. In many cases, this means using comprehensive tools involving diffraction, spectroscopy, and imaging to differentiate the surface from the bulk and to obtain structural/chemical information with different levels of spatial resolution. For example, hard X-ray spectroscopy can yield the bulk information and soft X-ray spectroscopy can give the surface information; X-ray based imaging techniques can obtain spatial resolution of tens of nanometers, and electron-based microcopy can go to angstroms. In addition to challenges associated with different spatial resolution, the dynamic nature of structural changes during high rate cycling and heating requires characterization tools to have the capability of collecting high quality data in a time-resolved fashion. Thanks to the advancement in synchrotron based techniques and high-resolution electron microscopy, high temporal and spatial resolutions can now be achieved. In this Account, we focus on the recent works studying kinetic and thermal properties of layer-structured cathode materials, especially the structural changes during high rate cycling and the thermal stability during heating. Advanced characterization techniques relating to the rate capability and thermal stability will be introduced. The different structure evolution behavior of cathode materials cycled at high rate will be compared with that cycled at low rate. Different response of individual transition metals and the inhomogeneity in chemical distribution will be discussed. For the thermal stability, the relationship between structural changes and oxygen release will be emphatically pointed out. In all these studies being reviewed, advanced characterization techniques are critically applied to reveal complexities at multiscale in layer-structured cathode materials.

What Hinders Electron Transfer Dissociation (ETD) of DNA Cations?

NASA Astrophysics Data System (ADS)

Hari, Yvonne; Leumann, Christian J.; Schürch, Stefan

2017-12-01

Radical activation methods, such as electron transfer dissociation (ETD), produce structural information complementary to collision-induced dissociation. Herein, electron transfer dissociation of 3-fold protonated DNA hexamers was studied to gain insight into the fragmentation mechanism. The fragmentation patterns of a large set of DNA hexamers confirm cytosine as the primary target of electron transfer. The reported data reveal backbone cleavage by internal electron transfer from the nucleobase to the phosphate linker leading either to a•/ w or d/ z• ion pairs. This reaction pathway contrasts with previous findings on the dissociation processes after electron capture by DNA cations, suggesting multiple, parallel dissociation channels. However, all these channels merely result in partial fragmentation of the precursor ion because the charge-reduced DNA radical cations are quite stable. Two hypotheses are put forward to explain the low dissociation yield of DNA radical cations: it is either attributed to non-covalent interactions between complementary fragments or to the stabilization of the unpaired electron in stacked nucleobases. MS3 experiments suggest that the charge-reduced species is the intact oligonucleotide. Moreover, introducing abasic sites significantly increases the dissociation yield of DNA cations. Consequently, the stabilization of the unpaired electron by π-π-stacking provides an appropriate rationale for the high intensity of DNA radical cations after electron transfer. [Figure not available: see fulltext.

The effect of the antioxidant on the properties of thiolated poly(aspartic acid) polymers in aqueous ocular formulations.

PubMed

Budai-Szűcs, Mária; Horvát, Gabriella; Gyarmati, Benjámin; Szilágyi, Barnabás Áron; Szilágyi, András; Berkó, Szilvia; Ambrus, Rita; Szabó-Révész, Piroska; Sandri, Giuseppina; Bonferoni, Maria Cristina; Caramella, Carla; Csányi, Erzsébet

2017-04-01

Thiolated polymers are a promising new group of excipients, but their stability against atmospheric oxidation has not been investigated in detail, and only a few efforts have been made to improve their stability. The oxidation of the thiol groups in solutions of thiolated polymers may result in a decrease of mucoadhesion and unpredictable in situ gelation. The aims of our work were to study the stability of aqueous solutions of thiolated polymers and the effects of stabilizing agents. We investigated thiolated poly(aspartic acid) polymers stabilized with dithiothreitol, glutathione or acetylcysteine. The effects of these antioxidants on the gel structure, mucoadhesion and drug release were determined by means of scanning electron microscopy, swelling, rheology, adhesion and drug release tests. It was concluded that the stability of polymer solutions containing antioxidants is sufficient for one day. Polymers stabilized with dithiotreitol demonstrated fast swelling and drug release, but weaker mucoadhesion as compared with the other samples. Polymers stabilized with glutathione displayed the weakest cohesive properties, resulting in fast and uncontrolled drug release and moderate mucoadhesion. Acetylcysteine-stabilized polymers exhibited an optimum cross-linked structure, with free thiol groups ensuring polymer-mucin interactions, resulting in the best mucoadhesive properties. Copyright © 2017 Elsevier B.V. All rights reserved.

X-ray source assembly having enhanced output stability, and fluid stream analysis applications thereof

DOEpatents

Radley, Ian; Bievenue, Thomas J.; Burdett Jr., John H.; Gallagher, Brian W.; Shakshober, Stuart M.; Chen, Zewu; Moore, Michael D.

2007-04-24

An x-ray source assembly (2700) and method of operation are provided having enhanced output stability. The assembly includes an anode (2125) having a source spot upon which electrons (2120) impinge and a control system (2715/2720) for controlling position of the anode source spot relative to an output structure. The control system can maintain the anode source spot location relative to the output structure (2710) notwithstanding a change in one or more operating conditions of the x-ray source assembly. One aspect of the disclosed invention is most amenable to the analysis of sulfur in petroleum-based fuels.

Different electronic and charge-transport properties of four organic semiconductors Tetraazaperopyrenes derivatives

NASA Astrophysics Data System (ADS)

Shi, Yarui; Wei, Huiling; Liu, Yufang

2015-03-01

Tetraazaperopyrenes (TAPPs) derivatives are high-performance n-type organic semiconductor material families with the remarkable long-term stabilities. The charge carrier mobilities in TAPPs derivatives crystals were calculated by the density functional theory (DFT) method combined with the Marcus-Hush electron-transfer theory. The existence of considerable C-H…F-C bonding defines the conformation of the molecular structure and contributes to its stability. We illustrated how it is possible to control the electronic and charge-transport parameters of TAPPs derivatives as a function of the positions, a type of the substituents. It is found that the core substitution of TAPPs has a drastic influence on the charge-transport mobilities. The maximum electron mobility value of the core-brominated 2,9-bis (perfluoroalkyl)-substituted TAPPs is 0.521 cm2 V-1 s-1, which appear in the orientation angle 95° and 275°. The results demonstrate that the TAPPs with bromine substituents in ortho positions exhibit the best charge-transfer efficiency among the four different TAPP derivatives.

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

Njema, H.; Debbichi, M., E-mail: mourad_fsm@yahoo.fr; Boughzala, K.

Highlights: • The structural and electronic properties of apatites with the general formula Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6−x}(SiO{sub 4}){sub x}F{sub 2} (0 ≤ x ≤ 6) have been investigated by means of the density functional theory. • The calculated enthalpy of formation of the compounds increased with the substitution degree. • The decrease in stability is probably due to the disorder induced in the Ca/LaO{sub 6}F polyhedron, following the substitution. - Abstract: The apatite-type compounds Ca{sub 10−x}La{sub x}(PO{sub 4}){sub 6−x}(SiO{sub 4}){sub x}F{sub 2} with 0 ≤ x ≤ 6 were prepared using a high temperature solid state reaction and weremore » characterized by X-ray diffraction. The crystal structure, chemical bonding, electronic structure and formation energy of all relaxed structures were analyzed by density functional theory (DFT). The calculated results show that the predicted geometry can well reproduce the structural parameters. The incorporation of La{sup 3+} into the fluorapatite (FA) structure induced especially at the level of the S(2) sites a certain disorder which is responsible for the weakening in the stability with x. Excellent agreement were obtained between the calculated and experimental results. Moreover, the band structure indicates that despite the reduction of the band gap with x content all materials remain insulating.« less

Stable monolayer honeycomb-like structures of RuX2 (X =S,Se)

NASA Astrophysics Data System (ADS)

Ersan, Fatih; Cahangirov, Seymur; Gökoǧlu, Gökhan; Rubio, Angel; Aktürk, Ethem

2016-10-01

Recent studies show that several metal oxides and dichalcogenides (M X2) , which exist in nature, can be stable in two-dimensional (2D) form and each year several new M X2 structures are explored. The unstable structures in H (hexagonal) or T (octahedral) forms can be stabilized through Peierls distortion. In this paper, we propose new 2D forms of RuS2 and RuSe2 materials. We investigate in detail the stability, electronic, magnetic, optical, and thermodynamic properties of 2D Ru X2 (X =S,Se) structures from first principles. While their H and T structures are unstable, the distorted T structures (T'-Ru X2) are stable and have a nonmagnetic semiconducting ground state. The molecular dynamic simulations also confirm that T'-Ru X2 systems are stable even at 500 K without any structural deformation. T'-RuS2 and T'-RuSe2 have indirect band gaps with 0.745 eV (1.694 eV with HSE) and 0.798 eV (1.675 eV with HSE) gap values, respectively. We also examine their bilayer and trilayer forms and find direct and smaller band gaps. We find that AA stacking is more favorable than the AB configuration. The new 2D materials obtained can be good candidates with striking properties for applications in semiconductor electronic, optoelectronic devices, and sensor technology.

Electronic structure of strongly reduced (1 ‾ 1 1) surface of monoclinic HfO2

NASA Astrophysics Data System (ADS)

Cheng, YingXing; Zhu, Linggang; Ying, Yile; Zhou, Jian; Sun, Zhimei

2018-07-01

Material surface is playing an increasingly important role in electronic devices as their size down to nanoscale. Here, by first-principles calculations we studied the surface oxygen-vacancies (Vos) induced electronic-structure variation of HfO2 , in order to explore its potential applications in surface-controlled electronic devices. Firstly, it is found that single Vo tends to segregate onto the surface and attracts each other as they form pairs, making the formation of vacancies-contained functional surface possible. Then extensive Vo-chains whose formation/rupture can represent the high/low conductivity state are constructed. The electronic states induced by the Vos remain localized in the band-gap region for most of the Vo-chains studied here. A transition to a metallic conductance is found in metastable Vo-chain with formation energy increased by 0.25 eV per Vo. Moreover, we highlight the significance of the Hubbard U correction for density functional theory when studying the electronic-structure based conductance in the oxides. By comprehensive calculations, we find a conductivity-stability dilemma of the Vo-chains, providing guideline for understanding and designing the electronic devices based on HfO2 surface.

High-rate and long-life lithium-ion battery performance of hierarchically hollow-structured NiCo 2O 4/CNT nanocomposite

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

Wang, Jie; Wu, Jianzhong; Wu, Zexing

In this paper, 3D-transition binary metal oxides have been considered as promising anode materials for lithium-ion batteries with improved reversible capacity, structural stability and electronic conductivity compared with single metal oxides. Here, carbon nanotube supported NiCo 2O 4 nanoparticles (NiCo 2O 4/CNT) with 3D hierarchical hollow structure are fabricated via a simple one-pot method. The NiCo 2O 4 nanoparticles with interconnected pores are consists of small nanocrystals. When used as anode material for the lithium-ion battery, NiCo 2O 4/CNT exhibits enhanced electrochemical performance than that of Co 3O 4/CNT and NiO/CNT. Moreover, ultra-high discharge/charge stability was obtained for 4000 cyclesmore » at a current density of 5 A g –1. The superior battery performance of NiCo 2O 4 nanoparticles is probably attributed to the special structural features and physical characteristics, including integrity, hollow structure with interconnected pores, which providing sufficient accommodation for the volume change during charge/discharge process. Besides, the consisting of ultra-small crystals enhanced the utility of active material, and intimate interaction with CNTs improved the electron-transfer rate.« less

High-rate and long-life lithium-ion battery performance of hierarchically hollow-structured NiCo 2O 4/CNT nanocomposite

DOE PAGES

Wang, Jie; Wu, Jianzhong; Wu, Zexing; ...

2017-05-17

In this paper, 3D-transition binary metal oxides have been considered as promising anode materials for lithium-ion batteries with improved reversible capacity, structural stability and electronic conductivity compared with single metal oxides. Here, carbon nanotube supported NiCo 2O 4 nanoparticles (NiCo 2O 4/CNT) with 3D hierarchical hollow structure are fabricated via a simple one-pot method. The NiCo 2O 4 nanoparticles with interconnected pores are consists of small nanocrystals. When used as anode material for the lithium-ion battery, NiCo 2O 4/CNT exhibits enhanced electrochemical performance than that of Co 3O 4/CNT and NiO/CNT. Moreover, ultra-high discharge/charge stability was obtained for 4000 cyclesmore » at a current density of 5 A g –1. The superior battery performance of NiCo 2O 4 nanoparticles is probably attributed to the special structural features and physical characteristics, including integrity, hollow structure with interconnected pores, which providing sufficient accommodation for the volume change during charge/discharge process. Besides, the consisting of ultra-small crystals enhanced the utility of active material, and intimate interaction with CNTs improved the electron-transfer rate.« less

Graphite carbon nitride/boron-doped graphene hybrid for efficient hydrogen generation reaction.

PubMed

Yang, Liang; Wang, Xin; Wang, Juan; Cui, Guomin; Liu, Daoping

2018-08-24

Metal-free carbon materials, with tuned surface chemical and electronic properties, hold great potential for the hydrogen evolution reaction (HER). We designed and synthesized a CN/BG hybrid electrocatalytic system with a porous and active graphite carbon nitride (CN) layer on boron-doped graphene (BG). A porous CN layer on graphene could provide exposed defects and edges that act as active sites for proton adsorption and reduction. The composition, structure, surface electronics, and chemical properties of this CN/BG hybrid system were tuned to obtain excellent HER activity and stability. Detailed surface chemical, morphological, and structural analyses demonstrated the synergetic effect arising from the electronic interaction between CN and BG, which contributed to the enhanced electrocatalytic performances.

Low-energy electron-induced dissociation in gas-phase nicotine, pyridine, and methyl-pyrrolidine

NASA Astrophysics Data System (ADS)

Ryszka, Michal; Alizadeh, Elahe; Li, Zhou; Ptasińska, Sylwia

2017-09-01

Dissociative electron attachment to nicotine, pyridine, and N-methyl-pyrrolidine was studied in the gas phase in order to assess their stability with respect to low-energy electron interactions. Anion yield curves for different products at electron energies ranging from zero to 15 eV were measured, and the molecular fragmentation pathways were proposed. Nicotine does not form a stable parent anion or a dehydrogenated anion, contrary to other biological systems. However, we have observed complex dissociation pathways involving fragmentation at the pyrrolidine side accompanied by isomerization mechanisms. Combining structure optimization and enthalpy calculations, performed with the Gaussian09 package, with the comparison with a deuterium-labeled N-methyl-d3-pyrrolidine allowed for the determination of the fragmentation pathways. In contrast to nicotine and N-methylpyrrolidine, the dominant pathway in dissociative electron attachment to pyridine is the loss of hydrogen, leading to the formation of an [M—H]- anion. The presented results provide important new information about the stability of nicotine and its constituent parts and contribute to a better understanding of the fragmentation mechanisms and their effects on the biological environment.

A Density Functional Theory Study of New Boron Nanotubes

NASA Astrophysics Data System (ADS)

Chen, Zhao-Hua; Xie, Zun

2017-11-01

Using first-principles calculations, a series of new boron nanotubes (BNTs), which show various electronic properties, were theoretically predicted. Stable nanotubes with various chiral vectors and diameters can be formed by rolling up the boron sheet with relative stability [H. Tang and S. I. Beigi, Phys. Rev. B 82, 115412 (2010).]. By increasing the diameter for BNT, the stability is enhanced. The calculated density of states and band structures demonstrate that all the predicted BNTs are metallic, regardless of their diameter and chirality. The multicentre chemical bonds of the relatively stable boron sheet and BNTs are analysed using the deformation electron density. Within our study, the BNTs all have metallic conductive characteristics, in addition to having a low effective quality and high carrier concentration, which are very good nanoconductive material properties and could be combined to form high-power electrodes for lithium-ion batteries such as those used in many modern electronics.

Gaining Control over Radiolytic Synthesis of Uniform Sub-3-nanometer Palladium Nanoparticles: Use of Aromatic Liquids in the Electron Microscope

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

Abellan Baeza, Patricia; Parent, Lucas R.; Al Hasan, Naila M.

2016-01-07

Synthesizing nanomaterials of uniform shape and size is of critical importance to access and manipulate the novel structure-property relationships arising at the nanoscale. In this work we synthesize Pd nanoparticles with well-controlled size using in situ liquid-stage scanning transmission electron microscopy (STEM) and demonstrate a match between the reaction kinetics and products of the radiolytic and chemical syntheses of size-stabilized Pd nanoparticles. We quantify the effect of electron dose on the nucleation kinetics, and compare these results with in situ small angle X-ray scattering (SAXS) experiments investigating the effect of temperature during chemical synthesis. This work introduces methods for precisemore » control of nanoparticle synthesis in the STEM and provides a means to uncover the fundamental processes behind the size and shape stabilization of nanoparticles.« less

Role of 5f electrons in the structural stability of light actinide (Th-U) mononitrides under pressure.

PubMed

Modak, P; Verma, Ashok K

2016-03-28

Pressure induced structural sequences and their mechanism for light actinide (Th-U) mononitrides were studied as a function of 5f-electron number using first-principles total energy and electronic structure calculations. Zero pressure lattice constants, bulk module and C11 elastic module vary systematically with 5f-electron number implying its direct role on crystal binding. There is a critical 5f-electron number below which the system makes B1-B2 and above it B1-R3̄m-B2 structural sequence under pressure. Also, the B1-B2 transition pressure increases with increasing 5f-electron number whereas an opposite trend is obtained for the B1-R3̄m transition pressure. The ascending of N p anti-bonding states through the Fermi level at high pressure is responsible for the structural instability of the system. Above the critical 5f-electron number in the system a narrow 5f-band occurs very close to the Fermi level which allows the system to lower its symmetry via band Jahn-Teller type lattice distortion and the system undergoes a B1-R3̄m phase transition. However, below the critical 5f-electron number this mechanism is not favorable due to a lack of sufficient 5f-state occupancy and thus the system undergoes a B1-B2 phase transition like other ionic solids.

Experimental observation of boron nitride chains.

PubMed

Cretu, Ovidiu; Komsa, Hannu-Pekka; Lehtinen, Ossi; Algara-Siller, Gerardo; Kaiser, Ute; Suenaga, Kazu; Krasheninnikov, Arkady V

2014-12-23

We report the formation and characterization of boron nitride atomic chains. The chains were made from hexagonal boron nitride sheets using the electron beam inside a transmission electron microscope. We find that the stability and lifetime of the chains are significantly improved when they are supported by another boron nitride layer. With the help of first-principles calculations, we prove the heteroatomic structure of the chains and determine their mechanical and electronic properties. Our study completes the analogy between various boron nitride and carbon polymorphs, in accordance with earlier theoretical predictions.

Ionic ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) stabilized by the covalent Si–N bonding: First-principles calculations

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

Zhang, Huijun; Ren, Jiadong, E-mail: jdren@ysu.edu.cn; Wu, Lailei

The structural, elastic and electronic properties of LiSi{sub 2}N{sub 3} and its substitutions by Na, K and Rb were investigated through first-principles computations. The expansion of lattice parameters of ASi{sub 2}N{sub 3} from Li, Na, K to Rb is found to be determined by the bond angle of Si–N1–Si, which suggests a possible way to improve the lithium ionic conductivity by substitutions. ASi{sub 2}N{sub 3} (A=Li, Na, K and Rb) shows the similar elastic behaviors, while the electronic band gap gradually decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. Interestingly, the analysis of electronicmore » structure, crystal orbital Hamiltonian populations and Bader charges shows that the covalence of Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3} phase. Among ASi{sub 2}N{sub 3} phases, there is a relatively high ionicity in NaSi{sub 2}N{sub 3}; the Si–N bond strength in [Si{sub 2}N{sub 3}]{sup −} net for KSi{sub 2}N{sub 3} and RbSi{sub 2}N{sub 3} is comparable to LiSi{sub 2}N{sub 3}, but stronger than NaSi{sub 2}N{sub 3}. - Graphic abstract: Universal trend of structural and electronic properties in alkaline metal silicon nitrides, ASi{sub 2}N{sub 3}, A=Li, Na, K and Rb. - Highlights: • Trend in structure, electronic and mechanical properties of ASi{sub 2}N{sub 3} (A=Li-Rb) were predicted. • Lattice expansion of ASi{sub 2}N{sub 3} induced by the bond angle of Si–N1–Si was found. • Calculated band gap decreases from 5.1 to 3.4 eV from LiSi{sub 2}N{sub 3} to RbSi{sub 2}N{sub 3}. • Covalent Si–N bonding is critical for the stability of ASi{sub 2}N{sub 3}.« less

Structural distortions in monolayers of binary semiconductors

NASA Astrophysics Data System (ADS)

Kumari, Poonam; Debnath, Saikat; Mahadevan, Priya

2018-01-01

We examine the structural properties of free-standing II-VI and III-V semiconductors at the monolayer limit within first principle density functional theory calculations. A nonpolar buckled structure was found to be favored over a polar buckled structure. While an obvious reason for this may be traced to the contribution from dipole-dipole interactions present in the polar structure which would destabilize it with respect to the nonpolar structure, Coulomb interactions between electrons on the cations and anions are found to be the reason for the nonpolar structure to be favoured. A route to tune the Coulomb interaction between the electrons on the cations and anions is through biaxial tensile strain. This allows for a planar graphitic phase in CdS to be stabilized at just 2% tensile strain. Strain also shifts the valence band maximum from the Γ point to the K point, opening up opportunities for exploring spin-valley physics in these materials.

Harnessing redox activity for the formation of uranium tris(imido) compounds

NASA Astrophysics Data System (ADS)

Anderson, Nickolas H.; Odoh, Samuel O.; Yao, Yiyi; Williams, Ursula J.; Schaefer, Brian A.; Kiernicki, John J.; Lewis, Andrew J.; Goshert, Mitchell D.; Fanwick, Phillip E.; Schelter, Eric J.; Walensky, Justin R.; Gagliardi, Laura; Bart, Suzanne C.

2014-10-01

Classically, late transition-metal organometallic compounds promote multielectron processes solely through the change in oxidation state of the metal centre. In contrast, uranium typically undergoes single-electron chemistry. However, using redox-active ligands can engage multielectron reactivity at this metal in analogy to transition metals. Here we show that a redox-flexible pyridine(diimine) ligand can stabilize a series of highly reduced uranium coordination complexes by storing one, two or three electrons in the ligand. These species reduce organoazides easily to form uranium-nitrogen multiple bonds with the release of dinitrogen. The extent of ligand reduction dictates the formation of uranium mono-, bis- and tris(imido) products. Spectroscopic and structural characterization of these compounds supports the idea that electrons are stored in the ligand framework and used in subsequent reactivity. Computational analyses of the uranium imido products probed their molecular and electronic structures, which facilitated a comparison between the bonding in the tris(imido) structure and its tris(oxo) analogue.

Physics of Ultrathin Films and Heterostructures of Rare-Earth Nickelates

DOE PAGES

Middey, Srimanta; Chakhalian, J.; Mahadevan, P.; ...

2016-04-06

The electronic structure of transition metal oxides featuring correlated electrons can be rationalized within the Zaanen-Sawatzky-Allen framework. Following a brief description of the present paradigms of electronic behavior, we focus on the physics of rare-earth nickelates as an archetype of complexity emerging within the charge transfer regime. The intriguing prospect of realizing the physics of high- Tc cuprates through heterostructuring resulted in a massive endeavor to epitaxially stabilize these materials in ultrathin form. A plethora of new phenomena unfolded in such artificial structures due to the effect of epitaxial strain, quantum confinement, and interfacial charge transfer. Here we review themore » present status of artificial rare-earth nickelates in an effort to uncover the interconnection between the electronic and magnetic behavior and the underlying crystal structure. Here, we conclude by discussing future directions to disentangle the puzzle regarding the origin of the metal-insulator transition, the role of oxygen holes, and the true nature of the antiferromagnetic spin configuration in the ultrathin limit.« less

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

Middey, Srimanta; Chakhalian, J.; Mahadevan, P.

The electronic structure of transition metal oxides featuring correlated electrons can be rationalized within the Zaanen-Sawatzky-Allen framework. Following a brief description of the present paradigms of electronic behavior, we focus on the physics of rare-earth nickelates as an archetype of complexity emerging within the charge transfer regime. The intriguing prospect of realizing the physics of high- Tc cuprates through heterostructuring resulted in a massive endeavor to epitaxially stabilize these materials in ultrathin form. A plethora of new phenomena unfolded in such artificial structures due to the effect of epitaxial strain, quantum confinement, and interfacial charge transfer. Here we review themore » present status of artificial rare-earth nickelates in an effort to uncover the interconnection between the electronic and magnetic behavior and the underlying crystal structure. Here, we conclude by discussing future directions to disentangle the puzzle regarding the origin of the metal-insulator transition, the role of oxygen holes, and the true nature of the antiferromagnetic spin configuration in the ultrathin limit.« less

Dynamic instabilities in strongly correlated VSe2 monolayers and bilayers

NASA Astrophysics Data System (ADS)

Esters, Marco; Hennig, Richard G.; Johnson, David C.

2017-12-01

With the emergence of graphene and other two-dimensional (2D) materials, transition-metal dichalcogenides have been investigated intensely as potential 2D materials using experimental and theoretical methods. VSe2 is an especially interesting material since its bulk modification exhibits a charge-density wave (CDW), the CDW is retained even for few-layer nanosheets, and monolayers of VSe2 are predicted to be ferromagnetic. In this work, we show that electron correlation has a profound effect on the magnetic properties and dynamic stability of VSe2 monolayers and bilayers. Including a Hubbard-U term in the density-functional-theory calculations strongly affects the magnetocrystalline anisotropy in the 1 T -VSe2 structure while leaving the 2 H -polytype virtually unchanged. This demonstrates the importance of electronic correlations for the electrical and magnetic properties of 1 T -VSe2 . The Hubbard-U term changes the dynamic stability and the presence of imaginary modes of ferromagnetic 1 T -VSe2 while affecting only the amplitudes in the nonmagnetic phase. The Fermi surface of nonmagnetic 1 T -VSe2 allows for nesting along the CDW vector, but it plays no role in ferromagnetic 1 T -VSe2 . Following the eigenvectors of the soft modes in nonmagnetic 1 T -VSe2 monolayers yields a CDW structure with a 4 ×4 supercell and Peierls-type distortion in the atomic positions and electronic structure. The magnetic order indicates the potential for spin-density-wave structures.

Oxidation state and interfacial effects on oxygen vacancies in tantalum pentoxide

DOE PAGES

Bondi, Robert J.; Marinella, Matthew J.

2015-02-28

First-principles density-functional theory (DFT) calculations are used to study the atomistic structure, structural energetics, and electron density near the O monovacancy (V O n; n=0,1+,2+) in both bulk, amorphous tantalum pentoxide (a-Ta 2O 5) and also at vacuum and metallic Ta interfaces. We calculate multivariate vacancy formation energies to evaluate stability as a function of oxidation state, distance from interface plane, and Fermi energy. V O n of all oxidation states preferentially segregate at both Ta and vacuum interfaces, where the metallic interface exhibits global formation energy minima. In a-Ta 2O 5, V O 0 are characterized by structural contractionmore » and electron density localization, while V O 2+ promote structural expansion and are depleted of electron density. In contrast, interfacial V O 0 and V O 2+ show nearly indistinguishable ionic and electronic signatures indicative of a reduced V O center. Interfacial V O 2+ extract electron density from metallic Ta indicating V O 2+ is spontaneously reduced at the expense of the metal. This oxidation/reduction behavior suggests careful selection and processing of both oxide layer and metal electrodes for engineering memristor device operation.« less

Hybrid density functional study of structural, bonding, and electronic properties of the manganite series La1-xCaxMnO3 (x =0,1/4,1)

NASA Astrophysics Data System (ADS)

Korotana, R.; Mallia, G.; Gercsi, Z.; Liborio, L.; Harrison, N. M.

2014-05-01

Hybrid-exchange density functional theory calculations are carried out to determine the effects of A-site doping on the electronic and magnetic properties of the manganite series La1-xCaxMnO3. This study focuses on the ground state of an ordered Ca occupancy in a periodic structure. It is shown that the hybrid-exchange functional, Becke three-parameter Lee-Yang-Parr (B3LYP), provides an accurate and consistent description of the electronic structure for LaMnO3, CaMnO3, and La0.75Ca0.25MnO3. We have quantified the relevant structural, magnetic, and electronic energy contributions to the stability of the doped compound. An insight into the exchange coupling mechanism for the low hole density region of the phase diagram, where a polaron (anti-Jahn-Teller) forms, is also provided. This study completes a microscopic description of the lightly doped insulator with an antiferromagnetic-to-ferromagnetic and metal-to-insulator transition.

Electrical, Chemical, And Microstructural Analysis of the Thermal Stability of Nickel-based Ohmic Contacts to Silicon Carbide for High-Temperature Electronics

NASA Astrophysics Data System (ADS)

Virshup, Ariel R.

With increasing attention on curbing the emission of pollutants into the atmosphere, chemical sensors that can be used to monitor and control these unwanted emissions are in great demand. Examples include monitoring of hydrocarbons from automobile engines and monitoring of flue gases such as CO emitted from power plants. One of the critical limitations in high-temperature SiC gas sensors, however, is the degradation of the metal-SiC contacts over time. In this dissertation, we investigated the high-temperature stability of Pt/TaSix/Ni/SiC ohmic contacts, which have been implemented in SiC-based gas sensors developed for applications in diesel engines and power plants. The high-temperature stability of a Pt/TaSi2/Ni/SiC ohmic contact metallization scheme was characterized using a combination of current-voltage measurements, Auger electron spectroscopy, secondary ion mass spectrometry, and transmission electron microscope imaging and associated analytical techniques. Increasing the thicknesses of the Pt and TaSi2 layers promoted electrical stability of the contacts, which remained ohmic at 600°C in air for over 300 h; the specific contact resistance showed only a gradual increase from an initial value of 5.2 x 10-5 O-cm 2. We observed a continuous silicon-oxide layer in the thinner contact structures, which failed after 36 h of heating. It was found that the interface between TaSix and NiySi was weakened by the accumulation of free carbon (produced by the reaction of Ni and SiC), which in turn facilitated oxygen diffusion from the contact edges. Additional oxygen diffusion occurred along grain boundaries in the Pt overlayer. Meanwhile, thicker contacts, with less interfacial free carbon and enhanced electrical stability contained a much lower oxygen concentration that was distributed across the contact layers, precluding the formation of an electrically insulating contact structure.

Theoretical Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2012-10-10

We use density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5- 1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, nonhollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity towards the oxygen reduction reaction of platinum nanowires was addressed by studying the change in the chemisorption energies of oxygen and hydroxyl groups, inducedmore » by inserting the inner chain of platinum atoms into the hollow nanotubes. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Nanotubes with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Density Functional Study of the Structure, Stability and Oxygen Reduction Activity of Ultrathin Platinum Nanowires

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

Matanovic, Ivana; Kent, Paul; Garzon, Fernando

2013-03-14

We used density functional theory to study the difference in the structure, stability and catalytic reactivity between ultrathin, 0.5–1.0 nm diameter, platinum nanotubes and nanowires. Model nanowires were formed by inserting an inner chain of platinum atoms in small diameter nanotubes. In this way more stable, non-hollow structures were formed. The difference in the electronic structure of platinum nanotubes and nanowires was examined by inspecting the density of surface states and band structure. Furthermore, reactivity toward the oxygen reduction reaction of platinum nanowires was assessed by studying the change in the chemisorption energies of oxygen, hydroxyl, and hydroperoxyl groups, inducedmore » by converting the nanotube models to nanowires. Both ultrathin platinum nanotubes and nanowires show distinct properties compared to bulk platinum. Single-wall nanotubes and platinum nanowires with diameters larger than 1 nm show promise for use as oxygen reduction catalysts.« less

Singlet fission in linear chains of molecules

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

Ambrosio, Francesco, E-mail: F.Ambrosio@warwick.ac.uk, E-mail: A.Troisi@warwick.ac.uk; Troisi, Alessandro, E-mail: F.Ambrosio@warwick.ac.uk, E-mail: A.Troisi@warwick.ac.uk

2014-11-28

We develop a model configuration interaction Hamiltonian to study the electronic structure of a chain of molecules undergoing singlet fission. We first consider models for dimer and trimer and then we use a matrix partitioning technique to build models of arbitrary size able to describe the relevant electronic structure for singlet fission in linear aggregates. We find that the multi-excitonic state (ME) is stabilized at short inter-monomer distance and the extent of this stabilization depends upon the size of orbital coupling between neighboring monomers. We also find that the coupling between ME states located on different molecules is extremely smallmore » leading to bandwidths in the order of ∼10 meV. This observation suggests that multi-exciton states are extremely localized by electron-phonon coupling and that singlet fission involves the transition between a relatively delocalized Frenkel exciton and a strongly localized multi-exciton state. We adopt the methodology commonly used to study non-radiative transitions to describe the singlet fission dynamics in these aggregates and we discuss the limit of validity of the approach. The results indicate that the phenomenology of singlet fission in molecular crystals is different in many important ways from what is observed in isolated dimers.« less

Thermoelectric properties and thermal stability of Bi-doped PbTe single crystal

NASA Astrophysics Data System (ADS)

Chen, Zhong; Li, Decong; Deng, Shuping; Tang, Yu; Sun, Luqi; Liu, Wenting; Shen, Lanxian; Yang, Peizhi; Deng, Shukang

2018-06-01

In this study, n-type Bi-doped single-crystal PbTe thermoelectric materials were prepared by melting and slow cooling method according to the stoichiometric ratio of Pb:Bi:Te = 1-x:x:1 (x = 0, 0.1, 0.15, 0.2, 0.25). The X-ray diffraction patterns of Pb1-xBixTe samples show that all main diffraction peaks are well matched with the PbTe matrix, which has a face-centered cubic structure with the space group Fm 3 bar m . Electron probe microanalysis reveals that Pb content decreases gradually, and Te content remains invariant basically with the increase of Bi content, indicating that Bi atoms are more likely to replace Pb atoms. Thermal analysis shows that the prepared samples possess relatively high thermal stability. Simultaneously, transmission electron microscopy and selected area electron diffraction pattern indicate that the prepared samples have typical single-crystal structures with good mechanical properties. Moreover, the electrical conductivity of the prepared samples improved significantly compared with that of the pure sample, and the maximum ZT value of 0.84 was obtained at 600 K by the sample with x = 0.2.

The stability of DOTA-chelated radiopharmaceuticals within 225Ac decay pathway studied with density functional theory.

NASA Astrophysics Data System (ADS)

Karolak, Aleksandra; Khabibullin, Artem; Budzevich, Mikalai; Martinez, M.; Doliganski, Michael; McLaughlin, Mark; Woods, Lilia; Morse, David

Ligand structures encapsulating metal ions play a central role as contrast agents in Magnetic Resonance Imaging (MRI) or as agents delivering toxic cargo directly to tumor cells in targeted cancer therapy. The structural stability and interaction with solutions of such complexes are the key elements in understanding the foundation of delivery process. We present a comparative study for the 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) chelated to radioactive isotopes of 225Ac, 221Fr, 217At, 213Bi and a control 68Gd. Using density functional theory methods we investigate the structural stability of complexes for cancer therapy including binding energies, charge transfer, electron densities. The van der Waals interactions are included in the simulations to take into account weak dispersion forces present in such structures. Our results reveal that Ac-DOTA, Bi-DOTA and Gd-DOTA are the most stable complexes in the group. We also show that the water environment is a key ingredient for the structural coordination of the DOTA structures. Support from the US Department of Energy under Grant No. DE-FG02-06ER46297 is acknowledged.

Deciphering Stability of Five-Membered Heterocyclic Radicals: Balancing Act Between Delocalization and Ring Strain.

PubMed

Sah, Chitranjan; Yadav, Ajit Kumar; Venkataramani, Sugumar

2018-06-21

Computational studies on five-membered heterocycles with single heteroatom and their isomeric dehydro-borole 1a-1c, cyclopentadiene 2a-2c, pyrrole 3a-3c, furan 4b-4c, phosphole 5a-5c, and thiophene 6b-6c radicals have been carried out. Geometrical aspects through ground state electronic structures and stability aspects using bond dissociation energies (BDE) and radical stabilization energies (RSE) have been envisaged in this regard. Spin densities, electrostatic potentials (ESP), and natural bond orbital (NBO) analysis unveiled the extent of spin delocalization. The estimated nucleus-independent chemical shifts (NICS) values revealed the difference in aromaticity characteristics of radicals. Particularly the heteroatom centered radicals exhibit odd electron π-delocalized systems with a quasi-antiaromatic character. Various factors such as, the relative position of the radical center with respect to heteroatoms, resonance, ring strain and orbital interactions influence the stability that follows the order: heteroatom centered > β-centered > α-centered radicals. Among the influences of various factors, we confirmed the existence of a competition between delocalization and the ring strain, and the interplay of both decides the overall stability order.

Thermal stability of mullite RMn₂O₅ (R  =  Bi, Y, Pr, Sm or Gd): combined density functional theory and experimental study.

PubMed

Li, Chenzhe; Thampy, Sampreetha; Zheng, Yongping; Kweun, Joshua M; Ren, Yixin; Chan, Julia Y; Kim, Hanchul; Cho, Maenghyo; Kim, Yoon Young; Hsu, Julia W P; Cho, Kyeongjae

2016-03-31

Understanding and effectively predicting the thermal stability of ternary transition metal oxides with heavy elements using first principle simulations are vital for understanding performance of advanced materials. In this work, we have investigated the thermal stability of mullite RMn2O5 (R  =  Bi, Pr, Sm, or Gd) structures by constructing temperature phase diagrams using an efficient mixed generalized gradient approximation (GGA) and the GGA  +  U method. Simulation predicted stability regions without corrections on heavy elements show a 4-200 K underestimation compared to our experimental results. We have found the number of d/f electrons in the heavy elements shows a linear relationship with the prediction deviation. Further correction on the strongly correlated electrons in heavy elements could significantly reduce the prediction deviations. Our corrected simulation results demonstrate that further correction of R-site elements in RMn2O5 could effectively reduce the underestimation of the density functional theory-predicted decomposition temperature to within 30 K. Therefore, it could produce an accurate thermal stability prediction for complex ternary transition metal oxide compounds with heavy elements.

Enhanced ferroelectric properties and thermal stability of nonstoichiometric 0.92(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3 single crystals

NASA Astrophysics Data System (ADS)

Zhang, Haiwu; Chen, Chao; Zhao, Xiangyong; Deng, Hao; Li, Long; Lin, Di; Li, Xiaobing; Ren, Bo; Luo, Haosu; Yan, Jun

2013-11-01

Bi deficient, Mn doped 0.92(Na0.5Bi0.5)TiO3-0.08(K0.5Bi0.5)TiO3 single crystals were grown by carefully controlled top-seeded solution growth method. Local structures were investigated by transmission electron microscopy. The site occupation and valence state of manganese were characterized by electron paramagnetic resonance spectrum. The leakage current density in the as-grown single crystals is effectively depressed. The introduced defect complexes suppress the temperature induced phase transformation, increasing the depolarization temperature (165 °C) and thermal stability of ferroelectric properties.

Fabrication of a form- and size-variable microcellular-polymer-stabilized metal nanocomposite using supercritical foaming and impregnation for catalytic hydrogenation

PubMed Central

2012-01-01

This article presents the fabrication of size-controllable and shape-flexible microcellular high-density polyethylene-stabilized palladium nanoparticles (Pd/m-HDPE) using supercritical foaming, followed by supercritical impregnation. These nanomaterials are investigated for use as heterogeneous hydrogenation catalysts of biphenyls in supercritical carbon dioxide with no significant surface and inner mass transfer resistance. The morphology of the Pd/m-HDPE is examined using scanning electron microscopy images of the pores inside Pd/m-HDPE catalysts and transmission electron microscopy images of the Pd particles confined in an HDPE structure. This nanocomposite simplifies industrial design and operation. These Pd/m-HDPE catalysts can be recycled easily and reused without complex recovery and cleaning procedures. PMID:22651135

Electronic and magnetic properties of MoSe2 armchair nanoribbons controlled by the different edge structures

NASA Astrophysics Data System (ADS)

Zhang, Hui; Zhao, Xu; Gao, Yonghui; Wang, Haiyang; Wang, Tianxing; Wei, Shuyi

2018-03-01

Tow-dimensional materials obviously have potential applications in next-generation nanodevices because of their extraordinary physical and chemical properties and the demands of the market. Using first-principle calculation based on density functional theory, we explore electronic and magnetic properties of the different nanoribbons with various edge structures, namely, with hydrogenation or not. In addition, we also calculate the binding energy to analyze the stability of the nanoribbon. Our calculations tell us that the passivated nanoribbons have the positive binding energies, which indicates the passivated nanoribbons are relative stable and hydrogenation can improve the stability of the bare nanoribbons due to the reduction of the dangling bonds. Among of them, full hydrogenation has the highest stability. We find all the nanoribbons with full and without hydrogenation are nonmagnetic semiconductors. It is worth mentioning that hydrogenation can induce the bare nanoribbons to transform gradually from indirect band gap semiconductor to direct band gap semiconductor, even to half-metal. In addition, the magnetic moment of the bare nanoribbon change bit by bit as the rate of hydrogenation increases. When the edge atoms are fully hydrogenated, the magnetic moment return to zero. What's more, our research results still confirm that electronic and magnetic properties of the nanorribons without and with different edge passivation are mainly contributed by the atoms at the edges. These studies about MoSe2 nanoribbons will shed light on the further development of the relevant nanodevices in versatile applications, such as spintronics and energy harvesting.

A comparative study of the effect of α-, β-, and γ-cyclodextrins as stabilizing agents in the synthesis of silver nanoparticles using a green chemistry method.

PubMed

Suárez-Cerda, Javier; Nuñez, Gabriel Alonso; Espinoza-Gómez, Heriberto; Flores-López, Lucía Z

2014-10-01

This paper describes the effect of different types of cyclodextrins (CDs) in the synthesis of silver nanoparticles (Ag-NPs), using an easy green chemistry method. The Ag-NPs were obtained using an aqueous silver nitrate solution (AgNO3) with α-, β-, or γ-CDs (aqueous solutions) as stabilizing agents, employing the chemical reduction method with citric acid as a reducing agent. A comparative study was done to determine which cyclodextrin (CD) was the best stabilizing agent, and we found out that β-CD was the best due to the number of glucopyranose units in its structure. The formation of the Ag-NPs was demonstrated by analysis of UV-vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and transmission electron microscopy (TEM). SEM-EDS showed the formation of a cluster with a significant amount of silver, for β-CD-Ag-NPs, spherical agglomerates can be observed. However, for α-, γ-CD, the agglomerates do not have a specific form, but their appearance is porous. TEM analysis shows spherical nanoparticles in shape and size between ~0.5 to 7 nm. The clear lattice fringes in TEM images and the typical selected area electron diffraction (SAED) pattern, showed that the Ag-NPs obtained were highly crystalline with a face cubic center structure (FCC). Copyright © 2014 Elsevier B.V. All rights reserved.

Computational evidence for stable inorganic fullerene-like structures of ceramic and semiconductor materials

NASA Astrophysics Data System (ADS)

Chang, Ch; Patzer, A. B. C.; Sedlmayr, E.; Steinke, T.; Sülzle, D.

2001-12-01

Theoretical electronic structure techniques have become an indispensible and powerful means for predicting molecular properties and designing new materials. Based on a density functional approach and guided by geometric considerations we provide evidence for some specific inorganic fullerene-like cage molecules of ceramic and semiconductor materials which exhibit high energetic stability and point group symmetry as well as nearly perfect spherical shape.

Phase-field model of insulator-to-metal transition in VO2 under an electric field

NASA Astrophysics Data System (ADS)

Shi, Yin; Chen, Long-Qing

2018-05-01

The roles of an electric field and electronic doping in insulator-to-metal transitions are still not well understood. Here we formulated a phase-field model of insulator-to-metal transitions by taking into account both structural and electronic instabilities as well as free electrons and holes in VO2, a strongly correlated transition-metal oxide. Our phase-field simulations demonstrate that in a VO2 slab under a uniform electric field, an abrupt universal resistive transition occurs inside the supercooling region, in sharp contrast to the conventional Landau-Zener smooth electric breakdown. We also show that hole doping may decouple the structural and electronic phase transitions in VO2, leading to a metastable metallic monoclinic phase which could be stabilized through a geometrical confinement and the size effect. This work provides a general mesoscale thermodynamic framework for understanding the influences of electric field, electronic doping, and stress and strain on insulator-to-metal transitions and the corresponding mesoscale domain structure evolution in VO2 and related strongly correlated systems.

Elucidating nitric oxide synthase domain interactions by molecular dynamics.

PubMed

Hollingsworth, Scott A; Holden, Jeffrey K; Li, Huiying; Poulos, Thomas L

2016-02-01

Nitric oxide synthase (NOS) is a multidomain enzyme that catalyzes the production of nitric oxide (NO) by oxidizing L-Arg to NO and L-citrulline. NO production requires multiple interdomain electron transfer steps between the flavin mononucleotide (FMN) and heme domain. Specifically, NADPH-derived electrons are transferred to the heme-containing oxygenase domain via the flavin adenine dinucleotide (FAD) and FMN containing reductase domains. While crystal structures are available for both the reductase and oxygenase domains of NOS, to date there is no atomic level structural information on domain interactions required for the final FMN-to-heme electron transfer step. Here, we evaluate a model of this final electron transfer step for the heme-FMN-calmodulin NOS complex based on the recent biophysical studies using a 105-ns molecular dynamics trajectory. The resulting equilibrated complex structure is very stable and provides a detailed prediction of interdomain contacts required for stabilizing the NOS output state. The resulting equilibrated complex model agrees well with previous experimental work and provides a detailed working model of the final NOS electron transfer step required for NO biosynthesis. © 2015 The Protein Society.

Rechargeable magnesium-ion battery based on a TiSe2-cathode with d-p orbital hybridized electronic structure

PubMed Central

Gu, Yunpeng; Katsura, Yukari; Yoshino, Takafumi; Takagi, Hidenori; Taniguchi, Kouji

2015-01-01

Rechargeable ion-batteries, in which ions such as Li+ carry charges between electrodes, have been contributing to the improvement of power-source performance in a wide variety of mobile electronic devices. Among them, Mg-ion batteries are recently attracting attention due to possible low cost and safety, which are realized by abundant natural resources and stability of Mg in the atmosphere. However, only a few materials have been known to work as rechargeable cathodes for Mg-ion batteries, owing to strong electrostatic interaction between Mg2+ and the host lattice. Here we demonstrate rechargeable performance of Mg-ion batteries at ambient temperature by selecting TiSe2 as a model cathode by focusing on electronic structure. Charge delocalization of electrons in a metal-ligand unit through d-p orbital hybridization is suggested as a possible key factor to realize reversible intercalation of Mg2+ into TiSe2. The viewpoint from the electronic structure proposed in this study might pave a new way to design electrode materials for multivalent-ion batteries. PMID:26228263

Stability and electronic structure of the low- Σ grain boundaries in CdTe: a density functional study

DOE PAGES

Park, Ji-Sang; Kang, Joongoo; Yang, Ji-Hui; ...

2015-01-15

Using first-principles density functional calculations, we investigate the relative stability and electronic structure of the grain boundaries (GBs) in zinc-blende CdTe. Among the low-Σ-value symmetric tilt Σ3 (111), Σ3 (112), Σ5 (120), and Σ5 (130) GBs, we show that the Σ3 (111)GB is always the most stable due to the absence of dangling bonds and wrong bonds. The Σ5 (120) GBs, however, are shown to be more stable than the Σ3 (112) GBs, even though the former has a higher Σ value, and the latter is often used as a model system to study GB effects in zinc-blende semiconductors. Furthermore,more » we find that although containing wrong bonds, the Σ5 (120) GBs are electrically benign due to the short wrong bond lengths, and thus are not as harmful as the Σ3 (112) GBs also having wrong bonds but with longer bond lengths.« less

Mechanical stability of heat-treated nanoporous anodic alumina subjected to repetitive mechanical deformation

NASA Astrophysics Data System (ADS)

Bankova, A.; Videkov, V.; Tzaneva, B.; Mitov, M.

2018-03-01

We report studies on the mechanical response and deformation behavior of heat-treated nanoporous anodic alumina using a micro-balance test and experimental test equipment especially designed for this purpose. AAO samples were characterized mechanically by a three-point bending test using a micro-analytical balance. The deformation behavior was studied by repetitive mechanical bending of the AAO membranes using an electronically controlled system. The nanoporous AAO structures were prepared electrochemically from Al sheet substrates using a two-step anodizing technique in oxalic acid followed by heat treatment at 700 °C in air. The morphological study of the aluminum oxide layer after the mechanical tests and mechanical deformation was conducted using scanning electron and optical microscopy, respectively. The experimental results showed that the techniques proposed are simple and accurate; they could, therefore, be combined to constitute a method for mechanical stability assessment of nanostructured AAO films, which are important structural components in the design of MEMS devices and sensors.

Folding of a helix is critically stabilized by polarization of backbone hydrogen bonds: study in explicit water.

PubMed

Duan, Li L; Gao, Ya; Mei, Ye; Zhang, Qing G; Tang, Bo; Zhang, John Z H

2012-03-15

Multiple single-trajectory molecular dynamics (MD) simulation at room temperature (300 K) in explicit water was carried out to study the folding dynamics of an α-helix (PDB 2I9M ) using a polarized charge scheme that includes electronic polarization of backbone hydrogen bonds. Starting from an extended conformation, the 17-residue peptide was successfully folded into the native structure (α-helix) between 80 and 130 ns with a root-mean-square deviation of ~1.0 Å. Analysis of the time-dependent trajectories revealed that helix formation of the peptide started at the terminals and progressed toward the center of the peptide. For comparison, MD trajectories generated under various versions of standard AMBER force fields failed to show any significant or stable helix formation in our simulation. Our result shows clear evidence that the electronic polarization of backbone hydrogen bonds energetically stabilizes the helix formation and is critical to the stable folding of the short helix structure. © 2012 American Chemical Society

Quantum Chemical Study of Water Adsorption on the Surfaces of SrTiO3 Nanotubes.

PubMed

Bandura, Andrei V; Kuruch, Dmitry D; Evarestov, Robert A

2015-07-20

We have studied the adsorption of water molecules on the inner and outer surfaces of nanotubes generated by rolling (001) layers of SrTiO3 cubic crystals. The stability and the atomic and electronic structures of the adsorbed layers are determined by using hybrid density functional theory. The absorption energy and the preferred adsorbate structure are essentially governed by the nature of the surface of the nanotube. Dissociative adsorption prevails on the outer nanotube surfaces. The stability of the adsorbed layers on the inner surfaces is related to the possibility of the formation of hydrogen bonds between water molecules and surface oxygen atoms, and depends on the surface curvature. The presence of water molecules on the inner surface of the nanotubes leads to an increase of the electronic band gap. Externally TiO2 -terminated nanotubes could be used for the photocatalytic decomposition of water by ultraviolet radiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Stability of rhombohedral phases in vanadium at high-pressure and high-temperature: first-principles investigations

PubMed Central

Wang, Yi X.; Wu, Q.; Chen, Xiang R.; Geng, Hua Y.

2016-01-01

The pressure-induced transition of vanadium from BCC to rhombohedral structures is unique and intriguing among transition metals. In this work, the stability of these phases is revisited by using density functional theory. At finite temperatures, a novel transition of rhombohedral phases back to BCC phase induced by thermal electrons is discovered. This reentrant transition is found not driven by phonons, instead it is the electronic entropy that stabilizes the latter phase, which is totally out of expectation. Parallel to this transition, we find a peculiar and strong increase of the shear modulus C44 with increasing temperature. It is counter-intuitive in the sense that it suggests an unusual harding mechanism of vanadium by temperature. With these stability analyses, the high-pressure and finite-temperature phase diagram of vanadium is proposed. Furthermore, the dependence of the stability of RH phases on the Fermi energy and chemical environment is investigated. The results demonstrate that the position of the Fermi level has a significant impact on the phase stability, and follows the band-filling argument. Besides the Fermi surface nesting, we find that the localization/delocalization of the d orbitals also contributes to the instability of rhombohedral distortions in vanadium. PMID:27581551

Experimental and Theoretical Investigations on d and f Electron Systems under High Pressure

NASA Astrophysics Data System (ADS)

Gupta, Satish C.; Joshi, K. D.; Banerjee, S.

2008-07-01

The pressure-induced electron transfer from sp to d band in transition elements, and spd to f band in the light actinides significantly influences the stability of crystal structures in these metals. Although α → ω → β phase transition with increasing pressure in group IV transition elements is well documented, the β → ω transition under pressure has not been reported until recently. Our experimental study on the β-stabilized Zr-20Nb alloy reveals that it transforms to ω phase on shock compression, whereas this transition is not seen in a hydrostatic pressure condition. The platelike morphology of ω formed under shock compression is in contrast to the fine particle morphology seen in this system under thermal treatment, which clearly indicates that the mechanism of the β → ω transformation under shock treatment involves a large shear component. In this article, we have analyzed why the ω → β transition pressures in Ti, Zr, and Hf do not follow the trend implied by the principle of corresponding states. Our analysis shows that the ω → β transition depends on how the increased d population caused by the sp → d transfer of electron is distributed among various d substates. In Th, we have analyzed the role of 5f electrons in determining the mechanical stability of fcc and bct structures under hydrostatic compressions. Our analysis shows that the fcc to bct transition in this metal, which has been reported by high-pressure experiments, occurs because of softening of the tetragonal shear modulus C' = ( C 11 - C 12)/2 under compression. From the total energy calculated as a function of specific volume, we have determined the 0 K isotherm, which is then used to deduce the shock Hugoniot. The theoretical Hugoniot compares well with the experimental data.

Spider-web inspired multi-resolution graphene tactile sensor.

PubMed

Liu, Lu; Huang, Yu; Li, Fengyu; Ma, Ying; Li, Wenbo; Su, Meng; Qian, Xin; Ren, Wanjie; Tang, Kanglai; Song, Yanlin

2018-05-08

Multi-dimensional accurate response and smooth signal transmission are critical challenges in the advancement of multi-resolution recognition and complex environment analysis. Inspired by the structure-activity relationship between discrepant microstructures of the spiral and radial threads in a spider web, we designed and printed graphene with porous and densely-packed microstructures to integrate into a multi-resolution graphene tactile sensor. The three-dimensional (3D) porous graphene structure performs multi-dimensional deformation responses. The laminar densely-packed graphene structure contributes excellent conductivity with flexible stability. The spider-web inspired printed pattern inherits orientational and locational kinesis tracking. The multi-structure construction with homo-graphene material can integrate discrepant electronic properties with remarkable flexibility, which will attract enormous attention for electronic skin, wearable devices and human-machine interactions.

Influence of valence electron concentration on Laves phases: Structures and phase stability of pseudo-binary MgZn 2-xPd x

DOE PAGES

Thimmaiah, Srinivasa; Miller, Gordon J.

2015-06-03

A series of pseudo-binary compounds MgZn 2-xPd x (0.15 ≤ x ≤ 1.0) were synthesized and structurally characterized to understand the role of valence electron concentration (vec) on the prototype Laves phase MgZn 2 with Pd-substitution. Three distinctive phase regions were observed with respect to Pd content, all exhibiting fundamental Laves phase structures: 0.1 ≤ x ≤ 0.3 (MgNi 2-type, hP24; MgZn 1.80Pd 0.20(2)), 0.4 ≤ x ≤ 0.6 (MgCu 2-type, cF24; MgZn 1.59Pd 0.41(2)), and 0.62 ≤ x ≤ 0.8 (MgZn 2-type, hP12: MgZn 1.37Pd 0.63(2)). Refinements from single-crystal X-ray diffraction indicated nearly statistical distributions of Pd and Znmore » atoms among the majority atom sites in these structures. Interestingly, the MgZn 2-type structure re-emerges in MgZn 2–xPd x at x ≈ 0.7 with the refined composition MgZn 1.37(2)Pd 0.63 and a c/a ratio of 1.59 compared to 1.64 for binary MgZn 2. Electronic structure calculations on a model “MgZn 1.25Pd 0.75” yielded a density of states (DOS) curve showing enhancement of a pseudogap at the Fermi level as a result of electronic stabilization due to the Pd addition. Moreover, integrated crystal orbital Hamilton population values show significant increases of orbital interactions for (Zn,Pd)–(Zn,Pd) atom pairs within the majority atom substructure, i.e., within the Kagomé nets as well as between a Kagomé net and an apical site, from binary MgZn 2 to the ternary “MgZn 1.25Pd 0.75”. Multi-centered bonding is evident from electron localization function plots for “MgZn 1.25Pd 0.75”, an outcome which is in accordance with analysis of other Laves phases.« less

Rational Design of ZnO:H/ZnO Bilayer Structure for High-Performance Thin-Film Transistors.

PubMed

Abliz, Ablat; Huang, Chun-Wei; Wang, Jingli; Xu, Lei; Liao, Lei; Xiao, Xiangheng; Wu, Wen-Wei; Fan, Zhiyong; Jiang, Changzhong; Li, Jinchai; Guo, Shishang; Liu, Chuansheng; Guo, Tailiang

2016-03-01

The intriguing properties of zinc oxide-based semiconductors are being extensively studied as they are attractive alternatives to current silicon-based semiconductors for applications in transparent and flexible electronics. Although they have promising properties, significant improvements on performance and electrical reliability of ZnO-based thin film transistors (TFTs) should be achieved before they can be applied widely in practical applications. This work demonstrates a rational and elegant design of TFT, composed of poly crystalline ZnO:H/ZnO bilayer structure without using other metal elements for doping. The field-effect mobility and gate bias stability of the bilayer structured devices have been improved. In this device structure, the hydrogenated ultrathin ZnO:H active layer (∼3 nm) could provide suitable carrier concentration and decrease the interface trap density, while thick pure-ZnO layer could control channel conductance. Based on this novel structure, a high field-effect mobility of 42.6 cm(2) V(-1) s(-1), a high on/off current ratio of 10(8) and a small subthreshold swing of 0.13 V dec(-1) have been achieved. Additionally, the bias stress stability of the bilayer structured devices is enhanced compared to the simple single channel layer ZnO device. These results suggest that the bilayer ZnO:H/ZnO TFTs have a great potential for low-cost thin-film electronics.

Geometric modeling of subcellular structures, organelles, and multiprotein complexes

PubMed Central

Feng, Xin; Xia, Kelin; Tong, Yiying; Wei, Guo-Wei

2013-01-01

SUMMARY Recently, the structure, function, stability, and dynamics of subcellular structures, organelles, and multi-protein complexes have emerged as a leading interest in structural biology. Geometric modeling not only provides visualizations of shapes for large biomolecular complexes but also fills the gap between structural information and theoretical modeling, and enables the understanding of function, stability, and dynamics. This paper introduces a suite of computational tools for volumetric data processing, information extraction, surface mesh rendering, geometric measurement, and curvature estimation of biomolecular complexes. Particular emphasis is given to the modeling of cryo-electron microscopy data. Lagrangian-triangle meshes are employed for the surface presentation. On the basis of this representation, algorithms are developed for surface area and surface-enclosed volume calculation, and curvature estimation. Methods for volumetric meshing have also been presented. Because the technological development in computer science and mathematics has led to multiple choices at each stage of the geometric modeling, we discuss the rationales in the design and selection of various algorithms. Analytical models are designed to test the computational accuracy and convergence of proposed algorithms. Finally, we select a set of six cryo-electron microscopy data representing typical subcellular complexes to demonstrate the efficacy of the proposed algorithms in handling biomolecular surfaces and explore their capability of geometric characterization of binding targets. This paper offers a comprehensive protocol for the geometric modeling of subcellular structures, organelles, and multiprotein complexes. PMID:23212797

Structure and mechanical properties of foils made of nanocrystalline beryllium

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

Zhigalina, O. M., E-mail: zhigal@ns.crys.ras.ru; Semenov, A. A.; Zabrodin, A. V.

2016-07-15

The phase composition and structural features of (45–90)-μm-thick foils obtained from nanocrystalline beryllium during multistep thermomechanical treatment have been established using electron microscopy, electron diffraction, electron backscattering diffraction, and energy-dispersive analysis. This treatment is shown to lead to the formation of a structure with micrometer- and submicrometer-sized grains. The minimum average size of beryllium grains is 352 nm. The inclusions of beryllium oxide (BeO) of different modifications with tetragonal (sp. gr. P4{sub 2}/mnm) and hexagonal (sp. gr. P6{sub 3}/mmc) lattices are partly ground during deformation to a size smaller than 100 nm and are located along beryllium grain boundaries inmore » their volume, significantly hindering migration during treatment. The revealed structural features of foils with submicrometer-sized crystallites provide the thermal stability of their structural state. Beryllium with this structure is a promising material for X-ray instrument engineering and for the production of ultrathin (less than 10 μm) vacuum-dense foils with very high physicomechanical characteristics.« less

First principles study on Fe based ferromagnetic quaternary Heusler alloys

NASA Astrophysics Data System (ADS)

Amudhavalli, A.; Rajeswarapalanichamy, R.; Iyakutti, K.

2017-11-01

The study of stable half-metallic ferromagnetic materials is important from various fundamental and application points of view in condensed matter Physics. Structural phase stability, electronic structure, mechanical and magnetic properties of Fe-based quaternary Heusler alloys XX‧YZ (X = Co, Ni; X‧ = Fe; Y = Ti; Z = Si, Ge, As) for three different phases namely α, β and γ phases of LiMgPdSn crystal structure have been studied by density functional theory with generalized gradient approximation formulated by Perdew, Burke and Ernzerhof (GGA-PBE) and the Hubbard formalism (GGA-PBE + U). This work aims to identify the ferromagnetic and half-metallic properties of XX‧YZ (X = Co, Ni, X‧ = Fe; Y = Ti; Z = Si, Ge, As) quaternary Heusler alloys. The predicted phase stability shows that α-phase is found to be the lowest energy phase at ambient pressure. A pressure-induced structural phase transition is observed in CoFeTiSi, CoFeTiGe, CoFeTiAs, NiFeTiSi, NiFeTiGe and NiFeTiAs at the pressures of 151.6 GPa, 33.7 GPa, 76.4 GPa, 85.3 GPa, 87.7 GPa and 96.5 GPa respectively. The electronic structure reveals that these materials are half metals at normal pressure whereas metals at high pressure. The investigation of electronic structure and magnetic properties are performed to reveal the underlying mechanism of half metallicity. The spin polarized calculations concede that these quaternary Heusler compounds may exhibit the potential candidate in spintronics application. The magnetic moments for these quaternary Heusler alloys in all the three different phases (α, β and γ) are estimated.

Stabilization of Si_60 Cage Structure: The Agony and the Ecstasy

NASA Astrophysics Data System (ADS)

Kawazoe, Y.; Sun, Q.; Wang, Q.; Rao, B. K.; Jena, P.

2003-03-01

The unique role of silicon in the micro-electronics industry has motivated many researchers to find ways to stabilize Si_60 with fullerene structure. In spite of numerous experimental attempts, synthesis of a theoretically predicted C_60-supported Si_60 cluster (C_60@Si_60) has not been possible. Using a state-of-the-art theoretical method, we provide the first answer for this long-standing contradiction between the experimental observation and the theoretical prediction. The flaws in earlier theoretical works are pointed out, and Si_60 is shown to be unstable in the fullerene structure either on its own or when supported on a C_60 fullerene (C_60@Si_60). On the other hand, we show that Si_60 cage can be stabilized by using magic clusters such as Al_12X (X = Si, Ge, Sn, Pb) as endohedral units, which have been identified in recent experiment as stable clusters and as suitable building blocks for cluster-assembled materials.

Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

DOE PAGES

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; ...

2017-07-28

While olivine LiFePO 4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li + migration pathways in the framework, replacing the [PO 4] 3- polyanion with a silicate [SO 4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO 4 and LiScSiO 4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc sitemore » were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo 2-x-ySiO 4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.« less

Conformational and NBO studies of serotonin as a radical scavenger. Changes induced by the OH group.

PubMed

Lobayan, Rosana M; Schmit, María Celia Pérez

2018-03-01

Serotonin (5-hydroxytryptamine, SER) is a neurotransmitter that affects many different processes within the human body. We studied the conformational space of SER, and explored in depth the significant stereoelectronic features for the structure stabilization and antioxidant activity. Forty-eight equilibrium structures were described at the B3LYP/6-311++G(d,p) level, characterizing four non-previously reported conformers. Electron distributions were analyzed by topological QTAIM (Quantum Theory of atoms in molecules) and natural bond orbital (NBO) studies. The study was supplemented by an exploration of molecular electrostatic potential (MEP). Intramolecular hydrogen interactions were also investigated; N10⋯HC4 or N10⋯HC2 hydrogen bondings were depicted in 5 conformers. The conformer stabilization and the corresponding energy arrangement were explained by hyperconjugation interactions obtained by NBO analysis. The present study is based on the effect of the 5-OH group on geometric and electronic behavior that we have previously reported on the similar structure tryptamine (TRA). Our interest also lies in SER's free radical scavenging capacity as a member of the indole family. The H-atom abstraction and single-electron transfer mechanisms were taken into account. Our results showed that donor-acceptor interactions play a major role in explaining the changes induced by the OH group, and free-radical scavenging capability of the indole compounds. Copyright © 2018 Elsevier Inc. All rights reserved.

Improving Density Functionals with Quantum Harmonic Oscillators

NASA Astrophysics Data System (ADS)

Tkatchenko, Alexandre

2013-03-01

Density functional theory (DFT) is the most widely used and successful approach for electronic structure calculations. However, one of the pressing challenges for DFT is developing efficient functionals that can accurately capture the omnipresent long-range electron correlations, which determine the structure and stability of many molecules and materials. Here we show that, under certain conditions, the problem of computing the long-range correlation energy of interacting electrons can be mapped to a system of coupled quantum harmonic oscillators (QHOs). The proposed model allows us to synergistically combine concepts from DFT, quantum chemistry, and the widely discussed random-phase approximation for the correlation energy. In the dipole limit, the interaction energy for a system of coupled QHOs can be calculated exactly, thereby leading to an efficient and accurate model for the many-body dispersion energy of complex molecules and materials. The studied examples include intermolecular binding energies, the conformational hierarchy of DNA structures, the geometry and stability of molecular crystals, and supramolecular host-guest complexes (A. Tkatchenko, R. A. DiStasio Jr., R. Car, M. Scheffler, Phys. Rev. Lett. 108, 236402 (2012); R. A. DiStasio Jr., A. von Lilienfeld, A. Tkatchenko, PNAS 109, 14791 (2012); A. Tkatchenko, D. Alfe, K. S. Kim, J. Chem. Theory and Comp. (2012), doi: 10.1021/ct300711r; A. Tkatchenko, A. Ambrosetti, R. A. DiStasio Jr., arXiv:1210.8343v1).

Stabilizing benzene-like planar N6 rings to form a single atomic honeycomb BeN3 sheet with high carrier mobility.

PubMed

Li, Xiaoyin; Zhang, Shunhong; Zhang, Cunzhi; Wang, Qian

2018-01-18

It is a longstanding quest to use the planar N 6 ring as a structural unit to build stable atomic sheets. However, unlike C 6 H 6 , the neutral N 6 ring is unstable due to the strong repulsion of the lone-pair of electrons. Using first-principles calculations and the global structure search method, we show that the N 6 unit can be stabilized by the linkage of Be atoms, forming a h-BeN 3 honeycomb monolayer, in which the geometry and the π-molecular orbitals of the N 6 rings are well kept. This sheet is not only energetically, dynamically and thermally stable, but also can withstand high temperatures up to 1000 K. Band structure calculation combined with a group theory analysis and a tight-binding model uncover that h-BeN 3 has a π-band dominated band structure with an indirect band gap of 1.67 eV. While it possesses a direct band gap of 2.07 eV at the Γ point lying in the photon energy region of visual light, its interband dipole transition is symmetrically allowed so that electrons can be excited by photons free of phonons. Based on deformation potential theory, a systematic study of the transport properties reveals that the h-BeN 3 sheet possesses a high carrier mobility of ∼10 3 cm 2 V -1 s -1 , superior to the extensively studied transition metal dichalcogenide monolayers. We further demonstrate that this sheet can be rolled up into either zigzag or armchair nanotubes. These nanotubes are also dynamically stable, and are all direct band gap semiconductors with carrier mobility comparable to that of their 2D counterparts, regardless of their chirality and diameter. The robust stability and novel electronic and transport properties of the h-BeN 3 sheet and its tubular derivatives endow them with great potential for applications in nanoelectronic devices.

Recent Advances in the Inverted Planar Structure of Perovskite Solar Cells.

PubMed

Meng, Lei; You, Jingbi; Guo, Tzung-Fang; Yang, Yang

2016-01-19

Inorganic-organic hybrid perovskite solar cells research could be traced back to 2009, and initially showed 3.8% efficiency. After 6 years of efforts, the efficiency has been pushed to 20.1%. The pace of development was much faster than that of any type of solar cell technology. In addition to high efficiency, the device fabrication is a low-cost solution process. Due to these advantages, a large number of scientists have been immersed into this promising area. In the past 6 years, much of the research on perovskite solar cells has been focused on planar and mesoporous device structures employing an n-type TiO2 layer as the bottom electron transport layer. These architectures have achieved champion device efficiencies. However, they still possess unwanted features. Mesoporous structures require a high temperature (>450 °C) sintering process for the TiO2 scaffold, which will increase the cost and also not be compatible with flexible substrates. While the planar structures based on TiO2 (regular structure) usually suffer from a large degree of J-V hysteresis. Recently, another emerging structure, referred to as an "inverted" planar device structure (i.e., p-i-n), uses p-type and n-type materials as bottom and top charge transport layers, respectively. This structure derived from organic solar cells, and the charge transport layers used in organic photovoltaics were successfully transferred into perovskite solar cells. The p-i-n structure of perovskite solar cells has shown efficiencies as high as 18%, lower temperature processing, flexibility, and, furthermore, negligible J-V hysteresis effects. In this Account, we will provide a comprehensive comparison of the mesoporous and planar structures, and also the regular and inverted of planar structures. Later, we will focus the discussion on the development of the inverted planar structure of perovskite solar cells, including film growth, band alignment, stability, and hysteresis. In the film growth part, several methods for obtaining high quality perovskite films are reviewed. In the interface engineering parts, the effect of hole transport layer on subsequent perovskite film growth and their interface band alignment, and also the effect of electron transport layers on charge transport and interface contact will be discussed. As concerns stability, the role of charge transport layers especially the top electron transport layer in the devices stability will be concluded. In the hysteresis part, possible reasons for hysteresis free in inverted planar structure are provided. At the end of this Account, future development and possible solutions to the remaining challenges facing the commercialization of perovskite solar cells are discussed.

Ab Initio Prediction of the Structural, Electronic, Elastic, and Thermoelectric Properties of Half-Heusler Ternary Compounds TiIrX (X = As and Sb)

NASA Astrophysics Data System (ADS)

Chibani, S.; Arbouche, O.; Zemouli, M.; Amara, K.; Benallou, Y.; Azzaz, Y.; Belgoumène, B.; Bentayeb, A.; Ameri, M.

2018-01-01

The structural, electronic, elastic, and thermoelectric properties of TiIrX (X = As and Sb) half-Heusler compounds with 18 valence electrons were studied using density functional theory. The generalized gradient approximation of Perdew-Burke and Ernzerhof used for calculation of the structural parameters and elastic properties of TiIrAs and TiIrSb denotes that the computed lattice constants were in excellent agreement with the available experimental data and previous theoretical works. Furthermore, the calculated elastic constants for both compounds satisfy the Born criteria indicating their mechanical stabilities. The modified Becke-Johnson potential (TB-mBJ) was used to provide a better description of the electronic structures, which indicate that both compounds are narrow-gap semiconductors. Additionally, the investigations of thermoelectric performance were carried out using the results of ab initio band-structure calculations and the semi-classical Boltzmann theory within the constant relaxation time approximations. The predicted values of the figure of merit ZT e are close to unity at room temperature. This reveals that TiIrAs and TiIrSb compounds are excellent candidates for practical applications in the thermoelectric devices.

Spirally Structured Conductive Composites for Highly Stretchable, Robust Conductors and Sensors.

PubMed

Wu, Xiaodong; Han, Yangyang; Zhang, Xinxing; Lu, Canhui

2017-07-12

Flexible and stretchable electronics are highly desirable for next generation devices. However, stretchability and conductivity are fundamentally difficult to combine for conventional conductive composites, which restricts their widespread applications especially as stretchable electronics. Here, we innovatively develop a new class of highly stretchable and robust conductive composites via a simple and scalable structural approach. Briefly, carbon nanotubes are spray-coated onto a self-adhesive rubber film, followed by rolling up the film completely to create a spirally layered structure within the composites. This unique spirally layered structure breaks the typical trade-off between stretchability and conductivity of traditional conductive composites and, more importantly, restrains the generation and propagation of mechanical microcracks in the conductive layer under strain. Benefiting from such structure-induced advantages, the spirally layered composites exhibit high stretchability and flexibility, good conductive stability, and excellent robustness, enabling the composites to serve as highly stretchable conductors (up to 300% strain), versatile sensors for monitoring both subtle and large human activities, and functional threads for wearable electronics. This novel and efficient methodology provides a new design philosophy for manufacturing not only stretchable conductors and sensors but also other stretchable electronics, such as transistors, generators, artificial muscles, etc.

Probing structure, thermochemistry, electron affinity, and magnetic moment of thulium-doped silicon clusters TmSi n (n = 3-10) and their anions with density functional theory.

PubMed

Huang, Xintao; Yang, Jucai

2017-12-26

The most stable structures and electronic properties of TmSi n (n = 3-10) clusters and their anions have been probed by using the ABCluster global search technique combined with the PBE, TPSSh, and B3LYP density functional methods. The results revealed that the most stable structures of neutral TmSi n and their anions can be regarded as substituting a Si atom of the ground state structure of Si n + 1 with a Tm atom. The reliable AEAs, VDEs and simulated PES of TmSi n (n = 3-10) are presented. Calculations of HOMO-LUMO gap revealed that introducing Tm atom to Si cluster can improve photochemical reactivity of the cluster. The NPA analyses indicated that the 4f electron of Tm atom in TmSi n (n = 3-10) and their anions do not participate in bonding. The total magnetic moments of TmSi n are mainly provided by the 4f electrons of Tm atom. The dissociation energy of Tm atom from the most stable structure of TmSi n and their anions has been calculated to examine relative stability.

Shift of semimetal-semiconductor bond direction on “0 1 1” to “1 1 1” Bismuth quazi-two-dimension system

NASA Astrophysics Data System (ADS)

Yazdani, Ahmad; Hamreh, Sajad

2018-03-01

The electronic structure of the nanocrystallines and quasi-two-dimensional systems strongly impressed by the thermodynamic- behavior mainly due to excess of hidden surface free energy. Therefore, the stability of crystalline structure’s change could be related to band-offset of bond rupturing of atomic displacements. whereas for the electronic-structure of "Bi" it seams the competition of L.S and bond exchange should be effectively dominated. Besides all of the characters behave spatial like strong sensitive oxidation here it is supposed that strong correlated electronic structure in the absence of oxygen is resulted on direction of redistribution of surface chemical bond formation before any reconstructive structure. Where • The metallic direction of electronic structure “0 1 1” is changed to “1 1 1” semiconductor direction. • the effect of L.S is more evident on the local density of state while it is not observable around the fermi level. • Strong effect of spin-orbit interaction on splitting of the valance to nearly conduction band around the fermi level is more evident.

Introduction of biotin or folic acid into polypyrrole magnetite core-shell nanoparticles

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

Nan, Alexandrina; Turcu, Rodica; Liebscher, Jürgen

2013-11-13

In order to contribute to the trend in contemporary research to develop magnetic core shell nanoparticles with better properties (reduced toxicity, high colloidal and chemical stability, wide scope of application) in straightforward and reproducible methods new core shell magnetic nanoparticles were developed based on polypyrrole shells functionalized with biotin and folic acid. Magnetite nanoparticles stabilized by sebacic acid were used as magnetic cores. The morphology of magnetite was determined by transmission electron microscopy TEM, while the chemical structure investigated by FT-IR.

Chain length effect on the structure and stability of antimicrobial peptides of the (RW)n series.

PubMed

Phambu, Nsoki; Almarwani, Bashiyar; Garcia, Arlette M; Hamza, Nafisa S; Muhsen, Amira; Baidoo, Jacqueline E; Sunda-Meya, Anderson

2017-08-01

Three peptides containing (RW) n -NH 2 units (where n=4, 6, and 8) have been chosen to study the effect of the chain length on the structure and stability of the peptide using Fourier transform infrared (FTIR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) techniques. Their interactions with Escherichia coli (E. coli) membrane mimetic vesicles are discussed. Infrared results indicate that addition of (RW) n -NH 2 units increases intermolecular H bonds with antiparallel orientation. TGA and DSC results reveal that (RW) 6 -NH 2 shows the optimal chain length in terms of stability and all three peptides show a preferential interaction with one of the anionic lipids in E. coli membranes. SEM images of (RW) 4 -NH 2 present large aggregates while those of (RW) 6 -NH 2 and (RW) 8 -NH 2 present layers of sheet-like structure. In the presence of model membranes, (RW) n -NH 2 show fibrillar peptide superstructures. This study suggests that repeating structures of (RW) n -NH 2 promotes lateral assembly. Copyright © 2017 Elsevier B.V. All rights reserved.

Three-dimensional Sponges with Super Mechanical Stability: Harnessing True Elasticity of Individual Carbon Nanotubes in Macroscopic Architectures

PubMed Central

Dai, Zhaohe; Liu, Luqi; Qi, Xiaoying; Kuang, Jun; Wei, Yueguang; Zhu, Hongwei; Zhang, Zhong

2016-01-01

Efficient assembly of carbon nanotube (CNT) based cellular solids with appropriate structure is the key to fully realize the potential of individual nanotubes in macroscopic architecture. In this work, the macroscopic CNT sponge consisting of randomly interconnected individual carbon nanotubes was grown by CVD, exhibiting a combination of super-elasticity, high strength to weight ratio, fatigue resistance, thermo-mechanical stability and electro-mechanical stability. To deeply understand such extraordinary mechanical performance compared to that of conventional cellular materials and other nanostructured cellular architectures, a thorough study on the response of this CNT-based spongy structure to compression is conducted based on classic elastic theory. The strong inter-tube bonding between neighboring nanotubes is examined, believed to play a critical role in the reversible deformation such as bending and buckling without structural collapse under compression. Based on in-situ scanning electron microscopy observation and nanotube deformation analysis, structural evolution (completely elastic bending-buckling transition) of the carbon nanotubes sponges to deformation is proposed to clarify their mechanical properties and nonlinear electromechanical coupling behavior. PMID:26732143

Theoretical investigations on diamondoids (CnHm, n = 10-41): Nomenclature, structural stabilities, and gap distributions

NASA Astrophysics Data System (ADS)

Wang, Ya-Ting; Zhao, Yu-Jun; Liao, Ji-Hai; Yang, Xiao-Bao

2018-01-01

Combining the congruence check and the first-principles calculations, we have systematically investigated the structural stabilities and gap distributions of possible diamondoids (CnHm) with the carbon numbers (n) from 10 to 41. A simple method for the nomenclature is proposed, which can be used to distinguish and screen the candidates with high efficiency. Different from previous theoretical studies, the possible diamondoids can be enumerated according to our nomenclature, without any pre-determination from experiments. The structural stabilities and electronic properties have been studied by density functional based tight binding and first-principles methods, where a nearly linear correlation is found between the energy gaps obtained by these two methods. According to the formation energy of structures, we have determined the stable configurations as a function of chemical potential. The maximum and minimum energy gaps are found to be dominated by the shape of diamondoids for clusters with a given number of carbon atoms, while the gap decreases in general as the size increases due to the quantum confinement.

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

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

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.

2015-09-01

The noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The findings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. The structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogen bonding with terminalmore » hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. These results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Understanding Defect-Stabilized Noncovalent Functionalization of Graphene

DOE PAGES

Zhou, Hua; Uysal, Ahmet; Anjos, Daniela M.; ...

2015-09-01

For the noncovalent functionalization of graphene by small molecule aromatic adsorbates, phenanthrenequinone (PQ), is investigated systematically by combining electrochemical characterization, high-resolution interfacial X-ray scattering, and ab initio density functional theory calculations. The fi ndings in this study reveal that while PQ deposited on pristine graphene is unstable to electrochemical cycling, the prior introduction of defects and oxygen functionality (hydroxyl and epoxide groups) to the basal plane by exposure to atomic radicals (i.e., oxygen plasma) effectively stabilizes its noncovalent functionalization by PQ adsorption. Moreover, the structure of adsorbed PQ molecules resembles the graphene layer stacking and is further stabilized by hydrogenmore » bonding with terminal hydroxyl groups that form at defect sites within the graphene basal plane. The stabilized PQ/graphene interface demonstrates persistent redox activity associated with proton-coupled-electron-transfer reactions. The resultant PQ adsorbed structure is essentially independent of electrochemical potentials. Finally, these results highlight a facile approach to enhance functionalities of the otherwise chemically inert graphene using noncovalent interactions.« less

Implication of the solvent effect, metal ions and topology in the electronic structure and hydrogen bonding of human telomeric G-quadruplex DNA.

PubMed

Poudel, Lokendra; Steinmetz, Nicole F; French, Roger H; Parsegian, V Adrian; Podgornik, Rudolf; Ching, Wai-Yim

2016-08-03

We present a first-principles density functional study elucidating the effects of solvent, metal ions and topology on the electronic structure and hydrogen bonding of 12 well-designed three dimensional G-quadruplex (G4-DNA) models in different environments. Our study shows that the parallel strand structures are more stable in dry environments and aqueous solutions containing K(+) ions within the tetrad of guanine but conversely, that the anti-parallel structure is more stable in solutions containing the Na(+) ions within the tetrad of guanine. The presence of metal ions within the tetrad of the guanine channel always enhances the stability of the G4-DNA models. The parallel strand structures have larger HOMO-LUMO gaps than antiparallel structures, which are in the range of 0.98 eV to 3.11 eV. Partial charge calculations show that sugar and alkali ions are positively charged whereas nucleobases, PO4 groups and water molecules are all negatively charged. Partial charges on each functional group with different signs and magnitudes contribute differently to the electrostatic interactions involving G4-DNA and favor the parallel structure. A comparative study between specific pairs of different G4-DNA models shows that the Hoogsteen OH and NH hydrogen bonds in the guanine tetrad are significantly influenced by the presence of metal ions and water molecules, collectively affecting the structure and the stability of G4-DNA.

Equilibrium geometries, electronic and magnetic properties of small AunNi- (n = 1-9) clusters

NASA Astrophysics Data System (ADS)

Tang, Cui-Ming; Chen, Xiao-Xu; Yang, Xiang-Dong

2014-05-01

Geometrical, electronic and magnetic properties of small AunNi- (n = 1-9) clusters have been investigated based on density functional theory (DFT) at PW91P86 level. An extensive structural search shows that the relative stable structures of AunNi- (n = 1-9) clusters adopt 2D structure for n = 1-5, 7 and 3D structure for n = 6, 8-9. And the substitution of a Ni atom for an Au atom in the Au-n+1 cluster obviously changes the structure of the host cluster. Moreover, an odd-even alternation phenomenon has been found for HOMO-LUMO energy gaps, indicating that the relative stable structures of the AunNi- clusters with odd-numbered gold atoms have a higher relative stability. Finally, the natural population analysis (NPA) and the vertical detachment energies (VDE) are studied, respectively. The theoretical values of VDE are reported for the first time to our best knowledge.

Structural, electronic and magnetic properties of chevron-type graphene, BN and BC{sub 2}N nanoribbons

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

Guerra, T.; Azevedo, S.; Kaschny, J.R.

2017-04-15

Graphene nanoribbons are predicted to be essential components in future nanoelectronics. The size, edge type, arrangement of atoms and width of nanoribbons drastically change their properties. Boronnitrogencarbon nanoribbons properties are not fully understood so far. In the present contribution it was investigated the structural, electronic and magnetic properties of chevron-type carbon, boron nitride and BC{sub 2}N nanoribbons, using first-principles calculations. The results indicate that the structural stability is closely related to the discrepancies in the bond lengths, which can induce structural deformations and stress. Such nanoribbons present a wide range of electronic behaviors, depending on their composition and particularities ofmore » the atomic arrangement. A net magnetic moment is found for structures that present carbon atoms at the nanoribbon borders. Nevertheless, the calculated magnetic moment depends on the peculiarities of the symmetric arrangement of atoms and imbalance of carbon atoms between different sublattices. It was found that all structures which have a significant energy gap do not present magnetic moment, and vice-versa. Such result indicates the strong correlation between the electronic and magnetic properties of the chevron-type nanoribbons. - Highlights: • Small discrepancies between distinct bond lengths can influence the formation energy of the BC{sub 2}N nanoribbons. • The electronic behavior of the BC{sub 2}N chevron-type nanoribbons depends on the atomic arrangement and structural symmetries. • There is a strong correlation between the electronic and magnetic properties for the BC{sub 2}N structures.« less

Structure and Stability of Molecular Crystals with Many-Body Dispersion-Inclusive Density Functional Tight Binding.

PubMed

Mortazavi, Majid; Brandenburg, Jan Gerit; Maurer, Reinhard J; Tkatchenko, Alexandre

2018-01-18

Accurate prediction of structure and stability of molecular crystals is crucial in materials science and requires reliable modeling of long-range dispersion interactions. Semiempirical electronic structure methods are computationally more efficient than their ab initio counterparts, allowing structure sampling with significant speedups. We combine the Tkatchenko-Scheffler van der Waals method (TS) and the many-body dispersion method (MBD) with third-order density functional tight-binding (DFTB3) via a charge population-based method. We find an overall good performance for the X23 benchmark database of molecular crystals, despite an underestimation of crystal volume that can be traced to the DFTB parametrization. We achieve accurate lattice energy predictions with DFT+MBD energetics on top of vdW-inclusive DFTB3 structures, resulting in a speedup of up to 3000 times compared with a full DFT treatment. This suggests that vdW-inclusive DFTB3 can serve as a viable structural prescreening tool in crystal structure prediction.

First principles studies of structure stability and lithium intercalation of ZnCo2 O4

NASA Astrophysics Data System (ADS)

Zhang, Yanning; Liu, Weiwei; Beijing Computational Science Research Center Team

Among the metal oxides, which are the most widely investigated alternative anodes for use in lithium ion batteries (LIBs), binary and ternary transition metal oxides have received special attention due to their high capacity values. ZnCo2O4 is a promising candidate as anode for LIB, and one can expect a total capacity corresponding to 7.0 - 8.33 mol of recyclable Li per mole of ZnCo2O4. Here we studied the structural stability, electronic properties, lithium intercalation and diffusion barrier of ZnCo2O4 through density functional calculations. The calculated structural and energetic parameters are comparable with experiments. Our theoretical studies provide insights in understanding the mechanism of lithium ion displacement reactions in this ternary metal oxide.

Prediction of the electronic structures, thermodynamic and mechanical properties in manganese doped magnesium-based alloys and their saturated hydrides based on density functional theory

NASA Astrophysics Data System (ADS)

Zhang, Ziying; Zhang, Huizhen; Zhao, Hui; Yu, Zhishui; He, Liang; Li, Jin

2015-04-01

The crystal structures, electronic structures, thermodynamic and mechanical properties of Mg2Ni alloy and its saturated hydride with different Mn-doping contents are investigated using first-principles density functional theory. The lattice parameters for the Mn-doped Mg2Ni alloys and their saturated hydrides decreased with an increasing Mn-doping content because of the smaller atomic size of Mn compared with that of Mg. Analysis of the formation enthalpies and electronic structures reveal that the partial substitution of Mg with Mn reduces the stability of Mg2Ni alloy and its saturated hydride. The calculated elastic constants indicate that, although the partial substitution of Mg with Mn lowers the toughness of the hexagonal Mg2Ni alloy, the charge/discharge cycles are elevated when the Mn-doping content is high enough to form the predicted intermetallic compound Mg3MnNi2.

Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams.

PubMed

Hong, Woong-Ki; Park, Jong Bae; Yoon, Jongwon; Kim, Bong-Joong; Sohn, Jung Inn; Lee, Young Boo; Bae, Tae-Sung; Chang, Sung-Jin; Huh, Yun Suk; Son, Byoungchul; Stach, Eric A; Lee, Takhee; Welland, Mark E

2013-04-10

We report a morphotropic phase transformation in vanadium dioxide (VO2) nanobeams annealed in a high-pressure hydrogen gas, which leads to the stabilization of metallic phases. Structural analyses show that the annealed VO2 nanobeams are hexagonal-close-packed structures with roughened surfaces at room temperature, unlike as-grown VO2 nanobeams with the monoclinic structure and with clean surfaces. Quantitative chemical examination reveals that the hydrogen significantly reduces oxygen in the nanobeams with characteristic nonlinear reduction kinetics which depend on the annealing time. Surprisingly, the work function and the electrical resistance of the reduced nanobeams follow a similar trend to the compositional variation due mainly to the oxygen-deficiency-related defects formed at the roughened surfaces. The electronic transport characteristics indicate that the reduced nanobeams are metallic over a large range of temperatures (room temperature to 383 K). Our results demonstrate the interplay between oxygen deficiency and structural/electronic phase transitions, with implications for engineering electronic properties in vanadium oxide systems.

Robust and adjustable C-shaped electron vortex beams

NASA Astrophysics Data System (ADS)

Mousley, M.; Thirunavukkarasu, G.; Babiker, M.; Yuan, J.

2017-06-01

Wavefront engineering is an important quantum technology, often applied to the production of states carrying orbital angular momentum (OAM). Here, we demonstrate the design and production of robust C-shaped beam states carrying OAM, in which the usual doughnut-shaped transverse intensity structure of the vortex beam contains an adjustable gap. We find that the presence of the vortex lines in the core of the beam is crucial for maintaining the stability of the C-shape structure during beam propagation. The topological charge of the vortex core controls mainly the size of the C-shape, while its opening angle is related to the presence of vortex-anti-vortex loops. We demonstrate the generation and characterisation of C-shaped electron vortex beams, although the result is equally applicable to other quantum waves. C-shaped electron vortex beams have potential applications in nanoscale fabrication of planar split-ring structures and three-dimensional chiral structures as well as depth sensing and magnetic field determination through rotation of the gap in the C-shape.

Electronic structure, thermodynamic properties and hydrogenation of LaPtIn and CePtIn compounds by ab-initio methods

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

Jezierski, Andrzej, E-mail: andrzej.jezierski@ifmpan.poznan.pl; Szytuła, Andrzej

2016-02-15

The electronic structures and thermodynamic properties of LaPtIn and CePtIn are studied by means of ab-initio full-relativistic full-potential local orbital basis (FPLO) method within densities functional (DFT) methodologies. We have also examined the influence of hydrogen on the electronic structure and stability of CePtInH and LaPtInH systems. The positions of the hydrogen atoms have been found from the minimum of the total energy. Our calculations have shown that band structure and topology of the Fermi surfaces changed significantly during the hydrogenation. The thermodynamic properties (bulk modulus, Debye temperatures, constant pressure heat capacity) calculated in quasi-harmonic Debye-Grüneisen model are in amore » good agreement with the experimental data. We have applied different methods of the calculation of the equation of states (EOS) (Murnaghan, Birch-Murnaghan, Poirier–Tarantola, Vinet). The thermodynamic properties are presented for the pressure 0« less

Oxide Thermoelectric Materials: A Structure-Property Relationship

NASA Astrophysics Data System (ADS)

Nag, Abanti; Shubha, V.

2014-04-01

Recent demand for thermoelectric materials for power harvesting from automobile and industrial waste heat requires oxide materials because of their potential advantages over intermetallic alloys in terms of chemical and thermal stability at high temperatures. Achievement of thermoelectric figure of merit equivalent to unity ( ZT ≈ 1) for transition-metal oxides necessitates a second look at the fundamental theory on the basis of the structure-property relationship giving rise to electron correlation accompanied by spin fluctuation. Promising transition-metal oxides based on wide-bandgap semiconductors, perovskite and layered oxides have been studied as potential candidate n- and p-type materials. This paper reviews the correlation between the crystal structure and thermoelectric properties of transition-metal oxides. The crystal-site-dependent electronic configuration and spin degeneracy to control the thermopower and electron-phonon interaction leading to polaron hopping to control electrical conductivity is discussed. Crystal structure tailoring leading to phonon scattering at interfaces and nanograin domains to achieve low thermal conductivity is also highlighted.

Theoretical study of isostructural compounds MTe2 (M = Ni, Pd and Pt) on structure and thermodynamic properties under high pressures

NASA Astrophysics Data System (ADS)

Lei, Jin-Qiao; Liu, Ke; Huang, Sha; Mao, Xiao-Chun; Hou, Bao-Sen; Tan, Jiao; Zhou, Xiao-Lin

2017-11-01

The mechanical, electronic and thermodynamic properties of MTe2 (M = Ni, Pd and Pt) under high pressure were investigated via the first-principles calculations. According to our calculations of these trigonal crystals (space group of P3M1, No: 164), we found that all of them are fulfilled by the mechanical stability criteria under 31 GPa (for NiTe2), 37 GPa (for PdTe2) and 73 GPa (for PtTe2). The study on their structures revealed the elastic anisotropy of these isostructural compounds. Electronic structure calculations show that MTe2 are semi-metal. On the basis of the quasi-harmonic Debye model, we also researches their thermodynamic properties.

Lattice stability and thermal properties of Fe2VAl and Fe2TiSn Heusler compounds

NASA Astrophysics Data System (ADS)

Shastri, Shivprasad S.; Pandey, Sudhir K.

2018-04-01

Fe2VAl and Fe2TiSn are two full-Heusler compounds with non-magnetic ground states. They have application as potential thermoelectric materials. Along with first-principles electronic structure calculations, phonon calculation is one of the important tools in condensed matter physics and material science. Phonon calculations are important in understanding mechanical properties, thermal properties and phase transitions of periodic solids. A combination of electronic structure code and phonon calculation code - phonopy is employed in this work. The vibrational spectra, phonon DOS and thermal properties are studied for these two Heusler compounds. Two compounds are found to be dynamically stable with absence of negative frequencies (energy) in the phonon band structure.

Theoretical simulations of the structural stabilities, elastic, thermodynamic and electronic properties of Pt3Sc and Pt3Y compounds

NASA Astrophysics Data System (ADS)

Boulechfar, R.; Khenioui, Y.; Drablia, S.; Meradji, H.; Abu-Jafar, M.; Omran, S. Bin; Khenata, R.; Ghemid, S.

2018-05-01

Ab-initio calculations based on density functional theory have been performed to study the structural, electronic, thermodynamic and mechanical properties of intermetallic compounds Pt3Sc and Pt3Y using the full-potential linearized augmented plane wave(FP-LAPW) method. The total energy calculations performed for L12, D022 and D024 structures confirm the experimental phase stability. Using the generalized gradient approximation (GGA), the values of enthalpies formation are -1.23 eV/atom and -1.18 eV/atom for Pt3Sc and Pt3Y, respectively. The densities of states (DOS) spectra show the existence of a pseudo-gap at the Fermi level for both compounds which indicate the strong spd hybridization and directing covalent bonding. Furthermore, the density of states at the Fermi level N(EF), the electronic specific heat coefficient (γele) and the number of bonding electrons per atom are predicted in addition to the elastic constants (C11, C12 and C44). The shear modulus (GH), Young's modulus (E), Poisson's ratio (ν), anisotropy factor (A), ratio of B/GH and Cauchy pressure (C12-C44) are also estimated. These parameters show that the Pt3Sc and Pt3Y are ductile compounds. The thermodynamic properties were calculated using the quasi-harmonic Debye model to account for their lattice vibrations. In addition, the influence of the temperature and pressure was analyzed on the heat capacities (Cp and Cv), thermal expansion coefficient (α), Debye temperature (θD) and Grüneisen parameter (γ).

Structure, reactivity, and electronic properties of V-doped Co clusters

NASA Astrophysics Data System (ADS)

Datta, Soumendu; Kabir, Mukul; Saha-Dasgupta, Tanusri; Mookerjee, Abhijit

2009-08-01

Structures and physicochemical properties of V-doped Co13 clusters have been studied in detail using density-functional-theory-based first-principles method. We have found anomalous variation in stability of the doped clusters with increasing V concentration, which has been nicely demonstrated in terms of energetics and electronic properties of the clusters. Our study explains the nonmonotonic variation in reactivity of Co13-mVm clusters toward H2 molecules as reported experimentally [Nonose , J. Phys. Chem. 94, 2744 (1990)]. Moreover, it provides useful insight into the cluster geometry and chemically active sites on the cluster surface, which can help to design better catalytic processes.

Pressure-induced phase transition of KTa1/2Nb1/2O3 solid solutions: A first-principles study

NASA Astrophysics Data System (ADS)

Zhang, Huadi; Liu, Bing; Zhang, Cong; Qiu, Chengcheng; Wang, Xuping; Zhang, Yuanyuan; Lv, Xianshun; Wei, Lei; Li, Qinggang

2018-05-01

The structures and electronic properties of KTa1/2Nb1/2O3 under high pressures have been investigated using the first-principles calculations. Three candidates with B site cation ordered along the [1 0 0], [1 1 0] and [1 1 1] directions are found stable under different pressures by thermodynamics, mechanics and dynamics stability criteria. Further electronic analysis indicates that three structures are semiconductors with different band-gap characteristics. The peculiar chemical bonds of Nb-O and Ta-O are expected to be related to the different electronegativity of the corresponding cations.

First principles study of electronic and structural properties of single walled zigzag boron nitride nanotubes doped with the elements of group IV

NASA Astrophysics Data System (ADS)

Bahari, Ali; jalalinejad, Amir; Bagheri, Mosahhar; Amiri, Masoud

2017-11-01

In this paper, structural and electronic properties and stability of (10, 0) born nitride nanotube (BNNT) are considered within density functional theory by doping group IV elements of the periodic table. The HOMO-LUMO gap has been strongly modified and treated a dual manner by choosing B or N sites for dopant atoms. Formation energy calculation shows that B site doping is more stable than N site doping. Results also show that all dopants turn the pristine BNNT into a p-type semiconductor except for carbon-doped BNNT at B site.

Electrochemical stability and postmortem studies of Pt/SiC catalysts for polymer electrolyte membrane fuel cells.

PubMed

Stamatin, Serban N; Speder, Jozsef; Dhiman, Rajnish; Arenz, Matthias; Skou, Eivind M

2015-03-25

In the presented work, the electrochemical stability of platinized silicon carbide is studied. Postmortem transmission electron microscopy and X-ray photoelectron spectroscopy were used to document the change in the morphology and structure upon potential cycling of Pt/SiC catalysts. Two different potential cycle aging tests were used in order to accelerate the support corrosion, simulating start-up/shutdown and load cycling. On the basis of the results, we draw two main conclusions. First, platinized silicon carbide exhibits improved electrochemical stability over platinized active carbons. Second, silicon carbide undergoes at least mild oxidation if not even silicon leaching.

Structural stability of DNA origami nanostructures in the presence of chaotropic agents

NASA Astrophysics Data System (ADS)

Ramakrishnan, Saminathan; Krainer, Georg; Grundmeier, Guido; Schlierf, Michael; Keller, Adrian

2016-05-01

DNA origami represent powerful platforms for single-molecule investigations of biomolecular processes. The required structural integrity of the DNA origami may, however, pose significant limitations regarding their applicability, for instance in protein folding studies that require strongly denaturing conditions. Here, we therefore report a detailed study on the stability of 2D DNA origami triangles in the presence of the strong chaotropic denaturing agents urea and guanidinium chloride (GdmCl) and its dependence on concentration and temperature. At room temperature, the DNA origami triangles are stable up to at least 24 h in both denaturants at concentrations as high as 6 M. At elevated temperatures, however, structural stability is governed by variations in the melting temperature of the individual staple strands. Therefore, the global melting temperature of the DNA origami does not represent an accurate measure of their structural stability. Although GdmCl has a stronger effect on the global melting temperature, its attack results in less structural damage than observed for urea under equivalent conditions. This enhanced structural stability most likely originates from the ionic nature of GdmCl. By rational design of the arrangement and lengths of the individual staple strands used for the folding of a particular shape, however, the structural stability of DNA origami may be enhanced even further to meet individual experimental requirements. Overall, their high stability renders DNA origami promising platforms for biomolecular studies in the presence of chaotropic agents, including single-molecule protein folding or structural switching.DNA origami represent powerful platforms for single-molecule investigations of biomolecular processes. The required structural integrity of the DNA origami may, however, pose significant limitations regarding their applicability, for instance in protein folding studies that require strongly denaturing conditions. Here, we therefore report a detailed study on the stability of 2D DNA origami triangles in the presence of the strong chaotropic denaturing agents urea and guanidinium chloride (GdmCl) and its dependence on concentration and temperature. At room temperature, the DNA origami triangles are stable up to at least 24 h in both denaturants at concentrations as high as 6 M. At elevated temperatures, however, structural stability is governed by variations in the melting temperature of the individual staple strands. Therefore, the global melting temperature of the DNA origami does not represent an accurate measure of their structural stability. Although GdmCl has a stronger effect on the global melting temperature, its attack results in less structural damage than observed for urea under equivalent conditions. This enhanced structural stability most likely originates from the ionic nature of GdmCl. By rational design of the arrangement and lengths of the individual staple strands used for the folding of a particular shape, however, the structural stability of DNA origami may be enhanced even further to meet individual experimental requirements. Overall, their high stability renders DNA origami promising platforms for biomolecular studies in the presence of chaotropic agents, including single-molecule protein folding or structural switching. Electronic supplementary information (ESI) available: Melting curves without baseline subtraction, AFM images of DNA origami after 24 h incubation, calculated melting temperatures of all staple strands. See DOI: 10.1039/c6nr00835f

First-principles investigation on structural and electronic properties of antimonene nanoribbons and nanotubes

NASA Astrophysics Data System (ADS)

Nagarajan, V.; Chandiramouli, R.

2018-03-01

The electronic properties of antimonene nanotubes and nanoribbons hydrogenated along the zigzag and armchair borders are investigated with the help of density functional theory (DFT) method. The structural stability of antimonene nanostructures is confirmed with the formation energy. The electronic properties of hydrogenated zigzag and armchair antimonene nanostructures are studied in terms of highest occupied molecular orbital (HOMO) & lowest unoccupied molecular orbital (LUMO) gap and density of states (DOS) spectrum. Moreover, due to the influence of buckled orientation, hydrogen passivation and width of antimonene nanostructures, the HOMO-LUMO gap widens in the range of 0.15-0.41 eV. The findings of the present study confirm that the electronic properties of antimonene nanostructures can be tailored with the influence of width, orientation of the edges, passivation with hydrogen and morphology of antimonene nanostructures (nanoribbons, nanotubes), which can be used as chemical sensor and for spintronic devices.

Ferromagnetic Phase Stability, Magnetic, Electronic, Elasto-Mechanical and Thermodynamic Properties of BaCmO3 Perovskite Oxide

NASA Astrophysics Data System (ADS)

Dar, Sajad Ahmad; Srivastava, Vipul; Sakalle, Umesh Kumar; Parey, Vanshree

2018-04-01

The structural, electronic, elasto-mechanical and thermodynamic properties of cubic ABO3 perovskites BaCmO3 has been successfully calculated within density functional theory via full potential linearized augmented plane wave. The structural study divulges ferromagnetic stability for the compound. For the precise calculation of electronic and magnetic properties a generalized gradient approximation (GGA), and a Hubbard approximation (GGA + U), (modified Becke Johnson approximation) mBJ have been incorporated. The electronic study portrays the half-metallic nature for the compound in all the approximations. The calculated magnetic moment with different approximations was found to be large and with an integer value of 6 μ b, this integer value of magnetic moment also proves the half-metallic nature for BaCmO3. The calculated elastic constants have been used to predict mechanical properties like the Young modulus (Y), the Shear modulus (G) and the Poisson ratio (ν). The calculated B/G and Cauchy pressure (C12-C44) present the brittle nature for BaCmO3. The thermodynamic parameters like heat capacity, thermal expansion, and Debye temperature have been calculated and examined in the temperature range of 0 K to 700 K and pressure between 0 GPa and 40 GPa. The melting temperature was also calculated and was found to be 1847 ± 300 K.

Effect of Fe and Co substitution on the martensitic stability and the elastic, electronic, and magnetic properties of Mn2NiGa : Insights from ab initio calculations

NASA Astrophysics Data System (ADS)

Kundu, Ashis; Ghosh, Sheuly; Ghosh, Subhradip

2017-11-01

We investigate the effects of Fe and Co substitutions on the phase stability of the martensitic phase and mechanical, electronic, and magnetic properties of the magnetic shape memory system Mn2NiGa by first-principles density functional theory calculations. The evolution of these aspects upon substitution of Fe and Co at different crystallographic sites is investigated by computing the electronic structure, mechanical properties (tetragonal shear constant, Pugh ratio, and Cauchy pressure), and magnetic exchange parameters. We find that the austenite phase of Mn2NiGa gradually stabilizes with increase in concentration of Fe/Co due to the weakening of the minority spin hybridization of Ni and Mn atoms occupying crystallographically equivalent sites. The interplay between relative structural stability and the compositional changes is understood from the variations in the elastic moduli and electronic structures. We find that like in the Ni2MnGa -based systems, the elastic shear modulus C' can be considered as a predictor of composition dependence of martensitic transformation temperature Tm in substituted Mn2NiGa , thus singling it out as the universally acceptable predictor for martensitic transformation in Ni-Mn-Ga compounds over a wide composition range. The magnetic properties of Mn2NiGa are found to be greatly improved by the substitutions due to stronger ferromagnetic interactions in the compounds. The gradually weaker (stronger) Jahn-Teller distortion (covalent bonding) in the minority spin densities of states due to substitutions leads to a half-metallic-like gap in these compounds resulting in materials with high spin polarization when the substitutions are complete. The substitutions at the Ga site result in the two compounds Mn2NiFe and Mn2NiCo with very high magnetic moments and Curie temperatures. Thus, our work indicates that although the substitutions destroy the martensitic transformation and thus the possibility of realization of shape memory properties in Mn2NiGa , magnetic materials with very good magnetic parameters that are potentially useful for novel magnetic applications can be obtained. This can trigger interest in the experimental community in further research on substituted Mn2NiGa .

Structure, electronic and magnetic properties of Mn{sub n} (n=2-8) clusters: A DFT investigation

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

Kumar, Vipin; Roy, Debesh R., E-mail: drr@ashd.svnit.ac.in

2016-05-06

A detail studyon the stability, electronic and magnetic properties of Mn{sub n} (n=2-8) cluster series is performed under the utilization ofdensity functional theory (DFT). The binding energy (B.E.), HOMO-LUMO energy gap (HLG), chemical hardness (η), ionization potential (I.P.), electron affinity (E.A)and electronegativity (χ) of these clusters are predicted. We have also studied the magnetic moments associated with the stable cluster isomers. The lowest energy structures for each cluster sizes aredetermined with a systematic search imposing all possible initial magnetic configuration on the cluster. All the calculations are carried out using a popular GGA functional PBE as proposed by Pardew, Burkemore » and Ernzerhof and implemented in the VASP program.« less

Multienergy gold ion implantation for enhancing the field electron emission characteristics of heterogranular structured diamond films grown on Au-coated Si substrates

NASA Astrophysics Data System (ADS)

Sankaran, K. J.; Manoharan, D.; Sundaravel, B.; Lin, I. N.

2016-09-01

Multienergy Au-ion implantation enhanced the electrical conductivity of heterogranular structured diamond films grown on Au-coated Si substrates to a high level of 5076.0 (Ω cm)-1 and improved the field electron emission (FEE) characteristics of the films to low turn-on field of 1.6 V/μm, high current density of 5.4 mA/cm2 (@ 2.65 V/μm), and high lifetime stability of 1825 min. The catalytic induction of nanographitic phases in the films due to Au-ion implantation and the formation of diamond-to-Si eutectic interface layer due to Au-coating on Si together encouraged the efficient conducting channels for electron transport, thereby improved the FEE characteristics of the films.

Strong interplay between structure and electronic properties in CuIn(S,Se){2}: a first-principles study.

PubMed

Vidal, Julien; Botti, Silvana; Olsson, Pär; Guillemoles, Jean-François; Reining, Lucia

2010-02-05

We present a first-principles study of the electronic properties of CuIn(S,Se){2} (CIS) using state-of-the-art self-consistent GW and hybrid functionals. The calculated band gap depends strongly on the anion displacement u, an internal structural parameter that measures lattice distortion. This contrasts with the observed stability of the band gap of CIS solar panels under operating conditions, where a relatively large dispersion of values for u occurs. We solve this apparent paradox considering the coupled effect on the band gap of copper vacancies and lattice distortions. The correct treatment of d electrons in these materials requires going beyond density functional theory, and GW self-consistency is critical to evaluate the quasiparticle gap and the valence band maximum.

Predicting the potentials, solubilities and stabilities of metal-acetylacetonates for non-aqueous redox flow batteries using density functional theory calculations

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

Kucharyson, J. F.; Cheng, L.; Tung, S. O.

New active materials are needed to improve the performance and reduce the cost of non-aqueous redox flow batteries (RFBs) for grid-scale energy storage applications. Efforts to develop better performing materials, which have largely been empirical, would benefit from a better understanding of relationships between structural, electronic and RFB-relevant functional properties. This paper focuses on metal-acetylacetonates, a class of metal coordination complexes that has shown promise for use in RFBs, and describes correlations between their experimentally measured standard potentials, solubilities, and stabilities (cycle lifes), and selected chemical, structural and electronic properties determined from Density Functional Theory (DFT) calculations. The training setmore » consisted of 16 complexes including 5 different metals and 11 different substituents on the acetylacetonate ligand. Standard potentials for those compounds were calculated and are in good agreement with experimentally measured results. A predictive equation based on the solvation energies and dipole moments, two easily computed properties, reasonably modeled the experimentally determined solubilities. Importantly, we were able to identify a descriptor for the stability of acetylacetonates. The experimentally determined stability, quantified as the cycle life to a given degree of degradation, correlated with the percentage of the highest occupied (HOMO) or lowest unoccupied molecular orbital (LUMO) on the metal of the complex. This percentage is influenced by the degree of ligand innocence (irreducibility), and complexes with the most innocent ligands yielded the most stable redox reactions. To this end, VO(acetylacetonate)(2) and Fe(acetylacetonate)(3), with nearly 80% of the HOMO and LUMO on the metal, possessed the most stable oxidation and reduction half-reactions, respectively. The structure-function relationships and correlations presented in this paper could be used to predict new, highly soluble and stable complexes for RFB applications.« less

Synthesis, characterization, and thermal stability of SiO2/TiO2/CR-Ag multilayered nanostructures

NASA Astrophysics Data System (ADS)

Díaz, Gabriela; Chang, Yao-Jen; Philipossian, Ara

2018-06-01

The controllable synthesis and characterization of novel thermally stable silver-based particles are described. The experimental approach involves the design of thermally stable nanostructures by the deposition of an interfacial thick, active titania layer between the primary substrate (SiO2 particles) and the metal nanoparticles (Ag NPs), as well as the doping of Ag nanoparticles with an organic molecule (Congo Red, CR). The nanostructured particles were composed of a 330-nm silica core capped by a granular titania layer (10 to 13 nm in thickness), along with monodisperse 5 to 30 nm CR-Ag NPs deposited on top. The titania-coated support (SiO2/TiO2 particles) was shown to be chemically and thermally stable and promoted the nucleation and anchoring of CR-Ag NPs, which prevented the sintering of CR-Ag NPs when the structure was exposed to high temperatures. The thermal stability of the silver composites was examined by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HRTEM). Larger than 10 nm CR-Ag NPs were thermally stable up to 300 °C. Such temperature was high enough to destabilize the CR-Ag NPs due to the melting point of the CR. On the other hand, smaller than 10 nm Ag NPs were stable at temperatures up to 500 °C because of the strong metal-metal oxide binding energy. Energy dispersion X-ray spectroscopy (EDS) was carried out to qualitatively analyze the chemical stability of the structure at different temperatures which confirmed the stability of the structure and the existence of silver NPs at temperatures up to 500 °C.

Effects of manganese doping on the structure evolution of small-sized boron clusters

NASA Astrophysics Data System (ADS)

Zhao, Lingquan; Qu, Xin; Wang, Yanchao; Lv, Jian; Zhang, Lijun; Hu, Ziyu; Gu, Guangrui; Ma, Yanming

2017-07-01

Atomic doping of clusters is known as an effective approach to stabilize or modify the structures and properties of resulting doped clusters. We herein report the effect of manganese (Mn) doping on the structure evolution of small-sized boron (B) clusters. The global minimum structures of both neutral and charged Mn doped B cluster \\text{MnB}nQ (n  =  10-20 and Q  =  0, ±1) have been proposed through extensive first-principles swarm-intelligence based structure searches. It is found that Mn doping has significantly modified the grow behaviors of B clusters, leading to two novel structural transitions from planar to tubular and then to cage-like B structures in both neutral and charged species. Half-sandwich-type structures are most favorable for small \\text{MnB}n-/0/+ (n  ⩽  13) clusters and gradually transform to Mn-centered double-ring tubular structures at \\text{MnB}16-/0/+ clusters with superior thermodynamic stabilities compared with their neighbors. Most strikingly, endohedral cages become the ground-state structures for larger \\text{MnB}n-/0/+ (n  ⩾  19) clusters, among which \\text{MnB}20+ adopts a highly symmetric structure with superior thermodynamic stability and a large HOMO-LUMO gap of 4.53 eV. The unique stability of the endohedral \\text{MnB}\\text{20}+ cage is attributed to the geometric fit and formation of 18-electron closed-shell configuration. The results significantly advance our understanding about the structure and bonding of B-based clusters and strongly suggest transition-metal doping as a viable route to synthesize intriguing B-based nanomaterials.

Synthesis, crystal structure and DFT studies of a dual fluorescent ketamine: Structural changes in the ground and excited states

NASA Astrophysics Data System (ADS)

Latha, V.; Balakrishnan, C.; Neelakantan, M. A.

2015-07-01

A fluorescent probe 2Z,2‧Z-3,3‧-(4,4‧-methylenebis(4,1-phenylene) bis(azanediyl))bis (1,3-diphenylprop-2-en-1-one) (L) was synthesized and characterized by IR, 1H NMR, ESI-mass, UV-visible and fluorescence spectral techniques. The single crystal analysis illustrates the existence of L in ketamine form. The crystal structure is stabilized by intramolecular and intermolecular hydrogen bonding. The thermal stability of L was studied by TG analysis. The fluorescence spectrum of L shows dual emission, and is due to excited state intramolecular proton transfer (ESIPT) process. This is supported by the high Stokes shift value. Electronic structure calculations of L in the ground and excited state have been carried out using DFT and TD-DFT at B3LYP/6-31G (d,p) level, respectively. The vibrational spectrum was computed at this level and compared with experimental values. Major orbital contributions for the electronic transitions were assigned with the help of TD-DFT. The changes in the Mulliken charge, bond lengths and bond angles between the ground and excited states of the tautomers demonstrate that twisted intramolecular charge transfer (TICT) process occurs along with ESIPT in the excited state.

Solvothermal Synthesis of a Hollow Micro-Sphere LiFePO4/C Composite with a Porous Interior Structure as a Cathode Material for Lithium Ion Batteries

PubMed Central

Liu, Yang; Zhang, Jieyu; Li, Ying; Hu, Yemin; Li, Wenxian; Zhu, Mingyuan; Hu, Pengfei; Chou, Shulei; Wang, Guoxiu

2017-01-01

To overcome the low lithium ion diffusion and slow electron transfer, a hollow micro sphere LiFePO4/C cathode material with a porous interior structure was synthesized via a solvothermal method by using ethylene glycol (EG) as the solvent medium and cetyltrimethylammonium bromide (CTAB) as the surfactant. In this strategy, the EG solvent inhibits the growth of the crystals and the CTAB surfactant boots the self-assembly of the primary nanoparticles to form hollow spheres. The resultant carbon-coat LiFePO4/C hollow micro-spheres have a ~300 nm thick shell/wall consisting of aggregated nanoparticles and a porous interior. When used as materials for lithium-ion batteries, the hollow micro spherical LiFePO4/C composite exhibits superior discharge capacity (163 mAh g−1 at 0.1 C), good high-rate discharge capacity (118 mAh g−1 at 10 C), and fine cycling stability (99.2% after 200 cycles at 0.1 C). The good electrochemical performances are attributed to a high rate of ionic/electronic conduction and the high structural stability arising from the nanosized primary particles and the micro-sized hollow spherical structure. PMID:29099814

Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems

NASA Astrophysics Data System (ADS)

Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

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

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Structural evolution of atomically precise thiolated bimetallic [Au(12+n)Cu₃₂(SR)(30+n)]⁴⁻ (n = 0, 2, 4, 6) nanoclusters.

PubMed

Yang, Huayan; Wang, Yu; Yan, Juanzhu; Chen, Xi; Zhang, Xin; Häkkinen, Hannu; Zheng, Nanfeng

2014-05-21

A series of all-thiol stabilized bimetallic Au-Cu nanoclusters, [Au(12+n)Cu32(SR)(30+n)](4-) (n = 0, 2, 4, 6 and SR = SPhCF3), are successfully synthesized and characterized by X-ray single-crystal analysis and density functional theory (DFT) calculations. Each cluster consists of a Keplerate two-shell Au12@Cu20 core protected by (6 - n) units of Cu2(SR)5 and n units of Cu2Au(SR)6 (n = 0, 2, 4, 6) motifs on its surface. The size and structural evolution of the clusters is atomically controlled by the Au precursors and countercations used in the syntheses. The clusters exhibit similar optical absorption properties that are not dependent on the number of surface Cu2Au(SR)6 units. Although DFT suggests an electronic structure with an 18-electron superatom shell closure, the clusters display different thermal stabilities. [Au(12+n)Cu32(SR)(30+n)](4-) clusters with n = 0 and 2 are more stable than those with n = 4 and 6. Moreover, an oxidation product of the clusters, [Au13Cu12(SR)20](4-), is structurally identified to gain insight into how the clusters are oxidized.

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

DOE PAGES

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng; ...

2017-05-24

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Au-induced deep groove nanowire structure on the Ge(001) surface: DFT calculations

NASA Astrophysics Data System (ADS)

Tsay, Shiow-Fon

2016-09-01

The atomic geometry, stability, and electronic properties of self-organized Au induced nanowires on the Ge(001) surface are investigated based on the density-functional theory in GGA and the stoichiometry of Au. A giant Ge zigzag chain structure is suggested for 0.75 ML Au coverage, which displays c(8 × 2) deep groove zigzag nanowire structure simulated STM images. The top layer Ge and Au atomic disorder introduces the chevron units into the zigzag nanowire structure STM image as per the experimental observations. The zigzag Ge nanowire exhibits a semi-metallic characteristic, and the electric transport occurs in between the Ge zigzag nanowire and the subsurface. The system exhibits obvious electronic correlations among the Ge nanowire, the nano-facet Au trimers and the deeper layer Ge atoms, that play an important role in the electronic structure. At surface Brillouin zone boundaries, an anisotropic two-dimensional upward parabolic surface-state band is consistent with the ARPES spectra reported by Nakatsuji et al. [Phys. Rev. B 80, 081406(R) (2009); Phys. Rev. B 84, 115411 (2011)]; this electronic structure is different from the quasi-one-dimensional energy trough reported by Schäfer et al. [Phys. Rev. Lett. 101, 236802 (2008); Phys. Rev. B 83, 121411(R) (2011)].

Recent progress in stabilizing hybrid perovskites for solar cell applications

NASA Astrophysics Data System (ADS)

Chen, Jianqing; Cai, Xin; Yang, Donghui; Song, Dan; Wang, Jiajia; Jiang, Jinghua; Ma, Aibin; Lv, Shiquan; Hu, Michael Z.; Ni, Chaoying

2017-07-01

Hybrid inorganic-organic perovskites have quickly evolved as a promising group of materials for solar cells and optoelectronic applications mainly owing to the inexpensive materials, relatively simple and versatile fabrication and high power conversion efficiency (PCE). The certified energy conversion efficiency for perovskite solar cell (PSC) has reached above 20%, which is compatible to the current best for commercial applications. However, long-term stabilities of the materials and devices remain to be the biggest challenging issue for realistic implementation of the PSCs. This article discusses the key issues related to the stability of perovskite absorbing layer including crystal structural stability, chemical stability under moisture, oxygen, illumination and interface reaction, effects of electron-transporting materials (ETM), hole-transporting materials (HTM), contact electrodes, ion migration and preparation conditions. Towards the end, prospective strategies for improving the stability of PSCs are also briefly discussed and summarized. We focus on recent understanding of the stability of materials and devices and our perspectives about the strategies for the stability improvement.

Hierarchical, porous CuS microspheres integrated with carbon nanotubes for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Lu, Yang; Liu, Xianming; Wang, Weixiao; Cheng, Jinbing; Yan, Hailong; Tang, Chengchun; Kim, Jang-Kyo; Luo, Yongsong

2015-11-01

Carbon nanotubes (CNTs) incorporated porous 3-dimensional (3D) CuS microspheres have been successfully synthesized via a simple refluxing method assisted by PVP. The composites are composed of flower-shaped CuS secondary microspheres, which in turn are assembled with primary nanosheets of 15-30 nm in thickness and fully integrated with CNT. The composites possess a large specific surface area of 189.6 m2 g-1 and a high conductivity of 0.471 S cm-1. As electrode materials for supercapacitors, the nanocomposites show excellent cyclability and rate capability and deliver an average reversible capacitance as high as 1960 F g-1 at a current density of 10 mA cm-2 over 10000 cycles. The high electrochemical performance can be attributed to the synergistic effect of CNTs and the unique microstructure of CuS. The CNTs serve as not only a conductive agent to accelerate the transfer of electrons in the composites, but also as a buffer matrix to restrain the volume change and stabilize the electrode structure during the charge/discharge process. The porous structure of CuS also helps to stabilize the electrode structure and facilitates the transport for electrons.

Hierarchical, porous CuS microspheres integrated with carbon nanotubes for high-performance supercapacitors.

PubMed

Lu, Yang; Liu, Xianming; Wang, Weixiao; Cheng, Jinbing; Yan, Hailong; Tang, Chengchun; Kim, Jang-Kyo; Luo, Yongsong

2015-11-16

Carbon nanotubes (CNTs) incorporated porous 3-dimensional (3D) CuS microspheres have been successfully synthesized via a simple refluxing method assisted by PVP. The composites are composed of flower-shaped CuS secondary microspheres, which in turn are assembled with primary nanosheets of 15-30 nm in thickness and fully integrated with CNT. The composites possess a large specific surface area of 189.6 m(2) g(-1) and a high conductivity of 0.471 S cm(-1). As electrode materials for supercapacitors, the nanocomposites show excellent cyclability and rate capability and deliver an average reversible capacitance as high as 1960 F g(-1) at a current density of 10 mA cm(-2) over 10000 cycles. The high electrochemical performance can be attributed to the synergistic effect of CNTs and the unique microstructure of CuS. The CNTs serve as not only a conductive agent to accelerate the transfer of electrons in the composites, but also as a buffer matrix to restrain the volume change and stabilize the electrode structure during the charge/discharge process. The porous structure of CuS also helps to stabilize the electrode structure and facilitates the transport for electrons.

Utilizing environmental friendly iron as a substitution element in spinel structured cathode materials for safer high energy lithium-ion batteries

DOE PAGES

Hu, Enyuan; Bak, Seong -Min; Liu, Yijin; ...

2015-12-03

Suppressing oxygen release from lithium ion battery cathodes during heating is a critical issue for the improvement of the battery safety characteristics because oxygen can exothermically react with the flammable electrolyte and cause thermal runaway. Previous studies have shown that oxygen release can be reduced by the migration of transition metal cations from octahedral sites to tetrahedral sites during heating. Such site-preferred migration is determined by the electronic structure of cations. In addition, taking advantage of the unique electronic structure of the environmental friendly Fe, this is selected as substitution element in a high energy density material LiNi 0.5Mn 1.5Omore » 4 to improve the thermal stability. The optimized LiNi 0.33Mn 1.33Fe 0.33O 4 material shows significantly improved thermal stability compared with the unsubstituted one, demonstrated by no observed oxygen release at temperatures as high as 500°C. Due to the electrochemical contribution of Fe, the high energy density feature of LiNi 0.5Mn 1.5O 4 is well preserved.« less

An ab initio study of the electronic structure and relative stability of the halogenated thiophosphorus compounds SPX (X = Cl, F, Br) and their isomers

NASA Astrophysics Data System (ADS)

Nowek, Andrzej; Richardson, Rhonda; Babinec, Peter; Leszczyński, Jerzy

1997-12-01

The electronic structure and relative stability of the halogenated thiophosphorus compounds SPCl, SPF, and SPBr and their isomers ClSP, FSP, and BrSP were investigated using ab initio post-Hartree-Fock methods. Molecular geometries of all these structures together with the transition states between isomers, have been optimized at the SCF, MP2, and CCSD levels. Single-point CCSD(T) and MP4 calculations have been performed at the optimal CCSD and MP2 geometries. All calculations have been done using the standard 6-311G(2d) basis set. Harmonic vibrational frequencies and IR intensities for all species were calculated at the correlated levels, and they are in good agreement with the available data from matrix-isolated IR spectroscopy. Because the isomers ClSP, FSP, and BrSP have not yet been experimentally observed, we extended our study by calculating of equilibrium constants of isomerization using Eyring transition state theory, and we have found that at sufficiently high temperatures (≈ 1000 K) the equilibrium constants are large enough for the possible detection of these isomers.

Octahedral tilting instabilities in inorganic halide perovskites

NASA Astrophysics Data System (ADS)

Bechtel, Jonathon S.; Van der Ven, Anton

2018-02-01

Dynamic instabilities, stabilized by anharmonic interactions in cubic and tetragonal halide perovskites at high temperature, play a role in the electronic structure and optoelectronic properties of halide perovskites. In particular, inorganic and hybrid perovskite materials undergo structural phase transitions associated with octahedral tilts of the metal-halide octahedra. We investigate the structural instabilities present in inorganic Cs M X3 perovskites with Pb or Sn on the metal site and Br or I on the X site. Defining primary order parameters in terms of symmetry-adapted collective displacement modes and secondary order parameters in terms of symmetrized Hencky strain components, we unravel the coupling between octahedral tilt modes and macroscopic strains as well as the role of A -site displacements in perovskite phase stability. Symmetry-allowed secondary strain order parameters are enumerated for the 14 unique perovskite tilt systems. Using first-principles calculations to explore the Born-Oppenheimer energy surface in terms of symmetrized order parameters, we find coupling between octahedral tilting and A -site displacements is necessary to stabilize P n m a ground states. Additionally, we show that the relative stability of an inorganic halide perovskite tilt system correlates with the volume decrease from the high-symmetry cubic phase to the low-symmetry distorted phase.

Crystal structure of a multi-domain human smoothened receptor in complex with a super stabilizing ligand

NASA Astrophysics Data System (ADS)

Zhang, Xianjun; Zhao, Fei; Wu, Yiran; Yang, Jun; Han, Gye Won; Zhao, Suwen; Ishchenko, Andrii; Ye, Lintao; Lin, Xi; Ding, Kang; Dharmarajan, Venkatasubramanian; Griffin, Patrick R.; Gati, Cornelius; Nelson, Garrett; Hunter, Mark S.; Hanson, Michael A.; Cherezov, Vadim; Stevens, Raymond C.; Tan, Wenfu; Tao, Houchao; Xu, Fei

2017-05-01

The Smoothened receptor (SMO) belongs to the Class Frizzled of the G protein-coupled receptor (GPCR) superfamily, constituting a key component of the Hedgehog signalling pathway. Here we report the crystal structure of the multi-domain human SMO, bound and stabilized by a designed tool ligand TC114, using an X-ray free-electron laser source at 2.9 Å. The structure reveals a precise arrangement of three distinct domains: a seven-transmembrane helices domain (TMD), a hinge domain (HD) and an intact extracellular cysteine-rich domain (CRD). This architecture enables allosteric interactions between the domains that are important for ligand recognition and receptor activation. By combining the structural data, molecular dynamics simulation, and hydrogen-deuterium-exchange analysis, we demonstrate that transmembrane helix VI, extracellular loop 3 and the HD play a central role in transmitting the signal employing a unique GPCR activation mechanism, distinct from other multi-domain GPCRs.

Structural and spectral comparisons between isomeric benzisothiazole and benzothiazole based aromatic heterocyclic dyes

NASA Astrophysics Data System (ADS)

Wang, Yin-Ge; Wang, Yue-Hua; Tao, Tao; Qian, Hui-Fen; Huang, Wei

2015-09-01

A pair of isomeric heterocyclic compounds, namely 3-amino-5-nitro-[2,1]-benzisothiazole and 2-amino-6-nitrobenzothiazole, are used as the diazonium components to couple with two N-substituted 4-aminobenzene derivatives. As a result, two pairs of isomeric aromatic heterocyclic azo dyes have been produced and they are structurally and spectrally characterized and compared including single-crystal structures, electronic spectra, solvatochromism and reversible acid-base discoloration, thermal stability and theoretically calculations. It is concluded that both benzisothiazole and benzothiazole based dyes show planar molecular structures and offset π-π stacking interactions, solvatochromism and reversible acid-base discoloration. Furthermore, benzisothiazole based aromatic heterocyclic dyes exhibit higher thermal stability, larger solvatochromic effects and maximum absorption wavelengths than corresponding benzothiazole based ones, which can be explained successfully by the differences of their calculated isomerization energy, dipole moment and molecular band gaps.

Stability of a Bifunctional Cu-Based Core@Zeolite Shell Catalyst for Dimethyl Ether Synthesis Under Redox Conditions Studied by Environmental Transmission Electron Microscopy and In Situ X-Ray Ptychography.

PubMed

Baier, Sina; Damsgaard, Christian D; Klumpp, Michael; Reinhardt, Juliane; Sheppard, Thomas; Balogh, Zoltan; Kasama, Takeshi; Benzi, Federico; Wagner, Jakob B; Schwieger, Wilhelm; Schroer, Christian G; Grunwaldt, Jan-Dierk

2017-06-01

When using bifunctional core@shell catalysts, the stability of both the shell and core-shell interface is crucial for catalytic applications. In the present study, we elucidate the stability of a CuO/ZnO/Al2O3@ZSM-5 core@shell material, used for one-stage synthesis of dimethyl ether from synthesis gas. The catalyst stability was studied in a hierarchical manner by complementary environmental transmission electron microscopy (ETEM), scanning electron microscopy (SEM) and in situ hard X-ray ptychography with a specially designed in situ cell. Both reductive activation and reoxidation were applied. The core-shell interface was found to be stable during reducing and oxidizing treatment at 250°C as observed by ETEM and in situ X-ray ptychography, although strong changes occurred in the core on a 10 nm scale due to the reduction of copper oxide to metallic copper particles. At 350°C, in situ X-ray ptychography indicated the occurrence of structural changes also on the µm scale, i.e. the core material and parts of the shell undergo restructuring. Nevertheless, the crucial core-shell interface required for full bifunctionality appeared to remain stable. This study demonstrates the potential of these correlative in situ microscopy techniques for hierarchically designed catalysts.

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

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

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Phase stability and large in-plane resistivity anisotropy in the 112-type iron-based superconductor Ca 1 - x La x FeAs 2

DOE PAGES

Kang, Chang-Jong; Birol, Turan; Kotliar, Gabriel

2017-01-17

The recently discovered high-T c superconductor Ca 1-xLa xFeAs 2 is a unique compound not just because of its low-symmetry crystal structure but also because of its electronic structure, which hosts Dirac-like metallic bands resulting from (spacer) zigzag As chains. We present a comprehensive first-principles theoretical study of the electronic and crystal structures of Ca 1-xLa xFeAs 2. After discussing the connection between the crystal structure of the 112 family, which Ca 1-xLa xFeAs 2 is a member of, with the other known structures of Fe pnictide superconductors, we check the thermodynamic phase stability of CaFeAs 2, and similar hyphotheticalmore » compounds SrFeAs 2 and BaFeAs 2 which, we find, are slightly higher in energy. We calculate the optical conductivity of Ca 1-xLa xFeAs 2 using the DFT+DMFT method and predict a large in-plane resistivity anisotropy in the normal phase, which does not originate from electronic nematicity, but is enhanced by the electronic correlations. In particular, we predict a 0.34 eV peak in the yy component of the optical conductivity of the 30% La-doped compound, which corresponds to coherent interband transitions within a fast-dispersing band arising from the zigzag As chains, which are unique to this compound. We also study the Landau free energy for Ca 1-xLa xFeAs 2 including the order parameter relevant for the nematic transition and find that the free energy does not have any extra terms that could induce ferro-orbital order. This explains why the presence of As chains does not broaden the nematic transition in Ca 1-xLa xFeAs 2.« less

Effects of surfactants on the microstructure of porous ceramic scaffolds fabricated by foaming for bone tissue engineering

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

Wang Xi, E-mail: nano-sun@hotmail.com; Ruan Jianming; Chen Qiyuan

2009-06-03

A porous scaffold comprising a {beta}-tricalcium phosphate matrix and bioactive glass powders was fabricated by foaming method and the effects of surfactants as foaming agent on microstructure of scaffolds were investigated. Foaming capacity and foam stability of different surfactants in water firstly were carried out to evaluate their foam properties. The porous structure and pore size distribution of the scaffolds were systematically characterized by scanning electron microscopy (SEM) and an optical microscopy connected to an image analyzer. The results showed that the foam stability of surfactant has more remarkable influence on their microstructure such as pore shape, size and interconnectivitymore » than the foaming ability of one. Porous scaffolds fabricated using nonionic surfactant Tween 80 with large foam stability exhibited higher open and total porosities, and fully interconnected porous structure with a pore size of 750-850 {mu}m.« less

Enhanced stabilization of collagen by furfural.

PubMed

Lakra, Rachita; Kiran, Manikantan Syamala; Usha, Ramamoorthy; Mohan, Ranganathan; Sundaresan, Raja; Korrapati, Purna Sai

2014-04-01

Furfural (2-furancarboxaldehyde), a product derived from plant pentosans, has been investigated for its interaction with collagen. Introduction of furfural during fibril formation enhanced the thermal and mechanical stability of collagen. Collagen films treated with furfural exhibited higher denaturation temperature (Td) (p<0.04) and showed a 3-fold increase in Young's modulus (p<0.04) at higher concentration. Furfural and furfural treated collagen films did not have any cytotoxic effect. Rheological characterization showed an increase in shear stress and shear viscosity with increasing shear rate for treated collagen. Circular dichroism (CD) studies indicated that the furfural did not have any impact on triple helical structure of collagen. Scanning electron microscopy (SEM) of furfural treated collagen exhibited small sized porous structure in comparison with untreated collagen. Thus this study provides an alternate ecologically safe crosslinking agent for improving the stability of collagen for biomedical and industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Electronic structure, stability and magnetic properties of small M1-2Cr (M = Fe, Co, and Ni) alloy encapsulated inside a (BN)48 cage

NASA Astrophysics Data System (ADS)

Liang, Wenjuan; Jia, Jianfeng; Lv, Jin; Wu, Haishun

2015-09-01

The geometrical structure and magnetic properties of M1-2Cr (M = Fe, Co, and Ni) alloy clusters inside a (BN)48 cage were calculated at the BPW91/LANL2DZ level of theory. The doping with Cr significantly changed the magnetic properties of the transition-metal clusters. When M1-2Cr alloys were placed inside a (BN)48 cage, the alloy clusters interacted strongly with the cage, and the M1-2Cr@(BN)48 clusters showed high stability. Moreover, Cr-doped magnetic metal clusters preferably occupied positions off-center and near the hexagonal rings of (BN)48 cages. Thus, the (BN)48 cages can be used to increase the stability of M1-2Cr alloys, and retain their magnetic nature, except for CoCr and Ni2Cr clusters.

Synthesis and Stability of Lanthanum Superhydrides

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

Geballe, Zachary M.; Liu, Hanyu; Mishra, Ajay K.

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1more » Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.« less

Electromagnetic Machines Which Utilize Microgeometry Field Structures

DTIC Science & Technology

1990-04-01

34Phenomenological Theory of Electret Discharge Including Incomplete Recombination of Ions". Acta Physica Polonica , A50(1)1 1. Mehendru, P.C. (177)(: "Electret...Resonance of Stabilized Electrons in PTFE Coronoelectrets". Physica Status Solidi, (a)90:K71-K74. Lagues, M. (1976): "Les Electrets: des Transducteurs

76 FR 12318 - Submission for OMB Review; Comment Request

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-07

... Number: 0607-0947. Form Number(s): None. All information will be collected electronically. Type of... extend that research to further specify the segments and to learn about their stability and structure. The results of CBAMS II will inform the market research program and communications for Census 2020...

Gold–promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction

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

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here, we report on a structurally ordered Au₁₀Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that via addition of gold atoms PdCo nanoparticles undergo at elevated temperatures an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets. The superior stability of this catalyst compared to platinum after 10,000 potential cycles in alkaline media is attributedmore » to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matters.« less

The Structure of the Mouse Serotonin 5-HT3 Receptor in Lipid Vesicles.

PubMed

Kudryashev, Mikhail; Castaño-Díez, Daniel; Deluz, Cédric; Hassaine, Gherici; Grasso, Luigino; Graf-Meyer, Alexandra; Vogel, Horst; Stahlberg, Henning

2016-01-05

The function of membrane proteins is best understood if their structure in the lipid membrane is known. Here, we determined the structure of the mouse serotonin 5-HT3 receptor inserted in lipid bilayers to a resolution of 12 Å without stabilizing antibodies by cryo electron tomography and subtomogram averaging. The reconstruction reveals protein secondary structure elements in the transmembrane region, the extracellular pore, and the transmembrane channel pathway, showing an overall similarity to the available X-ray model of the truncated 5-HT3 receptor determined in the presence of a stabilizing nanobody. Structural analysis of the 5-HT3 receptor embedded in a lipid bilayer allowed the position of the membrane to be determined. Interactions between the densely packed receptors in lipids were visualized, revealing that the interactions were maintained by the short horizontal helices. In combination with methodological improvements, our approach enables the structural analysis of membrane proteins in response to voltage and ligand gating. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electronic structure of the high-temperature oxide superconductors

NASA Astrophysics Data System (ADS)

Pickett, Warren E.

1989-04-01

Since the discovery of superconductivity above 30 K by Bednorz and Müller in the La copper oxide system, the critical temperature has been raised to 90 K in YBa2Cu3O7 and to 110 and 125 K in Bi-based and Tl-based copper oxides, respectively. In the two years since this Nobel-prize-winning discovery, a large number of electronic structure calculations have been carried out as a first step in understanding the electronic properties of these materials. In this paper these calculations (mostly of the density-functional type) are gathered and reviewed, and their results are compared with the relevant experimental data. The picture that emerges is one in which the important electronic states are dominated by the copper d and oxygen p orbitals, with strong hybridization between them. Photon, electron, and positron spectroscopies provide important information about the electronic states, and comparison with electronic structure calculations indicates that, while many features can be interpreted in terms of existing calculations, self-energy corrections ("correlations") are important for a more detailed understanding. The antiferromagnetism that occurs in some regions of the phase diagram poses a particularly challenging problem for any detailed theory. The study of structural stability, lattice dynamics, and electron-phonon coupling in the copper oxides is also discussed. Finally, a brief review is given of the attempts so far to identify interaction constants appropriate for a model Hamiltonian treatment of many-body interactions in these materials.

Formation of Supported Graphene Oxide: Evidence for Enolate Species.

PubMed

Novotny, Zbynek; Nguyen, Manh-Thuong; Netzer, Falko P; Glezakou, Vassiliki-Alexandra; Rousseau, Roger; Dohnálek, Zdenek

2018-04-18

Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the atomic oxygen (AO) binding and mobility on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared AO functionalities in different Gr regions. The AO diffusion is utilized to establish that in the regions that are close to the metal substrate the terminally bonded enolate groups are strongly preferred over bridge-bonded epoxy groups. No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the local structural, electronic factors and C-Ru bond strengthening/weakening processes that affect the stability of enolate and epoxy species.

Formation of Supported Graphene Oxide: Evidence for Enolate Species

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

Novotny, Zbynek; Nguyen, Manh-Thuong; Netzer, Falko P.

Graphene oxides are promising materials for novel electronic devices or anchoring of the active sites for catalytic applications. Here we focus on understanding the oxygen binding on different regions of graphene (Gr) on Ru(0001). Differences in the Gr/Ru lattices result in the superstructure, which offers an array of distinct adsorption sites. We employ scanning tunneling microscopy and density functional theory to map out the chemical identity and stability of prepared oxygen functionalities in different Gr regions. We demonstrate that in the regions that are close to the metal substrate, the terminally-bonded enolate groups are strongly preferred over bridge-bonded epoxy configurations.more » No oxygen species are observed on the graphene regions that are far from the underlying Ru, indicating their low relative stability. This study provides a clear fundamental basis for understanding the structural and electronic factors that affect the stability of enolate and epoxy species as a function of Gr/Ru interactions.« less

Thermally Stable Cellulose Nanocrystals toward High-Performance 2D and 3D Nanostructures.

PubMed

Jia, Chao; Bian, Huiyang; Gao, Tingting; Jiang, Feng; Kierzewski, Iain Michael; Wang, Yilin; Yao, Yonggang; Chen, Liheng; Shao, Ziqiang; Zhu, J Y; Hu, Liangbing

2017-08-30

Cellulose nanomaterials have attracted much attention in a broad range of fields such as flexible electronics, tissue engineering, and 3D printing for their excellent mechanical strength and intriguing optical properties. Economic, sustainable, and eco-friendly production of cellulose nanomaterials with high thermal stability, however, remains a tremendous challenge. Here versatile cellulose nanocrystals (DM-OA-CNCs) are prepared through fully recyclable oxalic acid (OA) hydrolysis along with disk-milling (DM) pretreatment of bleached kraft eucalyptus pulp. Compared with the commonly used cellulose nanocrystals from sulfuric acid hydrolysis, DM-OA-CNCs show several advantages including large aspect ratio, carboxylated surface, and excellent thermal stability along with high yield. We also successfully demonstrate the fabrication of high-performance films and 3D-printed patterns using DM-OA-CNCs. The high-performance films with high transparency, ultralow haze, and excellent thermal stability have the great potential for applications in flexible electronic devices. The 3D-printed patterns with porous structures can be potentially applied in the field of tissue engineering as scaffolds.

Influence of external extrusion on stability of hydrogen molecule and its chaotic behavior

NASA Astrophysics Data System (ADS)

Jarosik, M. W.; SzczÈ©śniak, R.; Durajski, A. P.; Kalaga, J. K.; Leoński, W.

2018-01-01

We have determined the stability conditions of the hydrogen molecule under the influence of an external force of harmonic-type explicitly dependent on the amplitude (A) and frequency (Ω). The ground state of the molecule has been determined in the framework of the Born-Oppenheimer approximation, whereas the energy of the electronic subsystem has been calculated using the Hubbard model including all two-site electron interactions. The diagram of RT0(A ,Ω) , where RT0 denotes the distance between protons after the fixed initial time T0, allowed us to visualize the area of the instability with the complicated structure. We have shown that the vibrations of the hydrogen molecule have a chaotic nature for some points of the instability region. In addition to the amplitude and frequency of the extrusion, the control parameter of the stability of the molecule is the external force associated with pressure. The increase in its value causes the disappearance of the area of the instability and chaotic vibrations.

Enhancing stability and efficiency of perovskite solar cells with crosslinkable silane-functionalized and doped fullerene

DOE PAGES

Bai, Yang; Dong, Qingfeng; Shao, Yuchuan; ...

2016-10-05

The instability of hybrid perovskite materials due to water and moisture arises as one major challenge to be addressed before any practical application of the demonstrated high efficiency perovskite solar cells. Here we report a facile strategy that can simultaneously enhance the stability and efficiency of p-i-n planar heterojunction-structure perovskite devices. Crosslinkable silane molecules with hydrophobic functional groups are bonded onto fullerene to make the fullerene layer highly water-resistant. Methylammonium iodide is introduced in the fullerene layer for n-doping via anion-induced electron transfer, resulting in dramatically increased conductivity over 100-fold. With crosslinkable silane-functionalized and doped fullerene electron transport layer, themore » perovskite devices deliver an efficiency of 19.5% with a high fill factor of 80.6%. Furthermore, a crosslinked silane-modified fullerene layer also enhances the water and moisture stability of the non-sealed perovskite devices by retaining nearly 90% of their original efficiencies after 30 days’ exposure in an ambient environment.« less

Enhancing stability and efficiency of perovskite solar cells with crosslinkable silane-functionalized and doped fullerene

PubMed Central

Bai, Yang; Dong, Qingfeng; Shao, Yuchuan; Deng, Yehao; Wang, Qi; Shen, Liang; Wang, Dong; Wei, Wei; Huang, Jinsong

2016-01-01

The instability of hybrid perovskite materials due to water and moisture arises as one major challenge to be addressed before any practical application of the demonstrated high efficiency perovskite solar cells. Here we report a facile strategy that can simultaneously enhance the stability and efficiency of p–i–n planar heterojunction-structure perovskite devices. Crosslinkable silane molecules with hydrophobic functional groups are bonded onto fullerene to make the fullerene layer highly water-resistant. Methylammonium iodide is introduced in the fullerene layer for n-doping via anion-induced electron transfer, resulting in dramatically increased conductivity over 100-fold. With crosslinkable silane-functionalized and doped fullerene electron transport layer, the perovskite devices deliver an efficiency of 19.5% with a high fill factor of 80.6%. A crosslinked silane-modified fullerene layer also enhances the water and moisture stability of the non-sealed perovskite devices by retaining nearly 90% of their original efficiencies after 30 days' exposure in an ambient environment. PMID:27703136

Structural and electronic properties of Aun-xPtx (n = 2-14; x ⩽ n) clusters: The density functional theory investigation

NASA Astrophysics Data System (ADS)

Yuan, H. K.; Kuang, A. L.; Tian, C. L.; Chen, H.

2014-03-01

The structural evolutions and electronic properties of bimetallic Aun-xPtx (n = 2-14; x ⩽ n) clusters are investigated by using the density functional theory (DFT) with the generalized gradient approximation (GGA). The monatomic doping Aun-1Pt clusters are emphasized and compared with the corresponding pristine Aun clusters. The results reveal that the planar configurations are favored for both Aun-1Pt and Aun clusters with size up to n = 13, and the former often employ the substitution patterns based on the structures of the latter. The most stable clusters are Au6 and Au6Pt, which adopt regular planar triangle (D3h) and hexagon-ring (D6h) structures and can be regarded as the preferential building units in designing large clusters. For Pt-rich bimetallic clusters, their structures can be obtained from the substitution of Pt atoms by Au atoms from the Ptn structures, where Pt atoms assemble together and occupy the center yet Au atoms prefer the apex positions showing a segregation effect. With respect to pristine Au clusters, AunPt clusters exhibit somewhat weaker and less pronounced odd-even oscillations in the highest occupied and lowest unoccupied molecular-orbital gaps (HOMO-LUMO gap), electron affinity (EA), and ionization potential (IP) due to the partially released electron pairing effect. The analyses of electronic structure indicate that Pt atoms in AuPt clusters would delocalize their one 6s and one 5d electrons to contribute the electronic shell closure. The sp-d hybridizations as well as the d-d interactions between the host Au and dopant Pt atoms result in the enhanced stabilities of AuPt clusters.

Abnormal thermal expansion, multiple transitions, magnetocaloric effect, and electronic structure of Gd{sub 6}Co{sub 4.85}

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

Zhang, Jiliang; Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716; Zheng, Zhigang

2015-10-07

The structure of known Gd{sub 4}Co{sub 3} compound is re-determined as Gd{sub 6}Co{sub 4.85}, adopting the Gd{sub 6}Co{sub 1.67}Si{sub 3} structure type, which is characterized by two disorder Co sites filling the Gd octahedral and a short Gd-Gd distance within the octahedra. The compound shows uniaxial negative thermal expansion in paramagnetic state, significant negative expansion in ferromagnetic state, and positive expansion below ca. 140 K. It also exhibits large magnetocaloric effect, with an entropy change of −6.4 J kg{sup −1} K{sup −1} at 50 kOe. In the lattice of the compound, Co atoms at different sites show different spin states. It was confirmed by themore » X-ray photoelectron spectra and calculation of electronic structure and shed lights on the abnormal thermal expansion. The stability of such compound and the origin of its magnetism are also discussed based on measured and calculated electronic structures.« less

Formation and electronic properties of palladium hydrides and palladium-rhodium dihydride alloys under pressure.

PubMed

Yang, Xiao; Li, Huijian; Ahuja, Rajeev; Kang, Taewon; Luo, Wei

2017-06-14

We present the formation possibility for Pd-hydrides and Pd-Rh hydrides system by density functional theory (DFT) in high pressure upto 50 GPa. Calculation confirmed that PdH 2 in face-centered cubic (fcc) structure is not stable under compression that will decomposition to fcc-PdH and H 2 . But it can be formed under high pressure while the palladium is involved in the reaction. We also indicate a probably reason why PdH 2 can not be synthesised in experiment due to PdH is most favourite to be formed in Pd and H 2 environment from ambient to higher pressure. With Rh doped, the Pd-Rh dihydrides are stabilized in fcc structure for 25% and 75% doping and in tetragonal structure for 50% doping, and can be formed from Pd, Rh and H 2 at high pressure. The electronic structural study on fcc type Pd x Rh 1-x H 2 indicates the electronic and structural transition from metallic to semi-metallic as Pd increased from x = 0 to 1.

High spatial resolution PEELS characterization of FeAl nanograins prepared by mechanical alloying

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

Valdre, G.; Botton, G.A.; Brown, L.M.

The authors investigate the nanograin ``chemical`` structure in a nanostructured material of possible industrial application (Fe-Al system) prepared by conventional mechanical alloying via ball milling in argon atmosphere. They restrict themselves to the structural and nanochemical behavior of ball-milled nanocrystalline Fe-Al powders with atomic composition Fe{sub 3}Al, corresponding to a well-known intermetallic compound of the Fe-Al system. Scanning transmission electron microscopy (STEM) equipped with a parallel detection electron energy loss spectrometer (PEELS) has provided an insight on the ``chemical`` structure of both nanograins and their surface at a spatial resolution of better than 1 nm. The energy loss near edgemore » structure of the Al L loss reveals that the Al coordination is similar to a B2 compound and the oxidation of the powder during processing may play a significant role in the stabilization of the intermetallic phases. Conventional transmission electron microscopy (TEM) was used for the structural characterization of the material after the ball milling; powder X-ray diffraction (XRD) aided the investigation.« less

Structural, electronic and spectral properties of carborane-containing boron dipyrromethenes (BODIPYs): A first-principles study

NASA Astrophysics Data System (ADS)

Li, Xiaojun

2017-10-01

In this work, we reported the geometrical structures, electronic and spectral properties of the carborane-containing BODIPYs complexes using the density functional theory calculations. In two structures, the calculated main bond lengths and bond angels of structural framework are consistent with X-ray experiment, and the two BODIPYs complexes are thermodynamically and kinetically stable. The strongest DOS band is mainly dominated by the Bsbnd B and Bsbnd H σ-bonds of carborane fragment, whereas the π-type MOs on the pyrromethene fragment contribute to the high-energy DOS bands. Analysis of the AdNDP chemical bonding indicates that the carborane cage can be stabilized by eleven delocalized 3csbnd 2e and two delocalized 4csbnd 2e σ-bonds, while the pyrromethene fragment corresponds to five delocalized 3csbnd 2e π-bonds. In addition, the main characteristic peaks of the two simulated IR spectra for the BODIPYs complexes are properly assigned. Hopefully, all these results will be helpful for understanding the electronic structures, and further stimulate the study on the biological and medical applications.

Formation Energies and Electronic Properties of Vanadium Carbides Found in High Strength Steel Alloys

NASA Astrophysics Data System (ADS)

Limmer, Krista; Medvedeva, Julia

2013-03-01

Carbide formation and stabilization in steels is of great interest owing to its effect on the microstructure and properties of the Fe-based alloys. The appearance of carbides with different metal/C ratios strongly depends on the carbon concentration, alloy composition as well as the heat treatment. Strong carbide-forming elements such as Ti, V, and Nb have been used in microalloyed steels; with VC showing an increased solubility in the iron matrix as compared with TiC and NbC. This allows for dissolution of the VC into the steel during heating and fine precipitation during cooling. In addition to VC, the primary vanadium carbide with cubic structure, a wide range of non-stoichiometric compositions VCy with y varying from 0.72 to 0.88, has been observed. This range includes two ordered compounds, V8C7 and V6C5. In this study, first-principles density functional theory (DFT) is employed to examine the stability of the binary carbides by calculating their formation energies. We compare the local structures (atomic coordination, bond distances and angles) and the density of states in optimized geometries of the carbides. Further, the effect of alloying additions, such as niobium and titanium, on the carbide stabilization is investigated. We determine the energetically preferable substitutional atom location in each carbide and study the impurity distribution as well as its role in the carbide formation energy and electronic structure.

Dimensionality-Driven Metal-Insulator Transition in Spin-Orbit-Coupled SrIrO3

NASA Astrophysics Data System (ADS)

Schütz, P.; Di Sante, D.; Dudy, L.; Gabel, J.; Stübinger, M.; Kamp, M.; Huang, Y.; Capone, M.; Husanu, M.-A.; Strocov, V. N.; Sangiovanni, G.; Sing, M.; Claessen, R.

2017-12-01

Upon reduction of the film thickness we observe a metal-insulator transition in epitaxially stabilized, spin-orbit-coupled SrIrO3 ultrathin films. By comparison of the experimental electronic dispersions with density functional theory at various levels of complexity we identify the leading microscopic mechanisms, i.e., a dimensionality-induced readjustment of octahedral rotations, magnetism, and electronic correlations. The astonishing resemblance of the band structure in the two-dimensional limit to that of bulk Sr2 IrO4 opens new avenues to unconventional superconductivity by "clean" electron doping through electric field gating.

Three Axes MEMS Combined Sensor for Electronic Stability Control System

NASA Astrophysics Data System (ADS)

Jeong, Heewon; Goto, Yasushi; Aono, Takanori; Nakamura, Toshiaki; Hayashi, Masahide

A microelectromechanical systems (MEMS) combined sensor measuring two-axis accelerations and an angular rate (rotation) has been developed for an electronic stability control system of automobiles. With the recent trend to mount the combined sensors in the engine compartment, the operation temperature range increased drastically, with the request of immunity to environmental disturbances such as vibration. In this paper, we report the combined sensor which has a gyroscopic part and two acceleration parts in single die. A deformation-robust MEMS structure has been adopted to achieve stable operation under wide temperature range (-40 to 125°C) in the engine compartment. A package as small as 10 × 19 × 4 mm is achieved by adopting TSV (through silicon via) and WLP (wafer-level package) technologies with enough performance as automotive grade.

Synthesis, crystal structure and electronic structure of the binary phase Rh2Cd5

NASA Astrophysics Data System (ADS)

Koley, Biplab; Chatterjee, S.; Jana, Partha P.

2017-02-01

A new phase in the Rh-Cd binary system - Rh2Cd5 has been identified and characterized by single crystal X-ray diffraction and Energy dispersive X-ray analysis. The stoichiometric compound Rh2Cd5 crystallizes with a unit cell containing 14 atoms, in the orthorhombic space group Pbam (55). The crystal structure of Rh2Cd5 can be described as a defect form of the In3Pd5 structure with ordered vacancies, formed of two 2D atomic layers with the stacking sequence: ABAB. The A type layers consist of (3.6.3.6)-Kagomé nets of Cd atoms while the B type layers consist of (35) (37)- nets of both Cd and Rh atoms. The stability of this line phase is investigated by first principle electronic structure calculations on the model of ordered Rh2Cd5.

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory

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

Weathersby, S. P.; Brown, G.; Chase, T. F.

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition ratemore » with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.« less

Mega-electron-volt ultrafast electron diffraction at SLAC National Accelerator Laboratory.

PubMed

Weathersby, S P; Brown, G; Centurion, M; Chase, T F; Coffee, R; Corbett, J; Eichner, J P; Frisch, J C; Fry, A R; Gühr, M; Hartmann, N; Hast, C; Hettel, R; Jobe, R K; Jongewaard, E N; Lewandowski, J R; Li, R K; Lindenberg, A M; Makasyuk, I; May, J E; McCormick, D; Nguyen, M N; Reid, A H; Shen, X; Sokolowski-Tinten, K; Vecchione, T; Vetter, S L; Wu, J; Yang, J; Dürr, H A; Wang, X J

2015-07-01

Ultrafast electron probes are powerful tools, complementary to x-ray free-electron lasers, used to study structural dynamics in material, chemical, and biological sciences. High brightness, relativistic electron beams with femtosecond pulse duration can resolve details of the dynamic processes on atomic time and length scales. SLAC National Accelerator Laboratory recently launched the Ultrafast Electron Diffraction (UED) and microscopy Initiative aiming at developing the next generation ultrafast electron scattering instruments. As the first stage of the Initiative, a mega-electron-volt (MeV) UED system has been constructed and commissioned to serve ultrafast science experiments and instrumentation development. The system operates at 120-Hz repetition rate with outstanding performance. In this paper, we report on the SLAC MeV UED system and its performance, including the reciprocal space resolution, temporal resolution, and machine stability.

A novel thin-film transistor with step gate-overlapped lightly doped drain and raised source/drain design

NASA Astrophysics Data System (ADS)

Chien, Feng-Tso; Chen, Jian-Liang; Chen, Chien-Ming; Chen, Chii-Wen; Cheng, Ching-Hwa; Chiu, Hsien-Chin

2017-11-01

In this paper, a novel step gate-overlapped lightly doped drain (GOLDD) with raised source/drain (RSD) structure (SGORSD) is proposed for TFT electronic device application. The new SGORSD structure could obtain a low electric field at channel near the drain side owing to a step GOLDD design. Compared to the conventional device, the SGORSD TFT exhibits a better kink effect and higher breakdown performance due to the reduced drain electric field (D-EF). In addition, the leakage current also can be suppressed. Moreover, the device stability, such as the threshold voltage shift and drain current degradation under a high gate bias, is improved by the design of SGORSD structure. Therefore, this novel step GOLDD structure can be a promising design to be used in active-matrix flat panel electronics.

Stable operating regime for traveling wave devices

DOEpatents

Carlsten, Bruce E.

2000-01-01

Autophase stability is provided for a traveling wave device (TWD) electron beam for amplifying an RF electromagnetic wave in walls defining a waveguide for said electromagnetic wave. An off-axis electron beam is generated at a selected energy and has an energy noise inherently arising from electron gun. The off-axis electron beam is introduced into the waveguide. The off-axis electron beam is introduced into the waveguide at a second radius. The waveguide structure is designed to obtain a selected detuning of the electron beam. The off-axis electron beam has a velocity and the second radius to place the electron beam at a selected distance from the walls defining the waveguide, wherein changes in a density of the electron beam due to the RF electromagnetic wave are independent of the energy of the electron beam to provide a concomitant stable operating regime relative to the energy noise.

Computational research on lithium ion battery materials

NASA Astrophysics Data System (ADS)

Tang, Ping

Crystals of LiFePO4 and related materials have recently received a lot of attention due to their very promising use as cathodes in rechargeable lithium ion batteries. This thesis studied the electronic structures of FePO 4 and LiMPO4, where M=Mn, Fe, Co and Ni within the framework of density-functional theory. The first study compared the electronic structures of the LiMPO 4 and FePO4 materials in their electrochemically active olivine form, using the LAPW (linear augmented plane wave) method [1]. A comparison of results for various spin configurations suggested that the ferromagnetic configuration can serve as a useful approximation for studying general features of these systems. The partial densities of states for the LiMPO4 materials are remarkably similar to each other, showing the transition metal 3d states forming narrow bands above the O 2p band. By contrast, in absence of Li, the majority spin transition metal 3d states are well-hybridized with the O 2p band in FePO4. The second study compared the electronic structures of FePO4 in several crystal structures including an olivine, monoclinic, quartz-like, and CrVO4-like form [2,3]. For this work, in addition to the LAPW method, PAW (Projector Augmented Wave) [4], and PWscf (plane-wave pseudopotential) [5] methods were used. By carefully adjusting the computational parameters, very similar results were achieved for the three independent computational methods. Results for the relative stability of the four crystal structures are reported. In addition, partial densities of state analyses show qualitative information about the crystal field splittings and bond hybridizations and help rationalize the understanding of the electrochemical and stability properties of these materials.

Angle Resolved Photoelectron and Auger Electron Diffraction as a Structural Probe for Surfaces, Interfaces, and Epitaxial Films.

NASA Astrophysics Data System (ADS)

Li, Hong

The recently developed techniques of angle-resolved photoelectron and Auger electron diffraction (ARXPD/AED) have shown promise in identifying the structures of epitaxial films. This is due to the realization that electrons scattered by other atoms are enhanced along the forward direction. In this dissertation research, we have further investigated the capabilities of the ARXPD/AED technique. First, the complete polar angle distribution of the Auger electron intensity from Cu(001) was measured from the (100) to the (110) azimuth. The presentation of the ARAED in the form of a contour map clearly shows the relationship of the constructive and destructive interference of electron scattering to the crystallographic index of the crystal. Secondly, the angular distributions of electron emissions with initial states of 3p, 3d, 4d, and the Auger emission with electron kinetic energies ranging from 348 eV to 1477 eV were measured for single crystal Ag(001). The results show that all of these electron emissions have similar electron forward scattering enhancements along the directions of nearest and next nearest neighbour atoms in the crystal. The forward scattering enhancements do not shift as the electron kinectic energy changes. The ARXPD/AED combined with low energy electron diffraction (LEED) has been demonstrated to be a very powerful technique in probing both the long range order and the short range order of the epitaxial films. The epitaxial films studied include Co on Cu(001), Fe on Ag(001), Co on Ag(001), and Co on an ultra-thin film of Fe(001), which was epitaxially grown on Ag(001). We find that up to 20 ML thickness of high quality metastable fcc Co can be stabilized on Cu(001) at room temperature. We have directly verified that the Fe on Ag(001) is bcc. The Co on Ag(001) is neither bcc nor fcc for coverages of less than 3 ML. Thick films of Co on Ag(001) are disordered, of which a very small portion has a local structure of bcc. The bcc Co phases has been successfully stabilized on an ultra-thin film of bcc Fe(001). This is the first example of bcc Co epitaxially grown on a metal substrate at room temperature.

Phase stabilities of pyrite-related MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te): A systematic DFT study

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

Bachhuber, Frederik; School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland; Krach, Alexander

2015-03-15

Pyrite-type and related systems appear for a wide range of binary and ternary combinations of transition metals and main group elements that form Zintl type dumbbell anion units. Those representatives with 20 valence electrons exhibit an extraordinary structural flexibility and interesting properties as low-gap semiconductors or thermoelectric and electrode materials. This work is devoted to the systematic exploration of novel compounds within the class of MTCh compounds (M=Ni, Pd, Pt; T=Si, Ge, Sn, Pb; Ch=S, Se, Te) by means of density functional calculations. Their preferred structures are predicted from an extended scheme of colored pyrites and marcasites. To determine theirmore » stabilities, competing binary MT{sub 2} and MCh{sub 2} boundary phases are taken into account as well as ternary M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} systems. Recently established stability diagrams are presented to account for MTCh ordering phenomena with a focus on a not-yet-reported ordering variant of the NiAs{sub 2} type. Due to the good agreement with experimental data available for several PtTCh systems, the predictions for the residual systems are considered sufficiently accurate. - Graphical abstract: Compositional and structural stability of MTCh compounds is investigated from first principle calculations. A conceptional approach is presented to study and predict novel stable and metastable compounds and structures of low gap semiconductors with TCh dumbbell units that are isoelectronic and structurally related to pyrite (FeS{sub 2}). - Highlights: • Study of compositional stability of MTCh vs. M{sub 3}T{sub 2}Ch{sub 2} and M{sub 2}T{sub 3}Ch{sub 3} compounds. • Study of structural stability of known and novel MTCh compounds. • Prediction of novel stable and metastable structures and compounds isoelectronic to pyrite, FeS{sub 2}.« less

Structure and dynamics of the umagnetized plasma around comet 67P/CG

NASA Astrophysics Data System (ADS)

Henri, P.; Vallières, X.; Gilet, N.; Hajra, R.; Moré, J.; Goetz, C.; Richter, I.; Glassmeier, K. H.; Galand, M. F.; Heritier, K. L.; Eriksson, A. I.; Nemeth, Z.; Tsurutani, B.; Rubin, M.; Altwegg, K.

2016-12-01

At distances close enough to the Sun, when comets are characterised by a significant outgassing, the cometary neutral density may become large enough for both the cometary plasma and the cometary gas to be coupled, through ion-neutral and electron-neutral collisions. This coupling enables the formation of an unmagnetised expanding cometary ionosphere around the comet nucleus, also called diamagnetic cavity, within which the solar wind magnetic field cannot penetrate. The instruments of the Rosetta Plasma Consortium (RPC), onboard the Rosetta Orbiter, enable us to better constrain the structure, dynamics and stability of the plasma around comet 67P/CG. Recently, magnetic field measurements (RPC-MAG) have shown the existence of such a diamagnetic region around comet 67P/CG [Götz et al., 2016]. Contrary to a single, large scale, diamagnetic cavity such as what was observed around comet Halley, Rosetta have crossed several diamagnetic structures along its trajectory around comet 67P/CG. Using electron density measurements from the Mutual Impedance Probe (RPC-MIP) during the different diamagnetic cavity crossings, identified by the flux gate magnetometer (RPC-MAG), we map the unmagnetised plasma density around comet 67P/CG. Our aims is to better constrain the structure, dynamics and stability of this inner cometary plasma layer characterised by cold electrons (as witnessed by the Langmuir Probes RPC-LAP). The ionisation ratio in these unmagnetised region(s) is computed from the measured electron (RPC-MIP) and neutral gas (ROSINA/COPS) densities. In order to assess the importance of solar EUV radiation as a source of ionisation, the observed electron density will be compared to a the density expected from an ionospheric model taking into account solar radiation absorption. The crossings of diamagnetic region(s) by Rosetta show that the unmagnetised cometary plasma is particularly homogeneous, compared to the highly dynamical magnetised plasma observed in adjacent magnetised regions. Moreover, during the crossings of multiple, successive diamagnetic region(s) over time scales of tens of minutes or hours, the plasma density is almost identical in the different unmagnetised regions, suggesting that these unmagnetised regions may be a single diamagnetic structure crossed several times by Rosetta.

Chemoselective Hydrodehalogenation of Organic Halides Utilizing Two-Dimensional Anionic Electrons of Inorganic Electride [Ca2N]+·e^.

PubMed

Kim, Ye Ji; Kim, Sun Min; Yu, Chunghyeon; Yoo, YoungMin; Cho, Eun Jin; Yang, Jung Woon; Kim, Sung Wng

2017-01-31

Halogenated organic compounds are important anthropogenic chemicals widely used in chemical industry, biology, and pharmacology; however, the persistence and inertness of organic halides cause human health problems and considerable environmental pollution. Thus, the elimination or replacement of halogen atoms with organic halides has been considered a central task in synthetic chemistry. In dehalogenation reactions, the consecutive single-electron transfer from reducing agents generates the radical and corresponding carbanion and thus removes the halogen atom as the leaving group. Herein, we report a new strategy for an efficient chemoselective hydrodehalogenation through the formation of stable carbanion intermediates, which are simply achieved by using highly mobile two-dimensional electrons of inorganic electride [Ca 2 N] + ·e - with effective electron transfer ability. The consecutive single-electron transfer from inorganic electride [Ca 2 N] + ·e - stabilized free carbanions, which is a key step in achieving the selective reaction. Furthermore, a determinant more important than leaving group ability is the stability control of free carbanions according to the s character determined by the backbone structure. We anticipate that this approach may provide new insight into selective chemical formation, including hydrodehalogenation.

Structural, electronic and vibrational properties of small GaxNy (x+y = 2 5) nanoclusters: a B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Yadav, P. S.; Yadav, R. K.; Agrawal, B. K.

2007-02-01

An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, GaxNy (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in experiments.

Structural, electronic and vibrational properties of GexCy (x+y=2-5) nanoclusters: A B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Goswami, Sohini; Saha, Sushmita; Yadav, R. K.

2015-11-01

An ab-initio study of the stability, structural and electronic properties has been made for 84 germanium carbide nanoclusters, GexCy (x+y=2-5). The configuration possessing the maximum value of final binding energy (FBE), among the various configurations corresponding to a fixed x+y=n value, is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize fully the geometries of the nanoclusters. The binding energies (BE), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps have been obtained for all the clusters and the bond lengths have been reported for the most stable clusters. We have considered the zero point energy (ZPE) corrections. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have also been investigated for the most stable structures. The configurations containing the carbon atoms in majority are seen to be the most stable structures. The strong C-C bond has important role in stabilizing the clusters. For the clusters containing one germanium atom and all the other as carbon atoms, the BE increases monotonically with the number of the carbon atoms. The HOMO-LUMO gap, IPs and EAs fluctuates with increase in the number of atoms. The nanoclusters containing even number of carbon atoms have large HOMO-LUMO gaps and IPs, whereas the nanoclusters containing even number of carbon atoms have small EAs. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA). The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in the experiments.

Electronic, phonon and superconducting properties of LaPtBi half-Heusler compound

NASA Astrophysics Data System (ADS)

Shrivastava, Deepika; Sanyal, Sankar P.

2018-05-01

In the framework of density functional theory based on plane wave pseudopotential method and linear response technique, we have studied the electronic, phonon and superconducting properties of LaPtBi half-Heusler compound. The electronic band structure and density of states show that it is gapless semiconductor which is consistent with previous results. The positive phonon frequencies confirm the stability of this compound in cubic MgAgAs phase. Superconductivity is studied in terms of Eliashberg spectral function (α2F(ω)), electron-phonon coupling constants (λ). The value of electron-phonon coupling parameter is found to be 0.41 and the superconducting transition temperature is calculated to be 0.76 K, in excellent agreement with the experimentally reported values.

Effect of charge and composition on the structural fluxionality and stability of nine atom tin-bismuth Zintl analogues.

PubMed

Gupta, Ujjwal; Reber, Arthur C; Clayborne, Penee A; Melko, Joshua J; Khanna, Shiv N; Castleman, A W

2008-12-01

Synergistic studies of bismuth doped tin clusters combining photoelectron spectra with first principles theoretical investigations establish that highly charged Zintl ions, observed in the condensed phase, can be stabilized as isolated gas phase clusters through atomic substitution that preserves the overall electron count but reduces the net charge and thereby avoids instability because of coulomb repulsion. Mass spectrometry studies reveal that Sn(8)Bi(-), Sn(7)Bi(2)(-), and Sn(6)Bi(3)(-) exhibit higher abundances than neighboring species, and photoelectron spectroscopy show that all of these heteroatomic gas phase Zintl analogues (GPZAs) have high adiabatic electron detachment energies. Sn(6)Bi(3)(-) is found to be a particularly stable cluster, having a large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. Theoretical calculations demonstrate that the Sn(6)Bi(3)(-) cluster is isoelectronic with the well know Sn(9)(-4) Zintl ion; however, the fluxionality reported for Sn(9)(-4) is suppressed by substituting Sn atoms with Bi atoms. Thus, while the electronic stability of the clusters is dominated by electron count, the size and position of the atoms affects the dynamics of the cluster as well. Substitution with Bi enlarges the cage compared with Sn(9)(-4) making it favorable for endohedral doping, findings which suggest that these cages may find use for building blocks of cluster assembled materials.

Aromaticity and Antiaromaticity in Zintl Clusters

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

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Atomistic modeling and HAADF investigations of misfit and threading dislocations in GaSb/GaAs hetero-structures for applications in high electron mobility transistors

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

Ruterana, Pierre, E-mail: pierre.ruterana@ensicaen.fr; Wang, Yi, E-mail: pierre.ruterana@ensicaen.fr; Chen, Jun, E-mail: pierre.ruterana@ensicaen.fr

A detailed investigation on the misfit and threading dislocations at GaSb/GaAs interface has been carried out using molecular dynamics simulation and quantitative electron microscopy techniques. The sources and propagation of misfit dislocations have been elucidated. The nature and formation mechanisms of the misfit dislocations as well as the role of Sb on the stability of the Lomer configuration have been explained.

Electronic speckle pattern interferometry using vortex beams.

PubMed

Restrepo, René; Uribe-Patarroyo, Néstor; Belenguer, Tomás

2011-12-01

We show that it is possible to perform electronic speckle pattern interferometry (ESPI) using, for the first time to our knowledge, vortex beams as the reference beam. The technique we propose is easy to implement, and the advantages obtained are, among others, environmental stability, lower processing time, and the possibility to switch between traditional ESPI and spiral ESPI. The experimental results clearly show the advantages of using the proposed technique for deformation studies of complex structures. © 2011 Optical Society of America

Aromaticity and Antiaromaticity in Zintl Clusters

DOE PAGES

Sun, Zhong -Ming; Liu, Chao; Popov, Ivan Aleksandrovich; ...

2018-05-18

Originally, the concepts of aromaticity and antiaromaticity were introduced to explain the stability and reactivity of unsaturated organic compounds. Since then, they have been extended to other species with delocalized electrons including various saturated systems, organometallic compounds, and even inorganic clusters and molecules. In this study, we focus on the most recent progress of using these concepts to guide experimental synthesis and rationalize geometrical and electronic structures of a particular family of polyanions composed of Group 14 and 15 elements, namely Zintl clusters.

Computational investigation of half-Heusler compounds for spintronics applications

NASA Astrophysics Data System (ADS)

Ma, Jianhua; Hegde, Vinay I.; Munira, Kamaram; Xie, Yunkun; Keshavarz, Sahar; Mildebrath, David T.; Wolverton, C.; Ghosh, Avik W.; Butler, W. H.

2017-01-01

We present first-principles density functional calculations of the electronic structure, magnetism, and structural stability of 378 XYZ half-Heusler compounds (with X = Cr, Mn, Fe, Co, Ni, Ru, Rh; Y = Ti, V, Cr, Mn, Fe, Ni; Z = Al, Ga, In, Si, Ge, Sn, P, As, Sb). We find that a "Slater-Pauling gap" in the density of states (i.e., a gap or pseudogap after nine states in the three atom primitive cell) in at least one spin channel is a common feature in half-Heusler compounds. We find that the presence of such a gap at the Fermi energy in one or both spin channels contributes significantly to the stability of a half-Heusler compound. We calculate the formation energy of each compound and systematically investigate its stability against all other phases in the open quantum materials database (OQMD). We represent the thermodynamic phase stability of each compound as its distance from the convex hull of stable phases in the respective chemical space and show that the hull distance of a compound is a good measure of the likelihood of its experimental synthesis. We find low formation energies and mostly correspondingly low hull distances for compounds with X = Co, Rh, or Ni, Y = Ti or V, and Z = P, As, Sb, or Si. We identify 26 18-electron semiconductors, 45 half-metals, and 34 near half-metals with negative formation energy that follow the Slater-Pauling rule of three electrons per atom. Our calculations predict several new, as-yet unknown, thermodynamically stable phases, which merit further experimental exploration—RuVAs, CoVGe, FeVAs in the half-Heusler structure, and NiScAs, RuVP, RhTiP in the orthorhombic MgSrSi-type structure. Further, two interesting zero-moment half-metals, CrMnAs and MnCrAs, are calculated to have negative formation energy. In addition, our calculations predict a number of hitherto unreported semiconducting (e.g., CoVSn and RhVGe), half-metallic (e.g., RhVSb), and near half-metallic (e.g., CoFeSb and CoVP) half-Heusler compounds to lie close to the respective convex hull of stable phases, and thus may be experimentally realized under suitable synthesis conditions, resulting in potential candidates for various semiconducting and spintronics applications.

Structure, stability, and electronic properties of AlP nanocages evolved from the world's smallest caged fullerene C20: A computational study at DFT

NASA Astrophysics Data System (ADS)

Baei, Mohammad T.; Koohi, Maryam; Shariati, Minoo

2018-05-01

The stability, geometry, and electronic properties of C20 and its AlnPnC20-2n heterofullerenic derivatives where n = 1-10 are probed, at density functional theory (DFT). Vibrational frequency calculations show that exclusive of Al6P6C8 and Al10P8C2, other species are true minima. Exploring of the optimized structures demonstrates the shrinkage of Cdbnd C double bonds to compensate for the longer Csbnd Al, Csbnd P and Alsbnd P single bonds. The calculated binding energy, HOMO-LUMO gap and nucleus independent chemical shift at the cage center (NICS (0)) of Al1P1C18 shows it the most stable structure. While substituting of 1, 2, 3, 4, 6, and 7 Alsbnd P units enhances kinetic stability of the resulting heterofullerenes against electronic excitations via increasing their HOMO-LUMO gap, doping of 5, 8, 9, and 10 Alsbnd P units increases the conductivity of heterofullerenes through decreasing their band gap. Substitutional doping leads to a high point charge upon the surfaces of all derivatives, especially the highest delocalization on Al6P6C8, with range of -2.056 to -1.261 charged carbons, +1.493 to +1.586 charged aluminums, and +0.513 to +0.801 charged phosphor atoms, followed by Al4P4C12. These high charge distributions on the surfaces of the studied analogous can develop their storage capacity and henceforth characterize them worthy of investigation for hydrogen storage. Also, Al1P1C18, Al2P2C16, and Al10P10 are shown as the most aromatic and anti-aromatic nanocages with NICS (0) of -41.60, -39.82, and +22.59 ppm, respectively, compared to C20 (-19.61 ppm). The computed higher dipole moment of Al1P1C18 and Al5P5C10 (4.06 and 3.29 Debye, respectively) exhibits higher reactivity potential and greater affinity of them to more polar solvents. Thus, in both gas phase and polar solvent, Al1P1C18 structure is expected to be stabilized to a greater extent than the other species, which has been confirmed by the thermodynamic and kinetic data.

Electronic Structure and Bonding in Transition Metal Inorganic and Organometallic Complexes: New Basis Sets, Linear Semibridging Carbonyls and Thiocarbonyls, and Oxidative Addition of Molecular Hydrogen to Square - Iridium Complexes.

NASA Astrophysics Data System (ADS)

Sargent, Andrew Landman

Approximate molecular orbital and ab initio quantum chemical techniques are used to investigate the electronic structure, bonding and reactivity of several transition metal inorganic and organometallic complexes. Modest-sized basis sets are developed for the second-row transition metal atoms and are designed for use in geometry optimizations of inorganic and organometallic complexes incorporating these atoms. The basis sets produce optimized equilibrium geometries which are slightly better than those produced with standard 3-21G basis sets, and which are significantly better than those produced with effective core potential basis sets. Linear semibridging carbonyl ligands in heterobimetallic complexes which contain a coordinatively unsaturated late transition metal center are found to accept electron density from, rather than donate electron density to, these centers. Only when the secondary metal center is a coordinatively unsaturated early transition metal center does the semibridging ligand donate electron density to this center. Large holes in the d shell around the metal center are more prominent and prevalent in early than in late transition metal centers, and the importance of filling in these holes outweighs the importance of mitigating the charge imbalance due to the dative metal-metal interaction. Semibridging thiocarbonyl ligands are more effective donors of electron density than the carbonyl ligands since the occupied donor orbitals of pi symmetry are higher in energy. The stereoselectivity of H_2 addition to d^8 square-planar transition metal complexes is controlled by the interactions between the ligands in the plane of addition and the concentrations of electronic charge around the metal center as the complex evolves from a four-coordinate to a six-coordinate species. Electron -withdrawing ligands help stabilize the five-coordinate species while strong electron donor ligands contribute only to the destabilizing repulsive interactions. The relative thermodynamic stabilities of the final complexes can be predicted based on the relative orientations of the strongest sigma-donor ligands.

One stone, two birds: silica nanospheres significantly increase photocatalytic activity and colloidal stability of photocatalysts

NASA Astrophysics Data System (ADS)

Rasamani, Kowsalya D.; Foley, Jonathan J., IV; Sun, Yugang

2018-03-01

Silver-doped silver chloride [AgCl(Ag)] nanoparticles represent a unique class of visible-light-driven photocatalysts, in which the silver dopants introduce electron-abundant mid-gap energy levels to lower the bandgap of AgCl. However, free-standing AgCl(Ag) nanoparticles, particularly those with small sizes and large surface areas, exhibit low colloidal stability and low compositional stability upon exposure to light irradiation, leading to easy aggregation and conversion to metallic silver and thus a loss of photocatalytic activity. These problems could be eliminated by attaching the small AgCl(Ag) nanoparticles to the surfaces of spherical dielectric silica particles with submicrometer sizes. The high optical transparency in the visible spectral region (400-800 nm), colloidal stability, and chemical/electronic inertness displayed by the silica spheres make them ideal for supporting photocatalysts and significantly improving their stability. The spherical morphology of the dielectric silica particles can support light scattering resonances to generate significantly enhanced electric fields near the silica particle surfaces, on which the optical absorption cross-section of the AgCl(Ag) nanoparticles is dramatically increased to promote their photocatalytic activity. The hybrid silica/AgCl(Ag) structures exhibit superior photocatalytic activity and stability, suitable for supporting photocatalysis sustainably; for instance, their efficiency in the photocatalytic decomposition of methylene blue decreases by only ˜9% even after ten cycles of operation.

Electronic Structure of a Self-Assembled Monolayer with Two Surface Anchors: 6-Mercaptopurine on Au(111).

PubMed

Fernández, Cynthia C; Pensa, Evangelina; Carro, Pilar; Salvarezza, Roberto; Williams, Federico J

2018-05-22

The electronic structure of aromatic and aliphatic thiols on Au(111) has been extensively studied in relation to possible applications in molecular electronics. In this work, the effect on the electronic structure of an additional anchor to the S-Au bond using 6-mercaptopurine as a model system has been investigated. Results from X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, and density functional theory (DFT) confirm that this molecule adsorbs on Au(111) with S-Au and iminic N-Au bonds. Combined ultraviolet photoelectron spectroscopy and DFT data reveal that formation of the 6MP self-assembled monolayer generates a molecular dipole perpendicular to the surface, with negative charges residing at the metal/monolayer interface and positive charges at the monolayer/vacuum interface, which lowers the substrate work function. Scanning tunneling microscopy shows two surface molecular domains: a well-ordered rectangular lattice where molecules are tilted on average 30° with respect to the substrate and aligned 6MP islands where molecules are standing upright. Finally, we found a new electronic state located at -1.7 eV with respect to the Fermi level that corresponds to a localized π molecular state, while the state corresponding to the N-Au bond is hybridized with Au d electrons and stabilized at much lower energies (-3 eV).

Computer-Assisted Inverse Design of Inorganic Electrides

NASA Astrophysics Data System (ADS)

Zhang, Yunwei; Wang, Hui; Wang, Yanchao; Zhang, Lijun; Ma, Yanming

2017-01-01

Electrides are intrinsic electron-rich materials enabling applications as excellent electron emitters, superior catalysts, and strong reducing agents. There are a number of organic electrides; however, their instability at room temperature and sensitivity to moisture are bottlenecks for their practical uses. Known inorganic electrides are rare, but they appear to have greater thermal stability at ambient conditions and are thus better characterized for application. Here, we develop a computer-assisted inverse-design method for searching for a large variety of inorganic electrides unbiased by any known electride structures. It uses the intrinsic property of interstitial electron localization of electrides as the global variable function for swarm intelligence structure searches. We construct two rules of thumb on the design of inorganic electrides pointing to electron-rich ionic systems and low electronegativity of the cationic elements involved. By screening 99 such binary compounds through large-scale computer simulations, we identify 24 stable and 65 metastable new inorganic electrides that show distinct three-, two-, and zero-dimensional conductive properties, among which 18 are existing compounds that have not been pointed to as electrides. Our work reveals the rich abundance of inorganic electrides by providing 33 hitherto unexpected structure prototypes of electrides, of which 19 are not in the known structure databases.

First principles study of structural, electronic and optical properties of polymorphic forms of Rb 2Te

NASA Astrophysics Data System (ADS)

Alay-e-Abbas, S. M.; Shaukat, A.

2011-05-01

First-principles density functional theory calculations have been performed for structural, electronic and optical properties of three polymorphic forms of rubidium telluride. Our calculations show that the sequence of pressure induced phase transitions for Rb 2Te is Fm3¯m → Pnma → P6 3/mmc which is governed by the coordination numbers of the anions. From our calculated low transition pressure value for the Fm3¯m phase to the Pnma phase transition of Rb 2Te, the experimentally observed meta-stability of Fm3¯m phase at ambient conditions seems reasonable. The electronic band structure has been calculated for all the three phases and the change in the energy band gap is discussed for the transitioning phases. The energy band gaps obtained for the three phases of Rb 2Te decrease on going from the meta-stable phase to the high-pressure phases. Total and partial density of states for the polymorphs of Rb 2Te has been computed to elucidate the contribution of various atomic states on the electronic band structure. Furthermore, optical properties for all the polymorphic forms have been presented in form of the complex dielectric function.

Density functional study of the structural, electronic, and magnetic properties of Mo n and Mo n S ( n = 1 - 10) clusters

NASA Astrophysics Data System (ADS)

Ziane, M.; Amitouche, F.; Bouarab, S.; Vega, A.

2017-12-01

Structural and electronic properties of pure molybdenum Mo n and molybdenum-sulfide Mo n S ( n = 1 - 10) clusters were investigated in the framework of the density functional theory within the generalized gradient approximation to exchange and correlation with the aim of addressing how doping with a single S atom affects the geometries, magnetic properties, and reactivity of pure molybdenum clusters. These clusters exhibit a less marked tendency to dimerization than their isoelectronic Cr counterparts despite sharing their half-filled valence shell configuration. Doping with a single S impurity is enough to change the structure of the host molybdenum cluster to a large extent, as well as to modify the bonding pattern, the magnetic state and the magnetic moment distribution in the Mo host. Vertical ionization potentials and electron affinities are calculated to determine global reactivity indicators like the electronegativity and the chemical hardness. The results are discussed in terms of the thermodynamical and relative stabilities, charge transfer effects, and spin-polarized densities of electronic states.

Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

NASA Technical Reports Server (NTRS)

Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

2003-01-01

Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

Controllable Spatial Configuration on Cathode Interface for Enhanced Photovoltaic Performance and Device Stability.

PubMed

Li, Jiangsheng; Duan, Chenghao; Wang, Ning; Zhao, Chengjie; Han, Wei; Jiang, Li; Wang, Jizheng; Zhao, Yingjie; Huang, Changshui; Jiu, Tonggang

2018-05-08

The molecular structure of cathode interface modification materials can affect the surface morphology of the active layer and key electron transfer processes occurring at the interface of polymer solar cells in inverted structures mostly due to the change of molecular configuration. To investigate the effects of spatial configuration of the cathode interfacial modification layer on polymer solar cells device performances, we introduced two novel organic ionic salts (linear NS2 and three-dimensional (3D) NS4) combined with the ZnO film to fabricate highly efficient inverted solar cells. Both organic ionic salts successfully decreased the surface traps of the ZnO film and made its work function more compatible. Especially NS4 in three-dimensional configuration increased the electron mobility and extraction efficiency of the interfacial film, leading to a significant improvement of device performance. Power conversion efficiency (PCE) of 10.09% based on NS4 was achieved. Moreover, 3D interfacial modification could retain about 92% of its initial PCE over 160 days. It is proposed that 3D interfacial modification retards the element penetration-induced degradation without impeding the electron transfer from the active layer to the ZnO film, which significantly improves device stability. This indicates that inserting three-dimensional organic ionic salt is an efficient strategy to enhance device performance.