Predictive methods of some optoelectronic properties for blends based on quaternized polysulfones

NASA Astrophysics Data System (ADS)

Dobos, Adina Maria; Filimon, Anca

2017-11-01

Blends based on quaternized polysulfones were investigated in terms of optical and electronic properties. By applying the Bicerano formalism the refractive index and dielectric constant were evaluated. Also, the dielectric constant of these blends was studied as a function of temperature and frequency. As the result of the main chain structure and charged groups, an increase in theoretical values of the refractive index and dielectric constant with increasing of the ionic quaternized units content in the polymer blend occurs. Additionally, decrease in the dielectric constant with the increase of frequency and decrease of temperature was observed. Refractive index and dielectric constant values indicate that the analyzed samples are transparent and can be used in obtaining of materials with applications involving a small polarizability. Thus, the results are important in prediction of the special optoelectronic features of new polymers blends to obtain high-performance materials with applications in electronic and biomedical fields.

Nuclear magnetic resonance spin-spin coupling constants from coupled perturbed density functional theory

NASA Astrophysics Data System (ADS)

Sychrovský, Vladimír; Gräfenstein, Jürgen; Cremer, Dieter

2000-09-01

For the first time, a complete implementation of coupled perturbed density functional theory (CPDFT) for the calculation of NMR spin-spin coupling constants (SSCCs) with pure and hybrid DFT is presented. By applying this method to several hydrides, hydrocarbons, and molecules with multiple bonds, the performance of DFT for the calculation of SSCCs is analyzed in dependence of the XC functional used. The importance of electron correlation effects is demonstrated and it is shown that the hybrid functional B3LYP leads to the best accuracy of calculated SSCCs. Also, CPDFT is compared with sum-over-states (SOS) DFT where it turns out that the former method is superior to the latter because it explicitly considers the dependence of the Kohn-Sham operator on the perturbed orbitals in DFT when calculating SSCCs. The four different coupling mechanisms contributing to the SSCC are discussed in connection with the electronic structure of the molecule.

Spectral parameters and Hamaker constants of silicon hydride compounds and organic solvents.

PubMed

Masuda, Takashi; Matsuki, Yasuo; Shimoda, Tatsuya

2009-12-15

Cyclopentasilane (CPS) and polydihydrosilane, which consist of hydrogen and silicon only, are unique materials that can be used to produce intrinsic silicon film in a liquid process, such as spin coating or an ink-jet method. Wettability and solubility of general organic solvents including the above can be estimated by Hamaker constants, which are calculated according to the Lifshitz theory. In order to calculate a Hamaker constant by the simple spectral method (SSM), it is necessary to obtain absorption frequency and function of oscillator strength in the ultraviolet region. In this report, these physical quantities were obtained by means of an optical method. As a result of examination of the relation between molecular structures and ultraviolet absorption frequencies, which were obtained from various liquid materials, it was concluded that ultraviolet absorption frequencies became smaller as electrons were delocalized. In particular, the absorption frequencies were found to be very small for CPS and polydihydrosilane due to sigma-conjugate of their electrons. The Hamaker constants of CPS and polydihydrosilane were successfully calculated based on the obtained absorption frequency and function of oscillator strength.

Connection formulas for thermal density functional theory

DOE PAGES

Pribram-Jones, A.; Burke, K.

2016-05-23

We show that the adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upward from the system's physical temperature. We also show how to relate different correlation components to each other, either in terms of temperature or coupling-constant integrations. Lastly, we illustrate our results on the uniform electron gas.

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

Lehtomäki, Jouko; Makkonen, Ilja; Harju, Ari

We present a computational scheme for orbital-free density functional theory (OFDFT) that simultaneously provides access to all-electron values and preserves the OFDFT linear scaling as a function of the system size. Using the projector augmented-wave method (PAW) in combination with real-space methods, we overcome some obstacles faced by other available implementation schemes. Specifically, the advantages of using the PAW method are twofold. First, PAW reproduces all-electron values offering freedom in adjusting the convergence parameters and the atomic setups allow tuning the numerical accuracy per element. Second, PAW can provide a solution to some of the convergence problems exhibited in othermore » OFDFT implementations based on Kohn-Sham (KS) codes. Using PAW and real-space methods, our orbital-free results agree with the reference all-electron values with a mean absolute error of 10 meV and the number of iterations required by the self-consistent cycle is comparable to the KS method. The comparison of all-electron and pseudopotential bulk modulus and lattice constant reveal an enormous difference, demonstrating that in order to assess the performance of OFDFT functionals it is necessary to use implementations that obtain all-electron values. The proposed combination of methods is the most promising route currently available. We finally show that a parametrized kinetic energy functional can give lattice constants and bulk moduli comparable in accuracy to those obtained by the KS PBE method, exemplified with the case of diamond.« less

Quantum size effects on the (0001) surface of double hexagonal close packed americium

NASA Astrophysics Data System (ADS)

Gao, D.; Ray, A. K.

2007-01-01

Electronic structures of double hexagonal close-packed americium and the (0001) surface have been studied via full-potential all-electron density-functional calculations with a mixed APW+lo/LAPW basis. The electronic and geometric properties of bulk dhcp Am as well as quantum size effects in the surface energies and the work functions of the dhcp Am (0001) ultra thin films up to seven layers have been examined at nonmagnetic, ferromagnetic, and antiferromagnetic configurations with and without spin orbit coupling. The anti-ferromagnetic state including spin-orbit coupling is found to be the ground state of dhcp Am with the 5f electrons primarily localized. Our results show that both magnetic configurations and spin-orbit coupling play important roles in determining the equilibrium lattice constant, the bulk modulus as well as the localized feature of 5f electrons for dhcp Am. Our calculated equilibrium lattice constant and bulk modulus at the ground state are in good agreement with the experimental values respectively. The work function of dhcp Am (0001) 7-layer surface at the ground state is predicted to be 2.90 eV. The surface energy for dhcp Am (0001) semi-infinite surface energy at the ground state is predicted to be 0.84 J/m2. Quantum size effects are found to be more pronounced in work functions than in surface energies.

Understanding the Effect of Plastic Deformation on Elastic Modulus of Metals Based on a Percolation Model with Electron Work Function

NASA Astrophysics Data System (ADS)

Li, Qingda; Hua, Guomin; Lu, Hao; Yu, Bin; Li, D. Y.

2018-05-01

The elastic modulus of materials is usually treated as a constant in engineering applications. However, plastic deformation may result in changes in the elastic modulus of metallic materials. Using brass, aluminum, and low-carbon steel as sample materials, it is demonstrated that plastic deformation decreased the elastic modulus of the materials by 10% to 20%. A percolation model incorporating the electron work function is proposed to correlate such plastic-strain-induced variations in the elastic modulus to corresponding changes in the electron work function. Efforts are made to understand the observed phenomenon on an electronic basis. The obtained experimental results are consistent with the theoretical analysis.

Shot noise at high temperatures

NASA Astrophysics Data System (ADS)

Gutman, D. B.; Gefen, Yuval

2003-07-01

We consider the possibility of measuring nonequilibrium properties of the current correlation functions at high temperatures (and small bias). Through the example of the third cumulant of the current (S3) we demonstrate that odd-order correlation functions represent nonequilibrium physics even at small external bias and high temperatures. We calculate S3=y(eV/T)e2I for a quasi-one-dimensional diffusive constriction. We calculate the scaling function y in two regimes: when the scattering processes are purely elastic and when the inelastic electron-electron scattering is strong. In both cases we find that y interpolates between two constants. In the low- (high-) temperature limit y is strongly (weakly) enhanced (suppressed) by the electron-electron scattering.

First-principles study of the structural, elastic, vibrational, thermodynamic and electronic properties of the Mo2B intermetallic under pressure

NASA Astrophysics Data System (ADS)

Escamilla, R.; Carvajal, E.; Cruz-Irisson, M.; Romero, M.; Gómez, R.; Marquina, V.; Galván, D. H.; Durán, A.

2016-12-01

The structural, elastic, vibrational, thermodynamic and electronic properties of the Mo2B intermetallic under pressure are assessed using first-principles calculations based on the generalized gradient approximation (GGA) proposed by Perdew-Wang (PW91). Our results show that the calculated structural parameters at a pressure of zero GPa are in good agreement with the available experimental data. The effect of high pressures on the lattice constants shows that the compression along the c-axis and along the a-axis are similar. The elastic constants were calculated using the static finite strain technique, and the bulk shear moduli are derived from the ideal polycrystalline aggregate. We find that the elastic constants, elastic modulus and hardness monotonically increase as a function of pressure; consequently, the structure is dynamically stable and tends from brittle to ductile behavior under pressure. The Debye temperature θD increases and the so-called Gru¨ neisen constant γ decreases due to stiffening of the crystal structure. The phonon dispersion curves were obtained using the direct method. Additionally, the internal energy (ΔE), the Helmholtz free energy (ΔF), the entropy (S) and the lattice contribution to the heat capacity Cv were calculated and analyzed with the help of the phonon dispersion curves. The N(EF) and the electron transfer between the B and Mo atoms increase as a function of pressure.

Structural, electronic, elastic, and thermal properties of CaNiH3 perovskite obtained from first-principles calculations

NASA Astrophysics Data System (ADS)

Benlamari, S.; Bendjeddou, H.; Boulechfar, R.; Amara Korba, S.; Meradji, H.; Ahmed, R.; Ghemid, S.; Khenata, R.; Omran, S. Bin

2018-03-01

A theoretical study of the structural, elastic, electronic, mechanical, and thermal properties of the perovskite-type hydride CaNiH3 is presented. This study is carried out via first-principles full potential (FP) linearized augmented plane wave plus local orbital (LAPW+lo) method designed within the density functional theory (DFT). To treat the exchange–correlation energy/potential for the total energy calculations, the local density approximation (LDA) of Perdew–Wang (PW) and the generalized gradient approximation (GGA) of Perdew–Burke–Ernzerhof (PBE) are used. The three independent elastic constants (C 11, C 12, and C 44) are calculated from the direct computation of the stresses generated by small strains. Besides, we report the variation of the elastic constants as a function of pressure as well. From the calculated elastic constants, the mechanical character of CaNiH3 is predicted. Pertaining to the thermal properties, the Debye temperature is estimated from the average sound velocity. To further comprehend this compound, the quasi-harmonic Debye model is used to analyze the thermal properties. From the calculations, we find that the obtained results of the lattice constant (a 0), bulk modulus (B 0), and its pressure derivative ({B}0^{\\prime }) are in good agreement with the available theoretical as well as experimental results. Similarly, the obtained electronic band structure demonstrates the metallic character of this perovskite-type hydride.

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

Pribram-Jones, A.; Burke, K.

We show that the adiabatic connection formula of ground-state density functional theory relates the correlation energy to a coupling-constant integral over a purely potential contribution, and is widely used to understand and improve approximations. The corresponding formula for thermal density functional theory is cast as an integral over temperatures instead, ranging upward from the system's physical temperature. We also show how to relate different correlation components to each other, either in terms of temperature or coupling-constant integrations. Lastly, we illustrate our results on the uniform electron gas.

Precision controlled atomic resolution scanning transmission electron microscopy using spiral scan pathways

NASA Astrophysics Data System (ADS)

Sang, Xiahan; Lupini, Andrew R.; Ding, Jilai; Kalinin, Sergei V.; Jesse, Stephen; Unocic, Raymond R.

2017-03-01

Atomic-resolution imaging in an aberration-corrected scanning transmission electron microscope (STEM) can enable direct correlation between atomic structure and materials functionality. The fast and precise control of the STEM probe is, however, challenging because the true beam location deviates from the assigned location depending on the properties of the deflectors. To reduce these deviations, i.e. image distortions, we use spiral scanning paths, allowing precise control of a sub-Å sized electron probe within an aberration-corrected STEM. Although spiral scanning avoids the sudden changes in the beam location (fly-back distortion) present in conventional raster scans, it is not distortion-free. “Archimedean” spirals, with a constant angular frequency within each scan, are used to determine the characteristic response at different frequencies. We then show that such characteristic functions can be used to correct image distortions present in more complicated constant linear velocity spirals, where the frequency varies within each scan. Through the combined application of constant linear velocity scanning and beam path corrections, spiral scan images are shown to exhibit less scan distortion than conventional raster scan images. The methodology presented here will be useful for in situ STEM imaging at higher temporal resolution and for imaging beam sensitive materials.

Precision controlled atomic resolution scanning transmission electron microscopy using spiral scan pathways.

PubMed

Sang, Xiahan; Lupini, Andrew R; Ding, Jilai; Kalinin, Sergei V; Jesse, Stephen; Unocic, Raymond R

2017-03-08

Atomic-resolution imaging in an aberration-corrected scanning transmission electron microscope (STEM) can enable direct correlation between atomic structure and materials functionality. The fast and precise control of the STEM probe is, however, challenging because the true beam location deviates from the assigned location depending on the properties of the deflectors. To reduce these deviations, i.e. image distortions, we use spiral scanning paths, allowing precise control of a sub-Å sized electron probe within an aberration-corrected STEM. Although spiral scanning avoids the sudden changes in the beam location (fly-back distortion) present in conventional raster scans, it is not distortion-free. "Archimedean" spirals, with a constant angular frequency within each scan, are used to determine the characteristic response at different frequencies. We then show that such characteristic functions can be used to correct image distortions present in more complicated constant linear velocity spirals, where the frequency varies within each scan. Through the combined application of constant linear velocity scanning and beam path corrections, spiral scan images are shown to exhibit less scan distortion than conventional raster scan images. The methodology presented here will be useful for in situ STEM imaging at higher temporal resolution and for imaging beam sensitive materials.

Structural, electronic and thermal properties of super hard ternary boride, WAlB

NASA Astrophysics Data System (ADS)

Rajpoot, Priyanka; Rastogi, Anugya; Verma, U. P.

2018-04-01

A first principle study of the structural, electronic and thermal properties of Tungsten Aluminum Boride (WAlB) using full-potential linearized augmented plane wave (FP-LAPW) in the frame work of density function theory (DFT) have been calculated. The calculated equilibrium structural parameters are in excellent agreement with available experimental results. The calculated electronic band structure reveals that WAlB is metallic in nature. The quasi-harmonic Debye model is applied to study of the temperature and pressure effect on volume, Debye temperature, thermal expansion coefficient and specific heat at constant volume and constant pressure. To the best of our knowledge theoretical investigation of these properties of WAlB is reported for the first time.

First-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound

NASA Astrophysics Data System (ADS)

Paliwal, U.; Joshi, K. B.

2018-05-01

In this work the first-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound is presented. The calculations are performed applying the QUANTUM ESPRESSO code utilizing the Perdew, Becke, Ernzerhof generalized gradient approximation in the framework of density functional theory. Adopting standard optimization strategy, the ground state equilibrium lattice constant and bulk modulus are calculated. After settling the structure the electronic band structure, bandgap and static dielectric constant are evaluated. In absence of any experimental work on this system our findings are compared with the available theoretical calculations which are found to follow well anticipated general trends.

Measuring the dependence of the decay curve on the electron energy deposit in NaI(Tl)

NASA Astrophysics Data System (ADS)

Choong, W.-S.; Bizarri, G.; Cherepy, N. J.; Hull, G.; Moses, W. W.; Payne, S. A.

2011-08-01

We report on the first measurement of the decay times of NaI(Tl) as a function of the deposited electron energy. It has been suggested that the decay curve depends on the ionization density, which is correlated with the electron energy deposit in the scintillator. The ionization creates excitation states, which can decay radiatively and non-radiatively through a number of competing processes. As a result, the rate at which the excitation decays depends on the ionization density. A measurement of the decay curve as a function of the ionization density will allow us to probe the kinetic rates of the competing processes. The Scintillator Light Yield Non-proportionality Characterization Instrument (SLYNCI) measures the electron response of scintillators utilizing fast sampling ADCs to digitize the raw signals from the detectors, and so can provide a measurement of the light pulse shape from the scintillator. Using data collected with the SLYNCI instrument, the intrinsic scintillation profile is extracted on an event-by-event basis by deconvolving the raw signal with the impulse response of the system. Scintillation profiles with the same electron energy deposit are summed to obtain decay curves as a function of the deposited electron energy. The decay time constants are obtained by fitting the decay curves with a two-component exponential decay. While a slight dependence of the decay time constants on the electron energy deposit is observed, the results are not statistically significant.

Nonempirical range-separated hybrid functionals for solids and molecules

DOE PAGES

Skone, Jonathan H.; Govoni, Marco; Galli, Giulia

2016-06-03

Dielectric-dependent hybrid (DDH) functionals were recently shown to yield accurate energy gaps and dielectric constants for a wide variety of solids, at a computational cost considerably less than that of GW calculations. The fraction of exact exchange included in the definition of DDH functionals depends (self-consistently) on the dielectric constant of the material. Here we introduce a range-separated (RS) version of DDH functionals where short and long-range components are matched using system dependent, non-empirical parameters. We show that RS DDHs yield accurate electronic properties of inorganic and organic solids, including energy gaps and absolute ionization potentials. Moreover, we show thatmore » these functionals may be generalized to finite systems.« less

Electronic structure of the BaO molecule with dipole moments and ro-vibrational calculations

NASA Astrophysics Data System (ADS)

Khatib, Mohamed; Korek, Mahmoud

2018-03-01

The twenty-three low-lying electronic states (singlet and triplet) of the BaO molecule have been studied by using an ab initio method. These electronic states have been investigated by using the Complete Active Apace Self-Consistent Field (CASSCF) followed by multi-reference configuration interaction (MRCI + Q) with Davidson correction. The potential energy curves, the internuclear distance Re, the harmonic frequency ωe, the rotational constant Be, the electronic energy with respect to the ground state Te and the static and transition dipole moment have been investigated. The Einstein spontaneous and induced emission coefficients A21 and B21ω as well as the spontaneous radiative lifetime τspon, emission wavelength λ21 and oscillator strength f21 have been calculated by using the transition dipole moment between some doublet electronic states. The calculation of the eigenvalues Ev, the rotational constant Bv, the centrifugal distortion constant Dv, and the abscissas of the turning points Rmin and Rmax have been done by using the canonical functions approach. A very good agreement is shown by comparing the values of our work to those found in the literature for many electronic states. Eighteen new electronic states have been studied here for the first time.

Dielectric properties of organic solvents from non-polarizable molecular dynamics simulation with electronic continuum model and density functional theory.

PubMed

Lee, Sanghun; Park, Sung Soo

2011-11-03

Dielectric constants of electrolytic organic solvents are calculated employing nonpolarizable Molecular Dynamics simulation with Electronic Continuum (MDEC) model and Density Functional Theory. The molecular polarizabilities are obtained by the B3LYP/6-311++G(d,p) level of theory to estimate high-frequency refractive indices while the densities and dipole moment fluctuations are computed using nonpolarizable MD simulations. The dielectric constants reproduced from these procedures are evaluated to provide a reliable approach for estimating the experimental data. An additional feature, two representative solvents which have similar molecular weights but are different dielectric properties, i.e., ethyl methyl carbonate and propylene carbonate, are compared using MD simulations and the distinctly different dielectric behaviors are observed at short times as well as at long times.

Theoretical study of orbital ordering induced structural phase transition in iron pnictides

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

Jena, Sushree Sangita, E-mail: sushree@iopb.res.in; Rout, G. C., E-mail: gcr@iopb.res.in; Panda, S. K., E-mail: skp@iopb.res.in

2016-05-06

We attribute the structural phase transition (SPT) in the parent compounds of the iron pnictides to orbital ordering. Due to anisotropy of the d{sub xz} and d{sub yz} orbitals in the xy plane, orbital ordering makes the orthorhombic structure more favorable and thus inducing the SPT. We consider a one band model Hamiltonian consisting of first and second-nearest-neighbor hopping of the electrons. We introduce Jahn-Tellar (JT) distortion in the system arising due to the orbital ordering present in this system. We calculate the electron Green’s function by using Zuvareb’s Green’s function technique and hence calculate an expression for the temperaturemore » dependent lattice strain which is computed numerically and self-consistently. The temperature dependent electron specific heat is calculated by minimizing the free energy of the system. The lattice strain is studied by varying the JT coupling and elastic constant of the system. The structural anomaly is studied through the electron occupation number and the specific heat by varying the physical parameters like JT coupling, lattice constant, chemical potential and hopping integrals of the system.« less

Computing sextic centrifugal distortion constants by DFT: A benchmark analysis on halogenated compounds

NASA Astrophysics Data System (ADS)

Pietropolli Charmet, Andrea; Stoppa, Paolo; Tasinato, Nicola; Giorgianni, Santi

2017-05-01

This work presents a benchmark study on the calculation of the sextic centrifugal distortion constants employing cubic force fields computed by means of density functional theory (DFT). For a set of semi-rigid halogenated organic compounds several functionals (B2PLYP, B3LYP, B3PW91, M06, M06-2X, O3LYP, X3LYP, ωB97XD, CAM-B3LYP, LC-ωPBE, PBE0, B97-1 and B97-D) were used for computing the sextic centrifugal distortion constants. The effects related to the size of basis sets and the performances of hybrid approaches, where the harmonic data obtained at higher level of electronic correlation are coupled with cubic force constants yielded by DFT functionals, are presented and discussed. The predicted values were compared to both the available data published in the literature and those obtained by calculations carried out at increasing level of electronic correlation: Hartree-Fock Self Consistent Field (HF-SCF), second order Møller-Plesset perturbation theory (MP2), and coupled-cluster single and double (CCSD) level of theory. Different hybrid approaches, having the cubic force field computed at DFT level of theory coupled to harmonic data computed at increasing level of electronic correlation (up to CCSD level of theory augmented by a perturbational estimate of the effects of connected triple excitations, CCSD(T)) were considered. The obtained results demonstrate that they can represent reliable and computationally affordable methods to predict sextic centrifugal terms with an accuracy almost comparable to that yielded by the more expensive anharmonic force fields fully computed at MP2 and CCSD levels of theory. In view of their reduced computational cost, these hybrid approaches pave the route to the study of more complex systems.

Quantitative structure-activity relationship analysis of substituted arylazo pyridone dyes in photocatalytic system: Experimental and theoretical study.

PubMed

Dostanić, J; Lončarević, D; Zlatar, M; Vlahović, F; Jovanović, D M

2016-10-05

A series of arylazo pyridone dyes was synthesized by changing the type of the substituent group in the diazo moiety, ranging from strong electron-donating to strong electron-withdrawing groups. The structural and electronic properties of the investigated dyes was calculated at the M062X/6-31+G(d,p) level of theory. The observed good linear correlations between atomic charges and Hammett σp constants provided a basis to discuss the transmission of electronic substituent effects through a dye framework. The reactivity of synthesized dyes was tested through their decolorization efficiency in TiO2 photocatalytic system (Degussa P-25). Quantitative structure-activity relationship analysis revealed a strong correlation between reactivity of investigated dyes and Hammett substituent constants. The reaction was facilitated by electron-withdrawing groups, and retarded by electron-donating ones. Quantum mechanical calculations was used in order to describe the mechanism of the photocatalytic oxidation reactions of investigated dyes and interpret their reactivities within the framework of the Density Functional Theory (DFT). According to DFT based reactivity descriptors, i.e. Fukui functions and local softness, the active site moves from azo nitrogen atom linked to benzene ring to pyridone carbon atom linked to azo bond, going from dyes with electron-donating groups to dyes with electron-withdrawing groups. Copyright © 2016 Elsevier B.V. All rights reserved.

Ab initio calculations of the electronic structure of the low-lying states for the ultracold LiYb molecule

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

Tohme, Samir N.; Korek, Mahmoud, E-mail: mahmoud.korek@bau.edu.lb, E-mail: fkorek@yahoo.com; Awad, Ramadan

Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born–Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ω{sub e}, R{sub e}, B{sub e}, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, E{sub v}, themore » rotational constant, B{sub v}, the centrifugal distortion constant, D{sub v}, and the abscissas of the turning points, R{sub min} and R{sub max}, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.« less

Lattice constant changes leading to significant changes of the spin-gapless features and physical nature in a inverse Heusler compound Zr2MnGa

NASA Astrophysics Data System (ADS)

Wang, Xiaotian; Cheng, Zhenxiang; Khenata, Rabah; Wu, Yang; Wang, Liying; Liu, Guodong

2017-12-01

The spin-gapless semiconductors with parabolic energy dispersions [1-3] have been recently proposed as a new class of materials for potential applications in spintronic devices. In this work, according to the Slater-Pauling rule, we report the fully-compensated ferrimagnetic (FCF) behavior and spin-gapless semiconducting (SGS) properties for a new inverse Heusler compound Zr2MnGa by means of the plane-wave pseudo-potential method based on density functional theory. With the help of GGA-PBE, the electronic structures and the magnetism of Zr2MnGa compound at its equilibrium and strained lattice constants are systematically studied. The calculated results show that the Zr2MnGa is a new SGS at its equilibrium lattice constant: there is an energy gap between the conduction and valence bands for both the majority and minority electrons, while there is no gap between the majority electrons in the valence band and the minority electrons in the conduction band. Remarkably, not only a diverse physical nature transition, but also different types of spin-gapless features can be observed with the change of the lattice constants. Our calculated results of Zr2MnGa compound indicate that this material has great application potential in spintronic devices.

Mesoporous aluminium organophosphonates: a reusable chemsensor for the detection of explosives

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

Li, Dongdong, E-mail: lidongdong@jlu.edu.cn; Yu, Xiang

Rapid and sensitive detection of explosives is in high demand for homeland security and public safety. In this work, electron-rich of anthracene functionalized mesoporous aluminium organophosphonates (En-AlPs) were synthesized by a one-pot condensation process. The mesoporous structure and strong blue emission of En-AlPs were confirmed by the N{sub 2} adsorption-desorption isotherms, transmission electron microscopy images and fluorescence spectra. The materials En-AlPs can serve as sensitive chemosensors for various electron deficient nitroderivatives, with the quenching constant and the detection limit up to 1.5×10{sup 6} M{sup −1} and 0.3 ppm in water solution. More importantly, the materials can be recycled for manymore » times by simply washed with ethanol, showing potential applications in explosives detection. - Graphical abstract: Electron-rich of anthracene functionalized mesoporous aluminium organophosphonates can serve as sensitive and recycled chemosensors for nitroderivatives with the quenching constant up to 1.5×10{sup 6} M{sup −1} in water solution. Display Omitted - Highlights: • Anthracene functionalized mesoporous aluminium organophosphonates were synthesized. • The materials serve as sensitive chemosensors for nitroderivatives. • The materials can be recycled for many times by simply washed with ethanol. • The materials show potential applications in explosives detection.« less

Precision controlled atomic resolution scanning transmission electron microscopy using spiral scan pathways

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

Sang, Xiahan; Lupini, Andrew R.; Ding, Jilai

Atomic-resolution imaging in an aberration-corrected scanning transmission electron microscope (STEM) can enable direct correlation between atomic structure and materials functionality. The fast and precise control of the STEM probe is, however, challenging because the true beam location deviates from the assigned location depending on the properties of the deflectors. To reduce these deviations, i.e. image distortions, we use spiral scanning paths, allowing precise control of a sub-Å sized electron probe within an aberration-corrected STEM. Although spiral scanning avoids the sudden changes in the beam location (fly-back distortion) present in conventional raster scans, it is not distortion-free. “Archimedean” spirals, with amore » constant angular frequency within each scan, are used to determine the characteristic response at different frequencies. We then show that such characteristic functions can be used to correct image distortions present in more complicated constant linear velocity spirals, where the frequency varies within each scan. Through the combined application of constant linear velocity scanning and beam path corrections, spiral scan images are shown to exhibit less scan distortion than conventional raster scan images. The methodology presented here will be useful for in situ STEM imaging at higher temporal resolution and for imaging beam sensitive materials.« less

Precision controlled atomic resolution scanning transmission electron microscopy using spiral scan pathways

DOE PAGES

Sang, Xiahan; Lupini, Andrew R.; Ding, Jilai; ...

2017-03-08

Atomic-resolution imaging in an aberration-corrected scanning transmission electron microscope (STEM) can enable direct correlation between atomic structure and materials functionality. The fast and precise control of the STEM probe is, however, challenging because the true beam location deviates from the assigned location depending on the properties of the deflectors. To reduce these deviations, i.e. image distortions, we use spiral scanning paths, allowing precise control of a sub-Å sized electron probe within an aberration-corrected STEM. Although spiral scanning avoids the sudden changes in the beam location (fly-back distortion) present in conventional raster scans, it is not distortion-free. “Archimedean” spirals, with amore » constant angular frequency within each scan, are used to determine the characteristic response at different frequencies. We then show that such characteristic functions can be used to correct image distortions present in more complicated constant linear velocity spirals, where the frequency varies within each scan. Through the combined application of constant linear velocity scanning and beam path corrections, spiral scan images are shown to exhibit less scan distortion than conventional raster scan images. The methodology presented here will be useful for in situ STEM imaging at higher temporal resolution and for imaging beam sensitive materials.« less

Infrared photoemitting diode having reduced work function

DOEpatents

Hirschfeld, T.B.

1982-05-06

In electro-optical detectors which include as elements a photoemitting photocathode and anode, a photoemitting diode is fabricated which lowers the diode's work function, thus reducing the cooling requirement typically needed for this type of device. The work function is reduced by sandwiching between the photocathode and anode a liquid meidum of the formula NR/sub 3/ and having an electron affinity for the electrons of the photocathode, which liquid medium permits free electrons leaving the photocathode to remain as stable solvated species in the liquid medium. Thus, highly light-absorbent, and therefore thin, metallic layers can be used for detection, thereby reducing dark current at a given temperature, with a consequent reduction in cooling requirements at constant detector performance.

Infrared photoemitting diode having reduced work function

DOEpatents

Hirschfeld, Tomas B.

1984-01-01

In electro-optical detectors which include as elements a photoemitting photocathode and anode, a photoemitting diode is fabricated which lowers the diode's work function, thus reducing the cooling requirement typically needed for this type of device. The work function is reduced by sandwiching between the photocathode and anode a liquid medium of the formula NR.sub.3 and having an electron affinity for the electrons of the photocathode, which liquid medium permits free electrons leaving the photocathode to remain as stable solvated species in the liquid medium. Thus, highly light-absorbent, and therefore thin, metallic layers can be used for detection, thereby reducing dark current at a given temperature, with a consequent reduction in cooling requirements at constant detector performance.

First-Principles Calculations of Structural, Electronic and Optical Properties of Ternary Semiconductor Alloys ZAs x Sb1- x ( Z = B, Al, Ga, In)

NASA Astrophysics Data System (ADS)

Bounab, S.; Bentabet, A.; Bouhadda, Y.; Belgoumri, Gh.; Fenineche, N.

2017-08-01

We have investigated the structural and electronic properties of the BAs x Sb 1- x , AlAs x Sb 1- x , GaAs x Sb 1- x and InAs x Sb 1- x semiconductor alloys using first-principles calculations under the virtual crystal approximation within both the density functional perturbation theory and the pseudopotential approach. In addition the optical properties have been calculated by using empirical methods. The ground state properties such as lattice constants, both bulk modulus and derivative of bulk modulus, energy gap, refractive index and optical dielectric constant have been calculated and discussed. The obtained results are in reasonable agreement with numerous experimental and theoretical data. The compositional dependence of the lattice constant, bulk modulus, energy gap and effective mass of electrons for ternary alloys show deviations from Vegard's law where our results are in agreement with the available data in the literature.

Interfacial charge separation and recombination in InP and quasi-type II InP/CdS core/shell quantum dot-molecular acceptor complexes.

PubMed

Wu, Kaifeng; Song, Nianhui; Liu, Zheng; Zhu, Haiming; Rodríguez-Córdoba, William; Lian, Tianquan

2013-08-15

Recent studies of group II-VI colloidal semiconductor heterostuctures, such as CdSe/CdS core/shell quantum dots (QDs) or dot-in-rod nanorods, show that type II and quasi-type II band alignment can facilitate electron transfer and slow down charge recombination in QD-molecular electron acceptor complexes. To explore the general applicability of this wave function engineering approach for controlling charge transfer properties, we investigate exciton relaxation and dissociation dynamics in InP (a group III-V semiconductor) and InP/CdS core/shell (a heterostructure beween group III-V and II-VI semiconductors) QDs by transient absorption spectroscopy. We show that InP/CdS QDs exhibit a quasi-type II band alignment with the 1S electron delocalized throughout the core and shell and the 1S hole confined in the InP core. In InP-methylviologen (MV(2+)) complexes, excitons in the QD can be dissociated by ultrafast electron transfer to MV(2+) from the 1S electron level (with an average time constant of 11.4 ps) as well as 1P and higher electron levels (with a time constant of 0.39 ps), which is followed by charge recombination to regenerate the complex in its ground state (with an average time constant of 47.1 ns). In comparison, InP/CdS-MV(2+) complexes show similar ultrafast charge separation and 5-fold slower charge recombination rates, consistent with the quasi-type II band alignment in these heterostructures. This result demonstrates that wave function engineering in nanoheterostructures of group III-V and II-VI semiconductors provides a promising approach for optimizing their light harvesting and charge separation for solar energy conversion applications.

Magnetic properties and core electron binding energies of liquid water

NASA Astrophysics Data System (ADS)

Galamba, N.; Cabral, Benedito J. C.

2018-01-01

The magnetic properties and the core and inner valence electron binding energies of liquid water are investigated. The adopted methodology relies on the combination of molecular dynamics and electronic structure calculations. Born-Oppenheimer molecular dynamics with the Becke and Lee-Yang-Parr functionals for exchange and correlation, respectively, and includes an empirical correction (BLYP-D3) functional and classical molecular dynamics with the TIP4P/2005-F model were carried out. The Keal-Tozer functional was applied for predicting magnetic shielding and spin-spin coupling constants. Core and inner valence electron binding energies in liquid water were calculated with symmetry adapted cluster-configuration interaction. The relationship between the magnetic shielding constant σ(17O), the role played by the oxygen atom as a proton acceptor and donor, and the tetrahedral organisation of liquid water are investigated. The results indicate that the deshielding of the oxygen atom in water is very dependent on the order parameter (q) describing the tetrahedral organisation of the hydrogen bond network. The strong sensitivity of magnetic properties on changes of the electronic density in the nuclei environment is illustrated by a correlation between σ(17O) and the energy gap between the 1a1[O1s] (core) and the 2a1 (inner valence) orbitals of water. Although several studies discussed the eventual connection between magnetic properties and core electron binding energies, such a correlation could not be clearly established. Here, we demonstrate that for liquid water this correlation exists although involving the gap between electron binding energies of core and inner valence orbitals.

Inelastic scattering of electrons at real metal surfaces

NASA Astrophysics Data System (ADS)

Ding, Z.-J.

1997-04-01

A theory is presented to calculate the electron inelastic scattering cross section for a moving electron near the surface region at an arbitrary takeoff angle. The theory is based on using a bulk plasmon-pole approximation to derive the numerically computable expression of the electron self-energy in the random-phase approximation for a surface system, through the use of experimental optical constants. It is shown that the wave-vector-dependent surface dielectric function satisfies the surface sum rules in this scheme. The theory provides a detailed knowledge of electron self-energy depending on the kinetic energy, distance from surface, and velocity vector of an electron moving in any metal of a known dielectric constant, accommodating the formulation to practical situation in surface electron spectroscopies. Numerical computations of the energy-loss cross section have been made for Si and Au. The contribution to the total differential scattering cross section from each component is analyzed. The depth dependence informs us in detail how the bulk excitation mode changes to a surface excitation mode with an electron approaching the surface from the interior of a medium.

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.

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

Verma, U. P.; Nayak, V.

Quantum mechanical first principle calculations have been performed to study the electronic and structural properties of TiN and TiAs in zinc blende (ZB) and rock salt (RS) structures. The full-potential linearized augmented plane wave (FP-LAPW) method has been used within the framework of density functional theory (DFT). The exchange correlation functional has been solved employing generalized gradient approximation (GGA). Our predicted results for lattice constants are in good agreement with the earlier findings. The electronic band structures of TiX are metallic in both the phases.

Ab-initio study of electronic structure and elastic properties of ZrC

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

Mund, H. S., E-mail: hmoond@gmail.com; Ahuja, B. L.

2016-05-23

The electronic and elastic properties of ZrC have been investigated using the linear combination of atomic orbitals method within the framework of density functional theory. Different exchange-correlation functionals are taken into account within generalized gradient approximation. We have computed energy bands, density of states, elastic constants, bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio, lattice parameters and pressure derivative of the bulk modulus by calculating ground state energy of the rock salt structure type ZrC.

Interstate vibronic coupling constants between electronic excited states for complex molecules

NASA Astrophysics Data System (ADS)

Fumanal, Maria; Plasser, Felix; Mai, Sebastian; Daniel, Chantal; Gindensperger, Etienne

2018-03-01

In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)3(N,N)(L)]n+ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.

Prediction of electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor: an ab-initio study

NASA Astrophysics Data System (ADS)

Mayengbam, Rishikanta; Tripathy, S. K.; Pandey, B. P.

2018-03-01

In this paper, we have investigated the structural, electronic and optical properties of ZnAl2Te4 defect chalcopyrite semiconductor using generalized gradient approximation (GGA) within density functional theory (DFT). We have calculated the optimized lattice constants (a and c) and compared with the available experimental values. The optimized lattice constants have been used to calculate the energy band gap and found to be 1.57 eV. The partial density of states and total density of states have been discussed in detail. The frequency dependent dielectric constant and refractive index have been calculated and plotted in the energy range 0-13 eV. All the above parameters have been compared with the available experimental and theoretical values and found good agreement between them.

Dielectric properties of carbon nanotubes/epoxy composites.

PubMed

Peng, Jin-Ping; Zhang, Hui; Tang, Long-Cheng; Jia, Yu; Zhang, Zhong

2013-02-01

Material with high dielectric properties possesses the effect of energy storage and electric field homogenization, which plays an important role in the electrical and electronics domain, especially in the capacitor, electrical machinery and cable realm. In this paper, epoxy-based nanocomposites with high dielectric constant were fabricated by adding pristine and ozone functionalized multi-wall carbon nanotubes (MWCNTs). In the process-related aspect, the favorable technological parameter was obtained via reasonable arrangement and consideration of the dispersing methods including high-speed stirring and three-roller mill. As a result, a uniform dispersion status of MWCNTs in matrix has been guaranteed, which was observed by scanning and transmission electron microscopy. Meanwhile, the influence of different MWCNTs contents and diverse frequencies on the dielectric properties was compared. It was found that the dielectric constant of nano-composites decreased gradually with the increasing of frequency (10(3)-10(6) Hz). Moreover, as the content of MWCNTs increasing, the dielectric constant reached to a maximum of about 1,328 at 10(3) Hz when the pristine MWCNTs content was 0.5 wt.%. Accordingly, the DC conductivity results could interpret the peak value phenomenon by percolation threshold of MWCNTs. In addition, at the fixed content, the dielectric constant of epoxy-based nano-composites with ozone functionalized MWCNTs was lower than that of pristine ones.

Temperature and energy effects on secondary electron emission from SiC ceramics induced by Xe17+ ions.

PubMed

Zeng, Lixia; Zhou, Xianming; Cheng, Rui; Wang, Xing; Ren, Jieru; Lei, Yu; Ma, Lidong; Zhao, Yongtao; Zhang, Xiaoan; Xu, Zhongfeng

2017-07-25

Secondary electron emission yield from the surface of SiC ceramics induced by Xe 17+ ions has been measured as a function of target temperature and incident energy. In the temperature range of 463-659 K, the total yield gradually decreases with increasing target temperature. The decrease is about 57% for 3.2 MeV Xe 17+ impact, and about 62% for 4.0 MeV Xe 17+ impact, which is much larger than the decrease observed previously for ion impact at low charged states. The yield dependence on the temperature is discussed in terms of work function, because both kinetic electron emission and potential electron emission are influenced by work function. In addition, our experimental data show that the total electron yield gradually increases with the kinetic energy of projectile, when the target is at a constant temperature higher than room temperature. This result can be explained by electronic stopping power which plays an important role in kinetic electron emission.

Multi-channel electronically scanned cryogenic pressure sensor

NASA Technical Reports Server (NTRS)

Chapman, John J. (Inventor); Hopson, Purnell, Jr. (Inventor); Kruse, Nancy M. H. (Inventor)

1995-01-01

A miniature, multi-channel, electronically scanned pressure measuring device uses electrostatically bonded silicon dies in a multielement array. These dies are bonded at specific sites on a glass, prepatterned substrate. Thermal data is multiplexed and recorded on each individual pressure measuring diaphragm. The device functions in a cryogenic environment without the need of heaters to keep the sensor at constant temperatures.

Generation of constant-amplitude radio-frequency sweeps at a tunnel junction for spin resonance STM

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

Paul, William; Lutz, Christopher P.; Heinrich, Andreas J.

2016-07-15

We describe the measurement and successful compensation of the radio-frequency transfer function of a scanning tunneling microscope over a wide frequency range (15.5–35.5 GHz) and with high dynamic range (>50 dB). The precise compensation of cabling resonances and attenuations is critical for the production of constant-voltage frequency sweeps for electric-field driven electron spin resonance (ESR) experiments. We also demonstrate that a well-calibrated tunnel junction voltage is necessary to avoid spurious ESR peaks that can arise due to a non-flat transfer function.

Anharmonic Potential Constants and Their Dependence Upon Bond Length

DOE R&D Accomplishments Database

Herschbach, D. R.; Laurie, V. W.

1961-01-01

Empirical study of cubic and quartic vibrational force constants for diatomic molecules shows them to be approximately exponential functions of internuclear distance. A family of curves is obtained, determined by the location of the bonded atoms in rows of the periodic table. Displacements between successive curves correspond closely to those in Badger's rule for quadratic force constants (for which the parameters are redetermined to accord with all data now available). Constants for excited electronic and ionic states appear on practically the same curves as those for the ground states. Predictions based on the diatomic correlations agree with the available cubic constants for bond stretching in polyatomic molecules, regardless of the type of bonding involved. Implications of these regularities are discussed. (auth)

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.

Theoretical investigation of structural, mechanical and electronic properties of GaAs1-xNx alloys under ambient and high pressure

NASA Astrophysics Data System (ADS)

Li, Jian; Han, Xiuxun; Dong, Chen; Fan, Changzeng

2017-12-01

Using first-principles total energy calculations, we have studied the structural, mechanical and electronic properties of GaAs1-xNx ternary semiconductor alloys with the zinc-blende crystal structure over the whole nitrogen concentration range (with x from 0 to 1) within density functional theory (DFT) framework. To obtain the ideal band gap, we employ the semi-empirical approach called local density approximation plus the multi-orbital mean-field Hubbard model (LDA+U). The calculated results illustrate the varying lattice constants and band gap in GaAs1-xNx alloys as functions of the nitrogen concentration x. According to the pressure dependence of the lattice constants and volume, the higher N concentration alloy exhibits the better anti-compressibility. In addition, an increasing band gap is predicted under 20 GPa pressure for GaAs1-xNx alloys.

Electronic Structure Calculation of Permanent Magnets using the KKR Green's Function Method

NASA Astrophysics Data System (ADS)

Doi, Shotaro; Akai, Hisazumi

2014-03-01

Electronic structure and magnetic properties of permanent magnetic materials, especially Nd2Fe14B, are investigated theoretically using the KKR Green's function method. Important physical quantities in magnetism, such as magnetic moment, Curie temperature, and anisotropy constant, which are obtained from electronics structure calculations in both cases of atomic-sphere-approximation and full-potential treatment, are compared with past band structure calculations and experiments. The site preference of heavy rare-earth impurities are also evaluated through the calculation of formation energy with the use of coherent potential approximations. Further, the development of electronic structure calculation code using the screened KKR for large super-cells, which is aimed at studying the electronic structure of realistic microstructures (e.g. grain boundary phase), is introduced with some test calculations.

Effect of strain on the electronic structure and optical properties of germanium

NASA Astrophysics Data System (ADS)

Wen, Shumin; Zhao, Chunwang; Li, Jijun; Hou, Qingyu

2018-05-01

The effects of biaxial strain parallel to the (001) plane on the electronic structures and optical properties of Ge are calculated using the first-principles plane-wave pseudopotential method based on density functional theory. The screened-exchange local-density approximation function was used to obtain more reliable band structures, while strain was changed from ‑4% to +4%. The results show that the bandgap of Ge decreases with the increase of strain. Ge becomes a direct-bandgap semiconductor when the tensile strain reaches to 2%, which is in good agreement with the experimental results. The density of electron states of strained Ge becomes more localized. The tensile strain can increase the static dielectric constant distinctly, whereas the compressive strain can decrease the static dielectric constant slightly. The strain makes the absorption band edge move toward low energy. Both the tensile strain and compressive strain can significantly increase the reflectivity in the range from 7 eV to 14 eV. The tensile strain can decrease the optical conductivity, but the compressive strain can increase the optical conductivity significantly.

Chemical and quantum simulation of electron transfer through a polypeptide

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

Ungar, L.W.; Voth, G.A.; Newton, M.D.

1999-08-26

Quantum rate theory, molecular dynamics simulations, and semiempirical electronic structure calculations are used to fully investigate electron transfer mediated by a solvated polypeptide for the first time. Using a stationary-phase approximation, the nonadiabatic electron-transfer rate constant is calculated from the nuclear free energies and the electronic coupling between the initial and final states. The former are obtained from quantum path integral and classical molecular dynamics simulations; the latter are calculated using semiempirical electronic structure calculations and the generalized Mulliken-Hush method. Importantly, no parameters are fit to kinetic data. The simulated system consists of a solvated four-proline polypeptide with a tris(bipyridine)rutheniummore » donor group and an oxypentamminecobalt acceptor group. From the simulation data entropy and energy contributions to the free energies are distinguished. Quantum suppression of the barrier, including important solvent contributions, is demonstrated. Although free energy profiles along the reaction coordinate are nearly parabolic, pronounced departures from harmonic behavior are found for the separate energy and entropy functions. Harmonic models of the system are compared to simulation results in order to quantify anharmonic effects. Electronic structure calculations show that electronic coupling elements vary considerably with system conformation, even when the effective donor-acceptor separation remains roughly constant. The calculations indicate that electron transfer in a significant range of conformations linking the polypeptide to the acceptor may contribute to the overall rate constant. After correction for limitations of the solvent model, the simulations and calculations agree well with the experimental activation energy and Arrhenius prefactor.« less

Electronic, thermoelectric and transport properties of cesium cadmium trifluoride: A DFT study

NASA Astrophysics Data System (ADS)

Abraham, Jisha Annie; Pagare, G.; Sanyal, Sankar P.

2018-04-01

The full potential linearized augmented plane wave method based on density functional theory is employed to investigate the electronic structure of CsCdF3. The electronic properties of this compound have been studied from the band structure plot and density of states. The presence of indirect energy gap reveals its insulating nature. Using constant relaxation time, the electrical conductivity, electronic thermal conductivity, Seebeck coefficient and figure of merit are calculated by using Boltzmann transport theory. We have also studied the temperature dependence of thermoelectric properties of this compound.

Thermal transport across metal silicide-silicon interfaces: First-principles calculations and Green's function transport simulations

NASA Astrophysics Data System (ADS)

Sadasivam, Sridhar; Ye, Ning; Feser, Joseph P.; Charles, James; Miao, Kai; Kubis, Tillmann; Fisher, Timothy S.

2017-02-01

Heat transfer across metal-semiconductor interfaces involves multiple fundamental transport mechanisms such as elastic and inelastic phonon scattering, and electron-phonon coupling within the metal and across the interface. The relative contributions of these different transport mechanisms to the interface conductance remains unclear in the current literature. In this work, we use a combination of first-principles calculations under the density functional theory framework and heat transport simulations using the atomistic Green's function (AGF) method to quantitatively predict the contribution of the different scattering mechanisms to the thermal interface conductance of epitaxial CoSi2-Si interfaces. An important development in the present work is the direct computation of interfacial bonding from density functional perturbation theory (DFPT) and hence the avoidance of commonly used "mixing rules" to obtain the cross-interface force constants from bulk material force constants. Another important algorithmic development is the integration of the recursive Green's function (RGF) method with Büttiker probe scattering that enables computationally efficient simulations of inelastic phonon scattering and its contribution to the thermal interface conductance. First-principles calculations of electron-phonon coupling reveal that cross-interface energy transfer between metal electrons and atomic vibrations in the semiconductor is mediated by delocalized acoustic phonon modes that extend on both sides of the interface, and phonon modes that are localized inside the semiconductor region of the interface exhibit negligible coupling with electrons in the metal. We also provide a direct comparison between simulation predictions and experimental measurements of thermal interface conductance of epitaxial CoSi2-Si interfaces using the time-domain thermoreflectance technique. Importantly, the experimental results, performed across a wide temperature range, only agree well with predictions that include all transport processes: elastic and inelastic phonon scattering, electron-phonon coupling in the metal, and electron-phonon coupling across the interface.

Density functional theory and an experimentally-designed energy functional of electron density.

PubMed

Miranda, David A; Bueno, Paulo R

2016-09-21

We herein demonstrate that capacitance spectroscopy (CS) experimentally allows access to the energy associated with the quantum mechanical ground state of many-electron systems. Priorly, electrochemical capacitance, C [small mu, Greek, macron] [ρ], was previously understood from conceptual and computational density functional theory (DFT) calculations. Thus, we herein propose a quantum mechanical experiment-based variational method for electron charging processes based on an experimentally-designed functional of the ground state electron density. In this methodology, the electron state density, ρ, and an energy functional of the electron density, E [small mu, Greek, macron] [ρ], can be obtained from CS data. CS allows the derivative of the electrochemical potential with respect to the electron density, (δ[small mu, Greek, macron][ρ]/δρ), to be obtained as a unique functional of the energetically minimised system, i.e., β/C [small mu, Greek, macron] [ρ], where β is a constant (associated with the size of the system) and C [small mu, Greek, macron] [ρ] is an experimentally observable quantity. Thus the ground state energy (at a given fixed external potential) can be obtained simply as E [small mu, Greek, macron] [ρ], from the experimental measurement of C [small mu, Greek, macron] [ρ]. An experimental data-set was interpreted to demonstrate the potential of this quantum mechanical experiment-based variational principle.

Multi-Channel Electronically Scanned Cryogenic Pressure Sensor And Method For Making Same

NASA Technical Reports Server (NTRS)

Chapman, John J. (Inventor); Hopson, Purnell, Jr. (Inventor); Holloway, Nancy M. (Inventor)

2001-01-01

A miniature, multi-channel, electronically scanned pressure measuring device uses electrostatically bonded silicon dies in a multi-element array. These dies are bonded at specific sites on a glass, pre-patterned substrate. Thermal data is multiplexed and recorded on each individual pressure measuring diaphragm. The device functions in a cryogenic environment without the need of heaters to keep the sensor at constant temperatures.

The Multicenter Aerobic Iron Respiratory Chain of Acidithiobacillus ferrooxidans Functions as an Ensemble with a Single Macroscopic Rate Constant

DOE PAGES

Li, Ting-Feng; Painter, Richard G.; Ban, Bhupal; ...

2015-06-03

Electron transfer reactions among three prominent colored proteins in intact cells of Acidithiobacillus ferrooxidans were monitored using an integrating cavity absorption meter that permitted the acquisition of accurate absorbance data in suspensions of cells that scattered light. The concentrations of proteins in the periplasmic space were estimated to be 350 and 25 mg/ml for rusticyanin and cytochrome c, respectively; cytochrome a was present as one molecule for every 91 nm2 in the cytoplasmic membrane. All three proteins were rapidly reduced to the same relative extent when suspensions of live bacteria were mixed with different concentrations of ferrous ions at pHmore » 1.5. The subsequent molecular oxygen-dependent oxidation of the multicenter respiratory chain occurred with a single macroscopic rate constant, regardless of the proteins' in vitro redox potentials or their putative positions in the aerobic iron respiratory chain. The crowded electron transport proteins in the periplasm of the organism constituted an electron conductive medium where the network of protein interactions functioned in a concerted fashion as a single ensemble with a standard reduction potential of 650 mV. The appearance of product ferric ions was correlated with the reduction levels of the periplasmic electron transfer proteins; the limiting first-order catalytic rate constant for aerobic respiration on iron was 7,400 s -1. The ability to conduct direct spectrophotometric studies under noninvasive physiological conditions represents a new and powerful approach to examine the extent and rates of biological events in situ without disrupting the complexity of the live cellular environment.« less

An ab-initio study of mechanical, dynamical and electronic properties of MgEu intermetallic

NASA Astrophysics Data System (ADS)

Kumar, S. Ramesh; Jaiganesh, G.; Jayalakshmi, V.

2018-04-01

The theoretical investigation on the mechanical, dynamical and electronic properties of MgEu in CsCl-type structure has been carried out through the ab-initio calculations within the framework of the density functional theory and the density functional perturbation theory. For the purpose, Vienna Ab initio Simulation Package and Phonopy packages were used. Our calculated ground-state properties of MgEu are in good agreement with other available results. Our computed elastic constants and phonon spectrum results suggest that MgEu is mechanically and dynamically stable up to 5 GPa. The thermodynamic quantities as a function of temperatures are also reported and discussed. The band structure, density of states and charge density also calculated to understand the electronic properties of MgEu.

Estimation of Hammett sigma constants of substituted benzenes through accurate density-functional calculation of core-electron binding energy shifts

NASA Astrophysics Data System (ADS)

Takahata, Yuji; Chong, Delano P.

For substituted benzenes such as (p-F-C6H4-Z), Linderberg et al. 1 demonstrated the validity of an equation similar to: ΔCEBE ≈ κσ, where ΔCEBE is the difference in core-electron binding energies (CEBEs) of the fluorinated carbon in p-F-C6H4-Z and that in FC6H5, the parameter κ is a function of the type of reaction, and σ is the Hammett substituent (σ) constant. In this work, CEBEs of ring carbon atoms for a series of para disubstituted molecules p-F-C6H4-Z were first calculated using Density Functional Theory (DFT) with the scheme ΔEKS (PW86-PW91)/TZP+Crel//HF/6-31G*. An average absolute deviation of 0.13 eV from experiment was obtained for the CEBEs. Then we performed a linear regression analysis in the form of Y = A+B*X for a plot of Hammett σp constants against calculated shifts ΔCEBEs (in eV) for the fluorinated carbon. The results were: A = -0.08 and B = 1.01, with correlation coefficient R = 0.973, standard deviation = 0.12, and P < 0.0001. The intercept A of the fitted line, close to zero, shows that the Hammett σp constant is proportional to the calculated ΔCEBEs. On the other hand, the slope B of the straight line gives an estimate of the parameter κ. Similar statistical correlations were obtained for the carbon atoms ortho and meta to the substituent Z.

Electronic structure and electron-phonon interaction in hexagonal yttrium by density functional calculations

NASA Astrophysics Data System (ADS)

Singh, Prabhakar P.

2007-03-01

To understand the pressure-induced changes in the electronic structure and the electron-phonon interaction in yttrium, we have studied hexagonal-close-packed (hcp) yttrium, stable at ambient pressure, and double hexagonal-close-packed (dhcp) yttrium, stable up to around 44GPa , using density-functional-based methods. Our results show that as one goes from hcp yttrium to dhcp yttrium, there are (i) a substantial charge transfer from s→d with extensive modifications of the d band and a sizable reduction in the density of states at the Fermi energy, (ii) a substantial stiffening of phonon modes with the electron-phonon coupling covering the entire frequency range, and (iii) an increase in the electron-phonon coupling constant λ from 0.55 to 1.24, leading to a change in the superconducting transition temperature Tc from 0.3to15.3K for μ*=0.2 .

Examination of the formation process of pre-solvated and solvated electron in n-alcohol using femtosecond pulse radiolysis

NASA Astrophysics Data System (ADS)

Toigawa, Tomohiro; Gohdo, Masao; Norizawa, Kimihiro; Kondoh, Takafumi; Kan, Koichi; Yang, Jinfeng; Yoshida, Yoichi

2016-06-01

The formation process of pre-solvated and solvated electron in methanol (MeOH), ethanol (EtOH), n-butanol (BuOH), and n-octanol (OcOH) were investigated using a fs-pulse radiolysis technique by observing the pre-solvated electron at 1400 nm. The formation time constants of the pre-solvated electrons were determined to be 1.2, 2.2, 3.1, and 6.3 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation time constants of the solvated electrons were determined to be 6.7, 13.6, 22.2, and 32.9 ps for MeOH, EtOH, BuOH, and OcOH, respectively. The formation dynamics and structure of the pre-solvated and solvated electrons in n-alcohols were discussed based on relation between the obtained time constant and dielectric relaxation time constant from the view point of kinetics. The observed formation time constants of the solvated electrons seemed to be strongly correlated with the second component of the dielectric relaxation time constants, which are related to single molecule motion. On the other hand, the observed formation time constants of the pre-solvated electrons seemed to be strongly correlated with the third component of the dielectric relaxation time constants, which are related to dynamics of hydrogen bonds.

Polarized pressure dependence of the anisotropic dielectric functions of highly oriented poly(p-phenylene vinylene)

NASA Astrophysics Data System (ADS)

Morandi, V.; Galli, M.; Marabelli, F.; Comoretto, D.

2010-04-01

In this work, we combined an experimental technique and a detailed data analysis to investigate the influence of an applied pressure on the anisotropic dielectric functions of highly oriented poly(p-phenylene vinylene) (PPV). The dielectric constants were derived from polarized reflectance spectra recorded through a diamond anvil cell up to 50 kbar. The presence of the diamond anvils strongly affects measured spectra requiring the development in an optical model able to take all spurious effects into account. A parametric procedure was then applied to derive the complex dielectric constants for both polarizations as a function of pressure. A detailed analysis of their pressure dependence allows addressing the role of intermolecular interactions and electron-phonon coupling in highly oriented PPV.

Composite polarizability and the construction of an invariant function of refraction and mass density for solutions.

PubMed

Szymański, Krzysztof; Petrache, Horia I

2011-04-14

Re-examination of dynamical ionic polarizabilities in water solutions leads to the formulation of a solution function r(c), which combines the indices of refraction and mass densities of solutions. We show that this function should be independent of ionic concentration if the composite polarizabilities of hydrated solute clusters are constant. Using existing experimental data for a number of aqueous salt and organic solutions, we find that the r(c) function is either constant or varies linearly with concentration, in most cases with negligible slope. We use this function to compare ionic polarizabilities of crystals and aqueous solutions and to highlight how solute polarizabilities at infinite dilution scale with the electronic valence shell of cations and anions. The proposed r(c) function can be used generally to verify the consistency of experimental measurements and of simulation results, and it provides a test of assumptions in current theories of ionic polarizabilities.

Nonadiabatic effects on the charge transfer rate constant: A numerical study of a simple model system

NASA Astrophysics Data System (ADS)

Shin, Seokmin; Metiu, Horia

1995-06-01

We use a minimal model to study the effects of the upper electronic states on the rate of a charge transfer reaction. The model consists of three ions and an electron, all strung on a line. The two ions at the ends of the structure are held fixed, but the middle ion and the electron are allowed to move in one dimension, along the line joining them. The system has two bound states, one in which the electron ties the movable ion to the fixed ion at the left, and the other in which the binding takes place to the fixed ion at the right. The transition between these bound states is a charge transfer reaction. We use the flux-flux correlation function theory to perform two calculations of the rate constant for this reaction. In one we obtain numerically the exact rate constant. In the other we calculate the exact rate constant for the case when the reaction proceeds exclusively on the ground adiabatic state. The difference between these calculations gives the magnitude of the nonadiabatic effects. We find that the nonadiabatic effects are fairly large even when the gap between the ground and the excited adiabatic state substantially exceeds the thermal energy. The rate in the nonadiabatic theory is always smaller than that of the adiabatic one. Both rate constants satisfy the Arrhenius formula. Their activation energies are very close but the nonadiabatic one is always higher. The nonadiabatic preexponential is smaller, due to the fact that the upper electronic state causes an early recrossing of the reactive flux. The description of this reaction in terms of two diabatic states, one for reactants and one for products, is not always adequate. In the limit when nonadiabaticity is small, we need to use a third diabatic state, in which the electron binds to the moving ion as the latter passes through the transition state; this is an atom transfer process. The reaction changes from an atom transfer to an electron transfer, as nonadiabaticity is increased.

High-Throughput Screening of Sulfide Thermoelectric Materials Using Electron Transport Calculations with OpenMX and BoltzTraP

NASA Astrophysics Data System (ADS)

Miyata, Masanobu; Ozaki, Taisuke; Takeuchi, Tsunehiro; Nishino, Shunsuke; Inukai, Manabu; Koyano, Mikio

2018-06-01

The electron transport properties of 809 sulfides have been investigated using density functional theory (DFT) calculations in the relaxation time approximation, and a material design rule established for high-performance sulfide thermoelectric (TE) materials. Benchmark electron transport calculations were performed for Cu12Sb4S13 and Cu26V2Ge6S32, revealing that the ratio of the scattering probability of electrons and phonons ( κ lat τ el -1 ) was constant at about 2 × 1014 W K-1 m-1 s-1. The calculated thermopower S dependence of the theoretical dimensionless figure of merit ZT DFT of the 809 sulfides showed a maximum at 140 μV K-1 to 170 μV K-1. Under the assumption of constant κ lat τ el -1 of 2 × 1014 W K-1 m-1 s-1 and constant group velocity v of electrons, a slope of the density of states of 8.6 states eV-2 to 10 states eV-2 is suitable for high- ZT sulfide TE materials. The Lorenz number L dependence of ZT DFT for the 809 sulfides showed a maximum at L of approximately 2.45 × 10-8 V2 K-2. This result demonstrates that the potential of high- ZT sulfide materials is highest when the electron thermal conductivity κ el of the symmetric band is equal to that of the asymmetric band.

Self-consistent average-atom scheme for electronic structure of hot and dense plasmas of mixture.

PubMed

Yuan, Jianmin

2002-10-01

An average-atom model is proposed to treat the electronic structures of hot and dense plasmas of mixture. It is assumed that the electron density consists of two parts. The first one is a uniform distribution with a constant value, which is equal to the electron density at the boundaries between the atoms. The second one is the total electron density minus the first constant distribution. The volume of each kind of atom is proportional to the sum of the charges of the second electron part and of the nucleus within each atomic sphere. By this way, one can make sure that electrical neutrality is satisfied within each atomic sphere. Because the integration of the electron charge within each atom needs the size of that atom in advance, the calculation is carried out in a usual self-consistent way. The occupation numbers of electron on the orbitals of each kind of atom are determined by the Fermi-Dirac distribution with the same chemical potential for all kinds of atoms. The wave functions and the orbital energies are calculated with the Dirac-Slater equations. As examples, the electronic structures of the mixture of Au and Cd, water (H2O), and CO2 at a few temperatures and densities are presented.

Large local lattice expansion in graphene adlayers grown on copper

NASA Astrophysics Data System (ADS)

Chen, Chaoyu; Avila, José; Arezki, Hakim; Nguyen, Van Luan; Shen, Jiahong; Mucha-Kruczyński, Marcin; Yao, Fei; Boutchich, Mohamed; Chen, Yue; Lee, Young Hee; Asensio, Maria C.

2018-05-01

Variations of the lattice parameter can significantly change the properties of a material, and, in particular, its electronic behaviour. In the case of graphene, however, variations of the lattice constant with respect to graphite have been limited to less than 2.5% due to its well-established high in-plane stiffness. Here, through systematic electronic and lattice structure studies, we report regions where the lattice constant of graphene monolayers grown on copper by chemical vapour deposition increases up to 7.5% of its relaxed value. Density functional theory calculations confirm that this expanded phase is energetically metastable and driven by the enhanced interaction between the substrate and the graphene adlayer. We also prove that this phase possesses distinctive chemical and electronic properties. The inherent phase complexity of graphene grown on copper foils revealed in this study may inspire the investigation of possible metastable phases in other seemingly simple heterostructure systems.

DFT investigations on mechanical stability, electronic structure and magnetism in Co2TaZ (Z = Al, Ga, In) heusler alloys

NASA Astrophysics Data System (ADS)

Khandy, Shakeel Ahmad; Gupta, Dinesh C.

2017-12-01

Ferromagnetic Heusler compounds have vast and imminent applications for novel devices, smart materials thanks to density functional theory (DFT) based simulations, which have scored out a new approach to study these materials. We forecast the structural stability of Co2TaZ alloys on the basis of total energy calculations and mechanical stability criteria. The elastic constants, robust spin-polarized ferromagnetism and electron densities in these half-metallic alloys are also discussed. The observed structural aspects calculated to predict the stability and equilibrium lattice parameters agree well with the experimental results. The elastic parameters like elastic constants, bulk, Young’s and shear moduli, poison’s and Pugh ratios, melting temperatures, etc have been put together to establish their mechanical properties. The elaborated electronic band structures along with indirect band gaps and spin polarization favour the application of these materials in spintronics and memory device technology.

Ab-initio calculations of electronic, transport, and structural properties of boron phosphide

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

Ejembi, J. I.; Nwigboji, I. H.; Franklin, L.

2014-09-14

We present results from ab-initio, self-consistent density functional theory calculations of electronic and related properties of zinc blende boron phosphide (zb-BP). We employed a local density approximation potential and implemented the linear combination of atomic orbitals formalism. This technique follows the Bagayoko, Zhao, and Williams method, as enhanced by the work of Ekuma and Franklin. The results include electronic energy bands, densities of states, and effective masses. The calculated band gap of 2.02 eV, for the room temperature lattice constant of a=4.5383 Å, is in excellent agreement with the experimental value of 2.02±0.05 eV. Our result for the bulk modulus,more » 155.7 GPa, agrees with experiment (152–155 GPa). Our predictions for the equilibrium lattice constant and the corresponding band gap, for very low temperatures, are 4.5269 Å and 2.01 eV, respectively.« less

Search for ionisation density effects in the radiation absorption stage in LiF:Mg,Ti.

PubMed

Nail, I; Horowitz, Y S; Oster, L; Brandan, M E; Rodríguez-Villafuerte, M; Buenfil, A E; Ruiz-Trejo, C; Gamboa-Debuen, I; Avila, O; Tovar, V M; Olko, P; Ipe, N

2006-01-01

Optical absorption (OA) dose-response of LiF:Mg,Ti (TLD-100) is studied as a function of electron energy (ionisation density) and irradiation dose. Contrary to the situation in thermoluminescence dose-response where the supralinearity is strongly energy-dependent, no dependence of the OA dose filling constants on energy is observed. This result is interpreted as indicating a lack of competitive process in the radiation absorption stage. The lack of an energy dependence of the dose filling constant also suggests that the charge carrier migration distances are sufficiently large to smear out the differences in the non-uniform distribution of ionisation events created by the impinging gamma/electron radiation of various energies.

Concentration Dependent Physical Properties of Ge1-xSnx Solid Solution

NASA Astrophysics Data System (ADS)

Jivani, A. R.; Jani, A. R.

2011-12-01

Our own proposed potential is used to investigate few physical properties like total energy, bulk modulus, pressure derivative of bulk modulus, elastic constants, pressure derivative of elastic constants, Poisson's ratio and Young's modulus of Ge1-xSnx solid solution with x is atomic concentration of α-Sn. The potential combines linear plus quadratic types of electron-ion interaction. First time screening function proposed by Sarkar et al is used to investigate the properties of the Ge-Sn solid solution system.

Functionalised graphene sheets as effective high dielectric constant fillers

PubMed Central

2011-01-01

A new functionalised graphene sheet (FGS) filled poly(dimethyl)siloxane insulator nanocomposite has been developed with high dielectric constant, making it well suited for applications in flexible electronics. The dielectric permittivity increased tenfold at 10 Hz and 2 wt.% FGS, while preserving low dielectric losses and good mechanical properties. The presence of functional groups on the graphene sheet surface improved the compatibility nanofiller/polymer at the interface, reducing the polarisation process. This study demonstrates that functionalised graphene sheets are ideal nanofillers for the development of new polymer composites with high dielectric constant values. PACS: 78.20.Ci, 72.80.Tm, 62.23.Kn PMID:21867505

Functionalised graphene sheets as effective high dielectric constant fillers

NASA Astrophysics Data System (ADS)

Romasanta, Laura J.; Hernández, Marianella; López-Manchado, Miguel A.; Verdejo, Raquel

2011-08-01

A new functionalised graphene sheet (FGS) filled poly(dimethyl)siloxane insulator nanocomposite has been developed with high dielectric constant, making it well suited for applications in flexible electronics. The dielectric permittivity increased tenfold at 10 Hz and 2 wt.% FGS, while preserving low dielectric losses and good mechanical properties. The presence of functional groups on the graphene sheet surface improved the compatibility nanofiller/polymer at the interface, reducing the polarisation process. This study demonstrates that functionalised graphene sheets are ideal nanofillers for the development of new polymer composites with high dielectric constant values. PACS: 78.20.Ci, 72.80.Tm, 62.23.Kn

Calibration of the fine-structure constant of graphene by time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Sindona, A.; Pisarra, M.; Vacacela Gomez, C.; Riccardi, P.; Falcone, G.; Bellucci, S.

2017-11-01

One of the amazing properties of graphene is the ultrarelativistic behavior of its loosely bound electrons, mimicking massless fermions that move with a constant velocity, inversely proportional to a fine-structure constant αg of the order of unity. The effective interaction between these quasiparticles is, however, better controlled by the coupling parameter αg*=αg/ɛ , which accounts for the dynamic screening due to the complex permittivity ɛ of the many-valence electron system. This concept was introduced in a couple of previous studies [Reed et al., Science 330, 805 (2010) and Gan et al., Phys. Rev. B 93, 195150 (2016)], where inelastic x-ray scattering measurements on crystal graphite were converted into an experimentally derived form of αg* for graphene, over an energy-momentum region on the eV Å -1 scale. Here, an accurate theoretical framework is provided for αg*, using time-dependent density-functional theory in the random-phase approximation, with a cutoff in the interaction between excited electrons in graphene, which translates to an effective interlayer interaction in graphite. The predictions of the approach are in excellent agreement with the above-mentioned measurements, suggesting a calibration method to substantially improve the experimental derivation of αg*, which tends to a static limiting value of ˜0.14 . Thus, the ab initio calibration procedure outlined demonstrates the accuracy of perturbation expansion treatments for the two-dimensional gas of massless Dirac fermions in graphene, in parallel with quantum electrodynamics.

Amino acid residues in Anabaena ferredoxin crucial to interaction with ferredoxin-NADP+ reductase: site-directed mutagenesis and laser flash photolysis.

PubMed

Hurley, J K; Salamon, Z; Meyer, T E; Fitch, J C; Cusanovich, M A; Markley, J L; Cheng, H; Xia, B; Chae, Y K; Medina, M

1993-09-14

Ferredoxin (Fd) functions in photosynthesis to transfer electrons from photosystem I to ferredoxin-NADP+ reductase (FNR). We have made several site-directed mutants of Anabaena 7120 Fd and have used laser flash photolysis to investigate the effects of these mutations on the kinetics of reduction of oxidized Fd by deazariboflavin semiquinone (dRfH.) and the reduction of oxidized Anabaena FNR by reduced Fd. None of the mutations influenced the second-order rate constant for dRfH. reduction by more than a factor of 2, suggesting that the ability of the [2Fe-2S] cluster to participate in electron transfer was not seriously affected. In contrast, a surface charge reversal mutation, E94K, resulted in a 20,000-fold decrease in the second-order rate constant for electron transfer from Fd to FNR, whereas a similar mutation at an adjacent site, E95K, produced little or no change in reaction rate constant compared to wild-type Fd. Such a dramatic difference between contiguous surface mutations suggests a very precise surface complementarity at the protein-protein interface. Mutations introduced at F65 (F65I and F65A) also decreased the rate constant for the Fd/FNR electron transfer reaction by more than 3 orders of magnitude. Spectroscopic and thermodynamic measurements with both the E94 and F65 mutants indicated that the kinetic differences cannot be ascribed to changes in gross conformation, redox potential, or FNR binding constant but rather reflect the protein-protein interactions that control electron transfer. Several mutations at other sites in the vicinity of E94 and F65 (R42, T48, D68, and D69) resulted in little or no perturbation of the Fd/FNR interaction.(ABSTRACT TRUNCATED AT 250 WORDS)

Exploratory studies of new avenues to achieve high electromechanical response and high dielectric constant in polymeric materials

NASA Astrophysics Data System (ADS)

Huang, Cheng

High performance soft electronic materials are key elements in advanced electronic devices for broad range applications including capacitors, actuators, artificial muscles and organs, smart materials and structures, microelectromechanical (MEMS) and microfluidic devices, acoustic devices and sensors. This thesis exploits new approaches to improve the electromechanical response and dielectric response of these materials. By making use of novel material phenomena such as large anisotropy in dipolar response in liquid crystals (LCs) and all-organic composites in which high dielectric constant organic solids and conductive polymers are either physically blended into or chemically grafted to a polymer matrix, we demonstrate that high dielectric constant and high electromechanical conversion efficiency comparable to that in ceramic materials can be achieved. Nano-composite approach can also be utilized to improve the performance of the electronic electroactive polymers (EAPs) and composites, for example, exchange coupling between the fillers and matrix with very large dielectric contrast can lead to significantly enhance the dielectric response as well as electromechanical response when the heterogeneity size of the composite is comparable to the exchange length. In addition to the dielectric composites, in which high dielectric constant fillers raise the dielectric constant of composites, conductive percolation can also lead to high dielectric constant in polymeric materials. An all-polymer percolative composite is introduced which exhibits very high dielectric constant (>7,000). The flexible all-polymer composites with a high dielectric constant make it possible to induce a high electromechanical response under a much reduced electric field in the field effect electroactive polymer (EAP) actuators (a strain of 2.65% with an elastic energy density of 0.18 J/cm3 can be achieved under a field of 16 V/mum). Agglomeration of the particles can also be effectively prevented by in situ preparation. High dielectric constant copper phthalocyanine oligomer and conductive polyaniline oligomer were successfully bonded to polyurethane backbone to form fully functionalized nano-phase polymers. Improvement of dispersibility of oligomers in polymer matrix makes the system self-organize the nanocomposites possessing oligomer nanophase (below 30nm) within the fully functionalized polymers. The resulting nanophase polymers significantly enhance the interface effect, which through the exchange coupling raises the dielectric response markedly above that expected from simple mixing rules for dielectric composites. Consequently, these nano-phase polymers offer a high dielectric constant (a dielectric constant near 1,000 at 20 Hz), improve the breakdown field and mechanical properties, and exhibit high electromechanical response. A longitudinal strain of more than -14% can be induced under a much reduced field, 23 V/mum, with an elastic energy density of higher than 1 J/cm3. The elastic modulus is as high as 100MPa, and a transverse strain is 7% under the same field. (Abstract shortened by UMI.)

Electron attachment to C{sub 2} fluorocarbon radicals at high temperature

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

Shuman, Nicholas S.; Miller, Thomas M.; Viggiano, Albert A., E-mail: afrl.rvborgmailbox@kirtland.af.mil

Thermal electron attachment to the radical species C{sub 2}F{sub 3} and C{sub 2}F{sub 5} has been studied over the temperature range 300–890 K using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Both radicals exclusively undergo dissociative attachment to yield F{sup −}. The rate constant for C{sub 2}F{sub 5} shows little dependence over the temperature range, remaining ∼4 × 10{sup −9} cm{sup 3} s{sup −1}. The rate constant for C{sub 2}F{sub 3} attachment rises steeply with temperature from 3 × 10{sup −11} cm{sup 3} s{sup −1} at 300 K to 1 × 10{sup −9} cm{sup 3} s{sup −1} at 890 K.more » The behaviors of both species at high temperature are in agreement with extrapolations previously made from data below 600 K using a recently developed kinetic modeling approach. Measurements were also made on C{sub 2}F{sub 3}Br and C{sub 2}F{sub 5}Br (used in this work as precursors to the radicals) over the same temperature range, and, for C{sub 2}F{sub 5}Br as a function of electron temperature. The attachment rate constants to both species rise with temperature following Arrhenius behavior. The attachment rate constant to C{sub 2}F{sub 5}Br falls with increasing electron temperature, in agreement with the kinetic modeling. The current data fall in line with past predictions of the kinetic modeling approach, again showing the utility of this simplified approach.« less

The derivative discontinuity of the exchange-correlation functional.

PubMed

Mori-Sánchez, Paula; Cohen, Aron J

2014-07-28

The derivative discontinuity is a key concept in electronic structure theory in general and density functional theory in particular. The electronic energy of a quantum system exhibits derivative discontinuities with respect to different degrees of freedom that are a consequence of the integer nature of electrons. The classical understanding refers to the derivative discontinuity of the total energy as a function of the total number of electrons (N), but it can also manifest at constant N. Examples are shown in models including several hydrogen systems with varying numbers of electrons or nuclear charge (Z), as well as the 1-dimensional Hubbard model (1DHM). Two sides of the problem are investigated: first, the failure of currently used approximate exchange-correlation functionals in DFT and, second, the importance of the derivative discontinuity in the exact electronic structure of molecules, as revealed by full configuration interaction (FCI). Currently, all approximate functionals, including hybrids, miss the derivative discontinuity, leading to basic errors that can be seen in many ways: from the complete failure to give the total energy of H2 and H2(+), to the missing gap in Mott insulators such as stretched H2 and the thermodynamic limit of the 1DHM, or a qualitatively incorrect density in the HZ molecule with two electrons and incorrect electron transfer processes. Description of the exact particle behaviour of electrons is emphasised, which is key to many important physical processes in real systems, especially those involving electron transfer, and offers a challenge for the development of new exchange-correlation functionals.

Electronic and thermal properties of germanene and stanene by first-principles calculations

NASA Astrophysics Data System (ADS)

Jomehpour Zaveh, S.; Roknabadi, M. R.; Morshedloo, T.; Modarresi, M.

2016-03-01

The electronic, vibrational and thermal properties of germanene and stanene have been investigated based on density functional theory (DFT) and density functional perturbation theory (DFPT). The electronic band structure, total and partial density of states and phonon dispersion spectrum and states are analyzed. The phonon spectrum is positive for all modes in the first Brillouin zone and there is a phonon energy band gap between acoustic and optical modes which is around 50 cm-1 for both structure. The constant-volume specific heats of two structures are calculated by using phonon spectrum and density of states. The spin-orbit coupling (SOC) opens a direct energy band gap at the Dirac point, softens phonon spectrum and decreases phonon group velocity of ZA mode.

An ab-initio investigation on SrLa intermetallic compound

NASA Astrophysics Data System (ADS)

Kumar, S. Ramesh; Jaiganesh, G.; Jayalakshmi, V.

2018-05-01

The electronic, elastic and thermodynamic property of CsCl-type SrLa are investigated through density functional theory. The energy-volume relation for this compound has been obtained. The band structure, density of states and charge density in (110) plane are also examined. The elastic constants (C11, C12 and C44) of SrLa is computed, then, using these elastic constants, the bulk moduli, shear moduli, Young's moduli and Poisson's ratio are also derived. The calculated results showed that CsCl-type SrLa is ductile at ambient conditions. The thermodynamic quantities such as free energy, entropy and heat capacity as a function of temperature are estimated and the results obtained are discussed.

Predicting the Rate Constant of Electron Tunneling Reactions at the CdSe-TiO2 Interface.

PubMed

Hines, Douglas A; Forrest, Ryan P; Corcelli, Steven A; Kamat, Prashant V

2015-06-18

Current interest in quantum dot solar cells (QDSCs) motivates an understanding of the electron transfer dynamics at the quantum dot (QD)-metal oxide (MO) interface. Employing transient absorption spectroscopy, we have monitored the electron transfer rate (ket) at this interface as a function of the bridge molecules that link QDs to TiO2. Using mercaptoacetic acid, 3-mercaptopropionic acid, 8-mercaptooctanoic acid, and 16-mercaptohexadecanoic acid, we observe an exponential attenuation of ket with increasing linker length, and attribute this to the tunneling of the electron through the insulating linker molecule. We model the electron transfer reaction using both rectangular and trapezoidal barrier models that have been discussed in the literature. The one-electron reduction potential (equivalent to the lowest unoccupied molecular orbital) of each molecule as determined by cyclic voltammetry (CV) was used to estimate the effective barrier height presented by each ligand at the CdSe-TiO2 interface. The electron transfer rate (ket) calculated for each CdSe-ligand-TiO2 interface using both models showed the results in agreement with the experimentally determined trend. This demonstrates that electron transfer between CdSe and TiO2 can be viewed as electron tunneling through a layer of linking molecules and provides a useful method for predicting electron transfer rate constants.

Exchange Energy Density Functionals that reproduce the Linear Response Function of the Free Electron Gas

NASA Astrophysics Data System (ADS)

García-Aldea, David; Alvarellos, J. E.

2009-03-01

We present several nonlocal exchange energy density functionals that reproduce the linear response function of the free electron gas. These nonlocal functionals are constructed following a similar procedure used previously for nonlocal kinetic energy density functionals by Chac'on-Alvarellos-Tarazona, Garc'ia-Gonz'alez et al., Wang-Govind-Carter and Garc'ia-Aldea-Alvarellos. The exchange response function is not known but we have used the approximate response function developed by Utsumi and Ichimaru, even we must remark that the same ansatz can be used to reproduce any other response function with the same scaling properties. We have developed two families of new nonlocal functionals: one is constructed with a mathematical structure based on the LDA approximation -- the Dirac functional for the exchange - and for the second one the structure of the second order gradient expansion approximation is took as a model. The functionals are constructed is such a way that they can be used in localized systems (using real space calculations) and in extended systems (using the momentum space, and achieving a quasilinear scaling with the system size if a constant reference electron density is defined).

Structural, elastic and electronic properties of transition metal carbides ZnC, NbC and their ternary alloys ZnxNb1-xC

NASA Astrophysics Data System (ADS)

Zidi, Y.; Méçabih, S.; Abbar, B.; Amari, S.

2018-02-01

We have investigated the structural, electronic and elastic properties of transition-metal carbides ZnxNb1-xC alloys in the range of 0 ≤ x ≤ 1 using the density functional theory (DFT). The full potential linearized augmented plane wave (FP-LAPW) method within a framework of the generalized gradient approximation (GGA) and GGA + U (where U is the Hubbard correlation terms) approach is used to perform the calculations presented here. The lattice parameters, the bulk modulus, its pressure derivative and the elastic constants were determined. We have obtained Young's modulus, shear modulus, Poisson's ratio, anisotropy factor by the aid of the calculated elastic constants. We discuss the total and partial densities of states and charge densities.

Probing the electronic transport on the reconstructed Au/Ge(001) surface

PubMed Central

Krok, Franciszek; Kaspers, Mark R; Bernhart, Alexander M; Nikiel, Marek; Jany, Benedykt R; Indyka, Paulina; Wojtaszek, Mateusz; Möller, Rolf

2014-01-01

Summary By using scanning tunnelling potentiometry we characterized the lateral variation of the electrochemical potential µec on the gold-induced Ge(001)-c(8 × 2)-Au surface reconstruction while a lateral current flows through the sample. On the reconstruction and across domain boundaries we find that µec shows a constant gradient as a function of the position between the contacts. In addition, nanoscale Au clusters on the surface do not show an electronic coupling to the gold-induced surface reconstruction. In combination with high resolution scanning electron microscopy and transmission electron microscopy, we conclude that an additional transport channel buried about 2 nm underneath the surface represents a major transport channel for electrons. PMID:25247129

Is back-electron transfer process in Betaine-30 coherent?

NASA Astrophysics Data System (ADS)

Rafiq, Shahnawaz; Scholes, Gregory D.

2017-09-01

The possible role of coherent vibrational motion in ultrafast photo-induced electron transfer remains unclear despite considerable experimental and theoretical advances. We revisited this problem by tracking the back-electron transfer (bET) process in Betaine-30 with broadband pump-probe spectroscopy. Dephasing time constant of certain high-frequency vibrations as a function of solvent shows a trend similar to the ET rates. In the purview of Bixon-Jortner model, high-frequency quantum vibrations bridge the reactant-product energy gap by providing activationless vibronic channels. Such interaction reduces the effective coupling significantly and thereby the coherence effects are eliminated due to energy gap fluctuations, making the back-electron transfer incoherent.

Paramagnet induced signal quenching in MAS-DNP experiments in frozen homogeneous solutions

NASA Astrophysics Data System (ADS)

Corzilius, Björn; Andreas, Loren B.; Smith, Albert A.; Ni, Qing Zhe; Griffin, Robert G.

2014-03-01

The effects of nuclear signal quenching induced by the presence of a paramagnetic polarizing agent are documented for conditions used in magic angle spinning (MAS)-dynamic nuclear polarization (DNP) experiments on homogeneous solutions. In particular, we present a detailed analysis of three time constants: (1) the longitudinal build-up time constant TB for 1H; (2) the rotating frame relaxation time constant T1ρ for 1H and 13C and (3) T2 of 13C, the transverse relaxation time constant in the laboratory frame. These relaxation times were measured during microwave irradiation at a magnetic field of 5 T (140 GHz) as a function of the concentration of four polarizing agents: TOTAPOL, 4-amino-TEMPO, trityl (OX063), and Gd-DOTA and are compared to those obtained for a sample lacking paramagnetic doping. We also report the EPR relaxation time constants T1S and T2S, the DNP enhancements, ε, and the parameter E, defined below, which measures the sensitivity enhancement for the four polarizing agents as a function of the electron concentration. We observe substantial intensity losses (paramagnetic quenching) with all of the polarizing agents due to broadening mechanisms and cross relaxation during MAS. In particular, the monoradical trityl and biradical TOTAPOL induce ∼40% and 50% loss of signal intensity. In contrast there is little suppression of signal intensity in static samples containing these paramagnetic species. Despite the losses due to quenching, we find that all of the polarizing agents provide substantial gains in signal intensity with DNP, and in particular that the net enhancement is optimal for biradicals that operate with the cross effect. We discuss the possibility that much of this polarization loss can be regained with the development of instrumentation and methods to perform electron decoupling.

Density functional perturbational orbital theory of spin polarization in electronic systems. II. Transition metal dimer complexes.

PubMed

Seo, Dong-Kyun

2007-11-14

We present a theoretical scheme for a semiquantitative analysis of electronic structures of magnetic transition metal dimer complexes within spin density functional theory (DFT). Based on the spin polarization perturbational orbital theory [D.-K. Seo, J. Chem. Phys. 125, 154105 (2006)], explicit spin-dependent expressions of the spin orbital energies and coefficients are derived, which allows to understand how spin orbitals form and change their energies and shapes when two magnetic sites are coupled either ferromagnetically or antiferromagnetically. Upon employment of the concept of magnetic orbitals in the active-electron approximation, a general mathematical formula is obtained for the magnetic coupling constant J from the analytical expression for the electronic energy difference between low-spin broken-symmetry and high-spin states. The origin of the potential exchange and kinetic exchange terms based on the one-electron picture is also elucidated. In addition, we provide a general account of the DFT analysis of the magnetic exchange interactions in compounds for which the active-electron approximation is not appropriate.

Evolution of the orbitals Dy-4f in the DyB2 compound using the LDA, PBE approximations, and the PBE0 hybrid functional

NASA Astrophysics Data System (ADS)

Rasero Causil, Diego; Ortega López, César; Espitia Rico, Miguel

2018-04-01

Computational calculations of total energy based on density functional theory were used to investigate the structural, electronic, and magnetic properties of the DyB2 compounds in the hexagonal structure. The calculations were carried out by means of the full-potential linearized augmented plane wave (FP-LAPW) method, employing the computational Wien2k package. The local density approximation (LDA) and the generalized gradient approximation (GGA) were used for the electron-electron interactions. Additionally, we used the functional hybrid PBE0 for a better description the electronic and magnetic properties, because the DyB2 compound is a strongly-correlated system. We found that the calculated lattice constant agrees well with the values reported theoretically and experimentally. The density of states (DOS) calculation shows that the compound exhibits a metallic behavior and has magnetic properties, with a total magnetic moment of 5.47 μ0/cell determined mainly by the 4f states of the rare earth elements. The functional PBE0 shows a strong localization of the Dy-4f orbitals.

New Ways of Treating Data for Diatomic Molecule 'shelf' and Double-Minimum States

NASA Astrophysics Data System (ADS)

Le Roy, Robert J.; Tao, Jason; Khanna, Shirin; Pashov, Asen; Tellinghuisen, Joel

2017-06-01

Electronic states whose potential energy functions have 'shelf' or double-minimum shapes have always presented special challenges because, as functions of vibrational quantum number, the vibrational energies/spacings and inertial rotational constants either have an abrupt change of character with discontinuous slope, or past a given point, become completely chaotic. The present work shows that a `traditional' methodology developed for deep `regular' single-well potentials can also provide accurate `parameter-fit' descriptions of the v-dependence of the vibrational energies and rotational constants of shelf-state potentials that allow a conventional RKR calculation of their Potential energy functions. It is also shown that a merging of Pashov's uniquely flexible 'spline point-wise' potential function representation with Le Roy's `Morse/Long-Range' (MLR) analytic functional form which automatically incorporates the correct theoretically known long-range form, yields an analytic function that incorporates most of the advantages of both approaches. An illustrative application of this method to data to a double-minimum state of Na_2 will be described.

Mechanistic information from the first volume profile analysis for a reversible intermolecular electron-transfer reaction involving pentaammine(isonicotinamide)ruthenium and cytochrome c

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

Baensch, B.; Meier, M.; Martinez, P.

1994-10-12

The reversible intermolecular electron-transfer reaction between pentaammine(isonicotinamide)ruthenium(II/III) and horse-heart cytochrome c iron(III/II) was subjected to a detailed kinetic and thermodynamic study as a function of temperature and pressure. Theoretical calculations based on the Marcus-Hush theory were employed to predict all rate and equilibrium constants as well as activation parameters. There is an excellent agreement between the kinetically and thermodynamically determined equilibrium constants and associated pressure parameters. These data are used to construct a volume profile for the overall process, from which it follows that the transition state lies halfway between the reactant and product states on a volume basis. Themore » reorganization in the transition state has reached a similar degree in both directions of the electron-transfer process and corresponds to a {lambda}{sup {double_dagger}} value of 0.44 for this reversible reaction. This is the first complete volume profile analysis for a reversible intermolecular electron-transfer reaction.« less

A potential half-Heusler thermoelectric material ScAuSn: A first principle study

NASA Astrophysics Data System (ADS)

Joshi, H.; Rai, D. P.; Thapa, R. K.

2018-04-01

Density Functional Theory along with semi classical Boltzmann transport theory have been applied to study the electronic and thermoelectric property of the Heusler alloy ScAuSn. It has been found that ScAuSn is an indirect band gap semiconductor with a gap of 0.344 eV. The thermoelectric properties such as electrical conductivity (σ), Seebeck coefficient (S), electronic thermal conductivity (κ) etc. are reported as a function of chemical potential in the region ± 2.0 eV, with respect to constant temperature. The calculated ZT value is almost equal to 1, thus making ScAuSn a potential thermoelectric candidate.

Dielectric constant of atomic fluids with variable polarizability

PubMed Central

Alder, B. J.; Beers, J. C.; Strauss, H. L.; Weis, J. J.

1980-01-01

The Clausius-Mossotti function for the dielectric constant is expanded in terms of single atom and pair polarizabilities, leading to contributions that depend on both the trace and the anisotropy of the pair-polarizability tensor. The short-range contribution of the anisotropic part to the pair polarizabilities has previously been obtained empirically from light scattering experiments, whereas the trace contribution is now empirically determined by comparison to dielectric experiments. For helium, the short-range trace part agrees well with electronic structure calculations, whereas for argon qualitative agreement is achieved. PMID:16592830

Dielectric constant of atomic fluids with variable polarizability.

PubMed

Alder, B J; Beers, J C; Strauss, H L; Weis, J J

1980-06-01

The Clausius-Mossotti function for the dielectric constant is expanded in terms of single atom and pair polarizabilities, leading to contributions that depend on both the trace and the anisotropy of the pair-polarizability tensor. The short-range contribution of the anisotropic part to the pair polarizabilities has previously been obtained empirically from light scattering experiments, whereas the trace contribution is now empirically determined by comparison to dielectric experiments. For helium, the short-range trace part agrees well with electronic structure calculations, whereas for argon qualitative agreement is achieved.

Thermophysical properties of liquid rare earth metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Patel, H. P.; Jani, A. R.

2013-06-01

The thermodynamical properties like long wavelength limit S(0), iso-thermal compressibility (χT), thermal expansion coefficient (αV), thermal pressure coefficient (γV), specific heat at constant volume (CV) and specific heat at constant pressure (CP) are calculated for liquid rare earth metals. Our newly constructed parameter free model potential is used to describe the electron ion interaction due to Sarkar et al (S) local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermophysical properties of liquid rare earth metals.

Resistivity of a simple metal from room temperature to 10 to the 6th K

NASA Astrophysics Data System (ADS)

Milchberg, H. M.; Freeman, R. R.; Davey, S. C.; More, R. M.

1988-11-01

The resistivity of nearly solid-density Al was measured as a function of temperature over 4 orders of magnitude above ambient by observing the self-reflection of an intense, less than 0.5 psec, 308-nm light pulse incident on a planar Al target. As an increasing function of electron temperature, the resistivity is observed initially to increase, reach a maximum which is relatively constant over an extended temperature range, and then decrease at the highest temperatures. The broad maximum is interpreted as resistivity saturation, a condition in which the mean free path of the conduction electrons reaches a minimum value as a function of temperature, regardless of the extent of any further disorder in the material.

Structural and electronic properties of GaAs and GaP semiconductors

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

Rani, Anita; Kumar, Ranjan

2015-05-15

The Structural and Electronic properties of Zinc Blende phase of GaAs and GaP compounds are studied using self consistent SIESTA-code, pseudopotentials and Density Functional Theory (DFT) in Local Density Approximation (LDA). The Lattice Constant, Equillibrium Volume, Cohesive Energy per pair, Compressibility and Band Gap are calculated. The band gaps calcultated with DFT using LDA is smaller than the experimental values. The P-V data fitted to third order Birch Murnaghan equation of state provide the Bulk Modulus and its pressure derivatives. Our Structural and Electronic properties estimations are in agreement with available experimental and theoretical data.

Structural and electronic properties of L-amino acids

NASA Astrophysics Data System (ADS)

Tulip, P. R.; Clark, S. J.

2005-05-01

The structural and electronic properties of four L-amino acids alanine, leucine, isoleucine, and valine have been investigated using density functional theory (DFT) and the generalized gradient approximation. Within the crystals, it is found that the constituent molecules adopt zwitterionic configurations, in agreement with experimental work. Lattice constants are found to be in good agreement with experimentally determined values, although certain discrepancies do exist due to the description of van der Waals interactions. We find that these materials possess wide DFT band gaps in the region of 5 eV, with electrons highly localized to the constituent molecules. It is found that the main mechanisms behind crystal formation are dipolar interactions and hydrogen bonding of a primarily electrostatic character, in agreement with current biochemical understanding of these systems. The electronic structure suggests that the amine and carboxy functional groups are dominant in determining band structure.

Coumaraz-2-on-4-ylidene: Ambiphilic N-heterocyclic Carbenes with a Fine-Tunable Electronic Structure.

PubMed

Song, Hayoung; Kim, Hyunho; Lee, Eunsung

2018-05-16

Herein, a coumaraz-2-on-4-ylidene (1) as a new example of ambiphilic N-heterocyclic carbenes with fine tunable electronic properties is reported. The N-carbamic and aryl groups on carbene carbon provide exceptionally high electrophilicity and nucleophilicity simultaneously to the carbene center, as evidenced by the 77Se NMR chemical shifts of their selenoketone derivatives and the CO stretching strengths of their rhodium carbonyl complexes. Since the precursors of 1 could be synthesized from various functionalized Schiff bases in a practical and scalable manner, the electronic properties of 1 can be fine-tuned in quantitative and predictable way using the Hammett σ constant of the functional groups on aryl ring. The facile electronic tuning capability of 1 may be further applicable to eliciting novel properties in main-group and transition metal chemistry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electron counting and a large family of two-dimensional semiconductors

NASA Astrophysics Data System (ADS)

Miao, Maosheng; Botana, Jorge; Zurek, Eva; Liu, Jingyao; Yang, Wen

Two-dimensional semiconductors (2DSC) are currently the focus of many studies, thanks to their novel and superior transport properties that may greatly influence future electronic devices. The potential applications of 2DSCs range from low-dimensional electronics, topological insulators and vallytronics all the way to novel photolysis. However, compared with the conventional semiconductors that are comprised of main group elements and cover a large range of band gaps and lattice constants, the choice of 2D materials is very limited. In this work, we propose and demonstrate a large family of 2DSCs, all adopting the same structure and consisting of only main group elements. Using advanced density functional calculations, we demonstrate the attainability of these materials, and show that they cover a large range of lattice constants, band gaps and band edge states, making them good candidate materials for heterojunctions. This family of two dimensional materials may be instrumental in the fabrication of 2DSC devices that may rival the currently employed 3D semiconductors.

Assessment of Scanning Tunneling Spectroscopy Modes Inspecting Electron Confinement in Surface-Confined Supramolecular Networks

PubMed Central

Krenner, Wolfgang; Kühne, Dirk; Klappenberger, Florian; Barth, Johannes V.

2013-01-01

Scanning tunneling spectroscopy (STS) enables the local, energy-resolved investigation of a samples surface density of states (DOS) by measuring the differential conductance (dI/dV) being approximately proportional to the DOS. It is popular to examine the electronic structure of elementary samples by acquiring dI/dV maps under constant current conditions. Here we demonstrate the intricacy of STS mapping of samples exhibiting a strong corrugation originating from electronic density and local work function changes. The confinement of the Ag(111) surface state by a porous organic network is studied with maps obtained under constant-current (CC) as well as open-feedback-loop (OFL) conditions. We show how the CC maps deviate markedly from the physically more meaningful OFL maps. By applying a renormalization procedure to the OFL data we can mimic the spurious effects of the CC mode and thereby rationalize the physical effects evoking the artefacts in the CC maps. PMID:23503526

Pressure-induced elastic, electronic and optical properties of Ba(Mg1/3Nb2/3)O3 using first principles calculations

NASA Astrophysics Data System (ADS)

Islam, A. K. M. Farid Ul; Liton, M. N. H.; Anowar, M. G. M.

2018-06-01

The pressure dependent mechanical stability, electronic structure and optical properties of Ba(Mg1/3Nb2/3)O3 (BMN) perovskite have been investigated in the framework of the density functional theory. Geometry optimization shows that the BMN possesses more compressibility along c-axis. The dependency of the elastic constants, the aggregated elastic moduli (B, G) and the elastic anisotropy on pressure has also been studied. BMN shows brittle character at ambient pressure but it becomes ductile, and also stiffer and anisotropic nature due to external pressure. Electronic structure indicates the conversion of indirect to direct band gap with increasing pressure. Dominated ionic character of BMN is confirmed from the bond population analysis. By analyzing the optical spectra, a red shift at the band edge is observed in the visible range indicating the band gap tuning. It is seen that the static dielectric constant increases with pressure.

Role of Excited Nitrogen In The Ionosphere

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.; Cartwright, D. C.; Bolorizadeh, M. A.

2006-12-01

Sunlight photoionises atoms and molecules in the Earth's upper atmosphere, producing ions and photoelectrons. The photoelectrons then produce further ionisation by electron impact. These processes produce the ionosphere, which contains various positive ions, such as NO+, N+, and O+, and an equal density of free electrons. O+(4S) ions are long-lived and so the electron density is determined mainly by the density of O+(4S). This density is dependent on ambipolar diffusion and on loss processes, which are principally reactions with O2 and N2. The reaction with N2 is known to be strongly dependent on the vibrational state of N2 but the rate constants are not well determined for the ionosphere. Vibrational excitation of N2 is produced by direct excitation by thermal electrons and photoelectrons and by cascade from the excited states of N2 that are produced by photoelectron impact. It can also be produced by a chemical reaction and by vibrational-translational transitions. The vibrational excitation is lost by deexcitation by electron impact, by step-wise quenching in collisions with O atoms, and in the reaction with O+(4S). The distribution of vibrational levels is rearranged by vibrational-vibrational transitions, and by molecular diffusion vertically in the atmosphere. A computational model that includes these processes and predicts the electron density as a function of height in the ionosphere is described. This model is a combination of a "statistical equilibrium" calculation, which is used to predict the populations of the excited states of N2, and a time-step calculation of the atmospheric reactions and processes. The latter includes a calculation of photoionisation down through the atmosphere as a function of time of day and solar activity, and calculations at 0.1 s intervals of the changing densities of positive ions, electrons and N2 in the different vibrational levels. The validity of the model is tested by comparison of the predicted electron densities with the International Reference Ionosphere (IRI) of electron density measurements. The contribution of various input parameters can be investigated by their effect on the accuracy of the calculated electron densities. Here the effects of two different sets of rate constants for the reaction of vibrationally excited N2 with O+(4S) are investigated. For reference, predictions using the different sets are compared with laboratory measurements. Then the effect of using the different sets in the computational model of the ionosphere is investigated. It is shown that one set gives predictions of electron densities that are in reasonable agreement with the IRI, while the other set does not. Both sets result in underestimation of the electron density at the height of the peak electron density in the atmosphere, suggesting that either the amount of vibrational excitation or the rate constants may be overestimated. Our comparison is made for two cases with different conditions, to give an indication of the limitations of the atmospheric modeling and also insight into ways in which the sets of rate constants may be deficient.

Delocalized and localized states of eg electrons in half-doped manganites.

PubMed

Winkler, E L; Tovar, M; Causa, M T

2013-07-24

We have studied the magnetic behaviour of half-doped manganite Y0.5Ca0.5MnO3 in an extended range of temperatures by means of magnetic susceptibility, χ(T), and electron spin resonance (ESR) experiments. At high temperature the system crystallizes in an orthorhombic structure. The resistivity value, ρ ≃ 0.05 Ω cm at 500 K, indicates a metallic behaviour, while the Curie-Weiss dependence of χ(T) and the thermal evolution of the ESR parameters are very well described by a model that considers a system conformed by localized Mn(4+) cores, [Formula: see text], and itinerant, eg, electrons. The strong coupling between t2g and eg electrons results in an enhanced Curie constant and an FM Curie-Weiss temperature that overcomes the AFM interactions between the [Formula: see text] cores. A transition to a more distorted phase is observed at T ≈ 500 K and signatures of localization of the eg electrons appear in the χ(T) behaviour below 300 K. A new Curie-Weiss regime is observed, where the Curie-constant value is consistent with dimer formation. Based on mean-field calculations, the dimer formation is predicted as a function of the interaction strength between the t2g and eg electrons.

Oxidation of β-blockers by birnessite: Kinetics, mechanism and effect of metal ions.

PubMed

Chen, Yong; Lu, Xiye; Liu, Lu; Wan, Dong; Chen, Huabin; Zhou, Danna; Sharma, Virender K

2018-03-01

Manganese dioxides are ubiquitous in natural waters, soils, and sediments and play an important role in oxidative transformation of organic pollutants. This work presents the kinetics of the oxidation of selected β-blockers, betaxolol, metoprolol, and atenolol by birnessite (δ-MnO 2 ) as a function of concentration of the β-blocker, dosage of δ-MnO 2 , and solution pH. The values of pseudo-first-order rate constants (k obs ) of β-blockers decreased in the order betaxolol > atenolol > metoprolol, which was positively correlated with their acid dissociation constants (K a ). Effect of series of metal ions (Fe 3+ , Cr 3+ , Al 3+ , Pb 2+ , Cu 2+ , Zn 2+ , Ni 2+ , Cd 2+ , Mg 2+ , and Ca 2+ ) on the degradation of β-blockers by δ-MnO 2 was systematically examined. All of these metal ions inhibited the oxidation reaction under the same constant ionic strength. The inhibition efficiency was positively correlated with the logarithm of stability constant of metal ions in aqueous solution (logK MeOH ). By LC-ESI-MS/MS analyses, the oxidation of β-blockers primarily involved hydroxylation and cleavage of the parent molecules to the short branched chain compounds. An electron transfer mechanism for the oxidation of β-blockers by δ-MnO 2 was proposed. The oxidation was initiated by the electron transfer from the nonbonding electrons on nitrogen (N-electrons) of β-blockers to δ-MnO 2 , followed by transformation of radical intermediates. These findings will help to understand the oxidation processes of β-blockers and predict the effect of metal ions on the removal of pollutants by δ-MnO 2 in the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural, electronic, mechanical, and thermoelectric properties of a novel half Heusler compound HfPtPb

NASA Astrophysics Data System (ADS)

Kaur, Kulwinder; Rai, D. P.; Thapa, R. K.; Srivastava, Sunita

2017-07-01

We explore the structural, electronic, mechanical, and thermoelectric properties of a new half Heusler compound HfPtPb, an all metallic heavy element, recently proposed to be stable [Gautier et al., Nat. Chem. 7, 308 (2015)]. In this work, we employ density functional theory and semi-classical Boltzmann transport equations with constant relaxation time approximation. The mechanical properties, such as shear modulus, Young's modulus, elastic constants, Poisson's ratio, and shear anisotropy factor, have been investigated. The elastic and phonon properties reveal that this compound is mechanically and dynamically stable. Pugh's ratio and Frantsevich's ratio demonstrate its ductile behavior, and the shear anisotropic factor reveals the anisotropic nature of HfPtPb. The band structure predicts this compound to be a semiconductor with a band gap of 0.86 eV. The thermoelectric transport parameters, such as Seebeck coefficient, electrical conductivity, electronic thermal conductivity, and lattice thermal conductivity, have been calculated as a function of temperature. The highest value of Seebeck coefficient is obtained for n-type doping at an optimal carrier concentration of 1.0 × 1020 e/cm3. We predict the maximum value of figure of merit (0.25) at 1000 K. Our investigation suggests that this material is an n-type semiconductor.

An experiment to verify that the weak interactions satisfy the strong equivalence principle. [electron capture and gravitational potential

NASA Technical Reports Server (NTRS)

Eby, P. B.

1978-01-01

The construction of a clock based on the beta decay process is proposed to test for any violations by the weak interaction of the strong equivalence principle bu determining whether the weak interaction coupling constant beta is spatially constant or whether it is a function of gravitational potential (U). The clock can be constructed by simply counting the beta disintegrations of some suitable source. The total number of counts are to be taken a measure of elapsed time. The accuracy of the clock is limited by the statistical fluctuations in the number of counts, N, which is equal to the square root of N. Increasing N gives a corresponding increase in accuracy. A source based on the electron capture process can be used so as to avoid low energy electron discrimination problems. Solid state and gaseous detectors are being considered. While the accuracy of this type of beta decay clock is much less than clocks based on the electromagnetic interaction, there is a corresponding lack of knowledge of the behavior of beta as a function of gravitational potential. No predictions from nonmetric theories as to variations in beta are available as yet, but they may occur at the U/sg C level.

Direct observation of 0.57 eV trap-related RF output power reduction in AlGaN/GaN high electron mobility transistors

NASA Astrophysics Data System (ADS)

Arehart, A. R.; Sasikumar, A.; Rajan, S.; Via, G. D.; Poling, B.; Winningham, B.; Heller, E. R.; Brown, D.; Pei, Y.; Recht, F.; Mishra, U. K.; Ringel, S. A.

2013-02-01

This paper reports direct evidence for trap-related RF output power loss in GaN high electron mobility transistors (HEMTs) grown by metal organic chemical vapor deposition (MOCVD) through increased concentration of a specific electron trap at EC-0.57 eV that is located in the drain access region, as a function of accelerated life testing (ALT). The trap is detected by constant drain current deep level transient spectroscopy (CID-DLTS) and the CID-DLTS thermal emission time constant precisely matches the measured drain lag. Both drain lag and CID-DLTS measurements show this state to already exist in pre-stressed devices, which coupled with its strong increase in concentration as a function of stress in the absence of significant increases in concentrations of other detected traps, imply its role in causing degradation, in particular knee walkout. This study reveals EC-0.57 eV trap concentration tracks degradation induced by ALT for MOCVD-grown HEMTs supplied by several commercial and university sources. The results suggest this defect has a common source and may be a key degradation pathway in AlGaN/GaN HEMTs and/or an indicator to predict device lifetime.

Laser collisional induced fluorescence electron density measurements as a function of ring bias and the onset of anode spot formation in a ring cusp magnetic field

NASA Astrophysics Data System (ADS)

Arthur, N. A.; Foster, J. E.; Barnat, E. V.

2018-05-01

Two-dimensional electron density measurements are made in a magnetic ring cusp discharge using laser collisional induced fluorescence. The magnet rings are isolated from the anode structure such that they can be biased independently in order to modulate electron flows through the magnetic cusps. Electron density images are captured as a function of bias voltage in order to assess the effects of current flow through the cusp on the spatial extent of the cusp. We anticipated that for a fixed current density being funneled through the magnetic cusp, the leak width would necessarily increase. Unexpectedly, the leak width, as measured by LCIF images, does not increase. This suggests that the current density is not constant, and that possibly either electrons are being heated or additional ionization events are occurring within the cusp. Spatially resolving electron temperature would be needed to determine if electrons are being heated within the cusp. We also observe breakdown of the anode magnetosheath and formation of anode spots at high bias voltage.

Rigorous Relativistic Methods for Addressing {P}- and {T}-NONCONSERVATION in Heavy-Element Molecules

NASA Astrophysics Data System (ADS)

Fleig, Timo

2013-06-01

A new and rigorous method for accurate ab-initio calculations of the electron electric dipole moment {P,T}-odd interaction constant is presented. The approach uses string-based Configuration Interaction wavefunctions and Dirac four-component spinors as one-particle basis functions, and the {P,T}-odd constant is obtained as an expectation value over these correlated wavefunctions. The method has been applied to the HfF^+ molecular ion to determine spectroscopic constants for four low-lying electronic states. For one of these states (Ω = 1) we have determined a new accurate benchmark value for the effective electric field E_{ eff} correlating 34 valence and outer atomic core electrons and using wavefunction expansions with nearly 5 \\cdot 10^8 coefficients. For the Ω = 1 state of the ThO molecule the first ab-initio result for the electron EDM interaction constant is presented. Aspects of modern all-electron relativistic many-body approaches applicable to both atoms and molecules will be discussed, including perspectives for the treatment of other interesting candidate systems and {P}- or {P,T}-non-conserving effects in molecular systems. %Zero-kinetic-energy (ZEKE) photoelectron spectroscopy was used to probe the vibrational levels in the ground electronic state of the chlorobenzene cation using a two-color photoionization scheme via the S{_1} electronic state of the neutral. Exciting through different S{_1} vibrational levels has revealed mixing of some S{_1} normal coordinates in the ground state of the cation. A previously-identified Fermi resonance in the S{_1} state of the neutral is also confirmed by the ZEKE spectra. The adiabatic ionization energy is measured as 73 170±5 cm^{-1}. S. Knecht, H. J. Å. Jensen and T. Fleig J. Chem. Phys. {132}, 014108 (2010 T. Fleig, H. J. Å. Jensen, J. Olsen and L. Visscher J. Chem. Phys. {124}, 104106 (2006) T. Fleig and M. K. Nayak Phys. Rev. X {XXX}, XXXX (submitted). T. G. Wright, S. I. Panov and T. A. Miller J. Chem. Phys. {102}(12), XXXX March 1995.

First-principles calculations of the structural, electronic, optical and thermal properties of the BNxAs1-x alloys

NASA Astrophysics Data System (ADS)

Hamioud, L.; Boumaza, A.; Touam, S.; Meradji, H.; Ghemid, S.; El Haj Hassan, F.; Khenata, R.; Omran, S. Bin

2016-06-01

The present paper aims to study the structural, electronic, optical and thermal properties of the boron nitride (BN) and BAs bulk materials as well as the BNxAs1-x ternary alloys by employing the full-potential-linearised augmented plane wave method within the density functional theory. The structural properties are determined using the Wu-Cohen generalised gradient approximation that is based on the optimisation of the total energy. For band structure calculations, both the Wu-Cohen generalised gradient approximation and the modified Becke-Johnson of the exchange-correlation energy and potential, respectively, are used. We investigated the effect of composition on the lattice constants, bulk modulus and band gap. Deviations of the lattice constants and the bulk modulus from the Vegard's law and the linear concentration dependence, respectively, were observed for the alloys where this result allows us to explain some specific behaviours in the electronic properties of the alloys. For the optical properties, the calculated refractive indices and the optical dielectric constants were found to vary nonlinearly with the N composition. Finally, the thermal effect on some of the macroscopic properties was predicted using the quasi-harmonic Debye model in which the lattice vibrations are taken into account.

The Kinetics of Heterogeneous Electron Transfer Reactions in Polar Solvents

DTIC Science & Technology

1994-04-20

focussed on systems for which rate constants and activation parameters are available as a function of the solvent, and as a function of temperature . The... temperature . The role of reactant structure in determining the kinetic parameters is also considered. Double layer effects both at unmodified and...that the Gibbs activation energy to form a monovalent cation from a neutral molecule via electrooxidation is different from that to form a monovalent

Electronic structure, mechanical and thermodynamic properties of BaPaO3 under pressure.

PubMed

Khandy, Shakeel Ahmad; Islam, Ishtihadah; Gupta, Dinesh C; Laref, Amel

2018-05-07

Density functional theory (DFT)-based investigations have been put forward on the elastic, mechanical, and thermo-dynamical properties of BaPaO 3 . The pressure dependence of electronic band structure and other physical properties has been carefully analyzed. The increase in Bulk modulus and decrease in lattice constant is seen on going from 0 to 30 GPa. The predicted lattice constants describe this material as anisotropic and ductile in nature at ambient conditions. Post-DFT calculations using quasi-harmonic Debye model are employed to envisage the pressure-dependent thermodynamic properties like Debye temperature, specific heat capacity, Grüneisen parameter, thermal expansion, etc. Also, the computed Debye temperature and melting temperature of BaPaO 3 at 0 K are 523 K and 1764.75 K, respectively.

Electronic and optical properties of RESn{sub 3} (RE=Pr & Nd) intermetallics: A first principles study

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

Pagare, G., E-mail: gita-pagare@yahoo.co.in; Abraham, Jisha A.; Department of Physics, National Defence Academy, Pune-411023

2015-06-24

A theoretical study of structural, electronic and optical properties of RESn{sub 3} (RE = Pr & Nd) intermetallics have been investigated systematically using first principles density functional theory. The calculations are carried out within the PBE-GGA and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and the calculated lattice parameters show well agreement with the experimental results. We first time predict elastic constants for these compounds. From energy dispersion curves, it is found that these compounds are metallic in nature. The linearmore » optical response of these compounds are also studied and the higher value of static dielectric constant shows the possibility to use them as good dielectric materials.« less

Bio-medical flow sensor. [intrvenous procedures

NASA Technical Reports Server (NTRS)

Winkler, H. E. (Inventor)

1981-01-01

A bio-medical flow sensor including a packageable unit of a bottle, tubing and hypodermic needle which can be pre-sterilized and is disposable. The tubing has spaced apart tubular metal segments. The temperature of the metal segments and fluid flow therein is sensed by thermistors and at a downstream location heat is input by a resistor to the metal segment by a control electronics. The fluids flow and the electrical power required for the resisto to maintain a constant temperature differential between the tubular metal segments is a measurable function of fluid flow through the tubing. The differential temperature measurement is made in a control electronics and also can be used to control a flow control valve or pump on the tubing to maintain a constant flow in the tubing and to shut off the tubing when air is present in the tubing.

Density functional study for crystalline structures and electronic properties of Si1- x Sn x binary alloys

NASA Astrophysics Data System (ADS)

Nagae, Yuki; Kurosawa, Masashi; Shibayama, Shigehisa; Araidai, Masaaki; Sakashita, Mitsuo; Nakatsuka, Osamu; Shiraishi, Kenji; Zaima, Shigeaki

2016-08-01

We have carried out density functional theory (DFT) calculation for Si1- x Sn x alloy and investigated the effect of the displacement of Si and Sn atoms with strain relaxation on the lattice constant and E- k dispersion. We calculated the formation probabilities for all atomic configurations of Si1- x Sn x according to the Boltzmann distribution. The average lattice constant and E- k dispersion were weighted by the formation probability of each configuration of Si1- x Sn x . We estimated the displacement of Si and Sn atoms from the initial tetrahedral site in the Si1- x Sn x unit cell considering structural relaxation under hydrostatic pressure, and we found that the breaking of the degenerated electronic levels of the valence band edge could be caused by the breaking of the tetrahedral symmetry. We also calculated the E- k dispersion of the Si1- x Sn x alloy by the DFT+U method and found that a Sn content above 50% would be required for the indirect-direct transition.

Third-order Douglas-Kroll Relativistic Coupled-Cluster Theory through Connected Single, Double, Triple, and Quadruple Substitutions: Applications to Diatomic and Triatomic Hydrides

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

Hirata, So; Yanai, Takeshi; De Jong, Wibe A.

Coupled-cluster methods including through and up to the connected single, double, triple, and quadruple substitutions (CCSD, CCSDT, and CCSDTQ) have been automatically derived and implemented for sequential and parallel executions for use in conjunction with a one-component third-order Douglas-Kroll (DK3) approximation for relativistic corrections. A combination of the converging electron-correlation methods, the accurate relativistic reference wave functions, and the use of systematic basis sets tailored to the relativistic approximation has been shown to predict the experimental singlet-triplet separations within 0.02 eV (0.5 kcal/mol) for five triatomic hydrides (CH2, NH2+, SiH2, PH2+, and AsH2+), the experimental bond lengths within 0.002 angstroms,more » rotational constants within 0.02 cm-1, vibration-rotation constants within 0.01 cm-1, centrifugal distortion constants within 2 %, harmonic vibration frequencies within 9 cm-1 (0.4 %), anharmonic vibrational constants within 2 cm-1, and dissociation energies within 0.03 eV (0.8 kcal/mol) for twenty diatomic hydrides (BH, CH, NH, OH, FH, AlH, SiH, PH, SH, ClH, GaH, GeH, AsH, SeH, BrH, InH, SnH, SbH, TeH, and IH) containing main-group elements across the second through fifth periods of the periodic table. In these calculations, spin-orbit effects on dissociation energies, which were assumed to be additive, were estimated from the measured spin-orbit coupling constants of atoms and diatomic molecules, and an electronic energy in the complete-basis-set, complete-electron-correlation limit has been extrapolated by the formula which was in turn based on the exponential-Gaussian extrapolation formula of the basis set dependence.« less

Theory of Valence Transition

NASA Astrophysics Data System (ADS)

Misawa, S.; Takano, F.

1981-01-01

The valence transition phenomena occurring in rare-earth compounds are studied by using the periodic Anderson model with the electron-phonon coupling. This electron-phonon interaction G is treated in the Hartree-Fock approximation. The Coulomb repulsion U between f-electrons on the same site is taken to be ∞, and the decoupling method of Roth is used for the higher order Green function considering the mixing interaction to be small. We put the condition that the total number of electrons is a constant, and calculate the numbers of f- and d-electrons as functions of the original energy of f-electron by using the Green functions. The first order transition is shown to occur if G ≳ (1/2)W, where W is the width of the original d-band. The energy of f-electron at which the insulator and the metallic phase have the same ground state energy is calculated asɛc ≃ (1/2)(G-(1/2)W) + (2V^2/W) log |(G-W/2)/(G+W/2)|- (V^2/8W) log | (G-W/2)(G-(3/2)W) |. The magnetic susceptibilities of both phases are also calculated, but the result is not good, showing the decoupling method used here is not appropriate for the calculation of magnetic properties.

First-principle calculations of crystal structures, electronic structures, and optical properties of RETaO4 (RE = Y, La, Sm, Eu, Dy, Er)

NASA Astrophysics Data System (ADS)

Ma, Zhuang; Zheng, Jiayi; Wang, Song; Gao, Lihong

2018-01-01

It is an effective method to protect components from high power laser damage using high reflective materials. The rare earth tantalates RETaO4 with high dielectric constant suggests that they may have very high reflectivity, according to the relationship between dielectric constant and reflectivity. The crystal structures, electronic structures, and optical properties of RETaO4 (RE=Y, La, Sm, Eu, Dy, Er) have been studied by first-principle calculations. With the increasing atomic number of RE (i.e., the number of 4f electrons), a 4f electron shell moves from the bottom of conduction band to the forbidden gap and then to the valence band. The relationship between the electronic structures and optical properties is explored. The electron transitions among O 2p states, RE 4f states, and Ta 5d states have a key effect on optical properties such as dielectric function, absorption coefficient, and reflectivity. For the series of RETaO4, the appearance of the 4f electronic states will obviously promote the improvement of reflectivity. When the 4f states appear at the middle of the forbidden gap, the reflectivity reaches the maximum. The reflectivity of EuTaO4 at 1064 nm is up to 93.47%, indicating that it has potential applications in the antilaser radiation area.

Lattice dynamic properties of Rh2XAl (X=Fe and Y) alloys

NASA Astrophysics Data System (ADS)

Al, Selgin; Arikan, Nihat; Demir, Süleyman; Iyigör, Ahmet

2018-02-01

The electronic band structure, elastic and vibrational spectra of Rh2FeAl and Rh2YAl alloys were computed in detail by employing an ab-initio pseudopotential method and a linear-response technique based on the density-functional theory (DFT) scheme within a generalized gradient approximation (GGA). Computed lattice constants, bulk modulus and elastic constants were compared. Rh2YAl exhibited higher ability to resist volume change than Rh2FeAl. The elastic constants, shear modulus, Young modulus, Poisson's ratio, B/G ratio electronic band structure, total and partial density of states, and total magnetic moment of alloys were also presented. Rh2FeAl showed spin up and spin down states whereas Rh2YAl showed none due to being non-magnetic. The calculated total densities of states for both materials suggest that both alloys are metallic in nature. Full phonon spectra of Rh2FeAl and Rh2YA1 alloys in the L21 phase were collected using the ab-initio linear response method. The obtained phonon frequencies were in the positive region indicating that both alloys are dynamically stable.

Plasma parameters in a multidipole plasma system

NASA Astrophysics Data System (ADS)

Ruscanu, D.; Anita, V.; Popa, G.

Plasma potential and electron number densities and electron temperatures under bi-Maxwellian approximation for electron distribution function of the multidipole argon plasma source system were measured for a gas pressure ranging between 10-4 and 10-3 mbar and an anode-cathode voltage ranging between 40 and 120 V but a constant discharge current intensity. The first group, as ultimate or cold electrons and main electron plasma population, results by trapping of the slow electrons produced by ionisation process due to primary-neutral collisions. The trapping process is produced by potential well due to positive plasma potential with respect to the anode so that electron temperature of the ultimate electrons does not depend on both the gas pressure and discharge voltage. The second group, as secondary or hot electrons, results as degrading process of the primaries and their number density increases while their temperature decreases with the increase of both the gas pressure and discharge voltage.

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice–Ramsperger–Kassel theory

PubMed Central

Bao, Junwei Lucas; Zhang, Xin

2016-01-01

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C2F4), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice–Ramsperger–Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements. PMID:27834727

Barrierless association of CF2 and dissociation of C2F4 by variational transition-state theory and system-specific quantum Rice-Ramsperger-Kassel theory.

PubMed

Bao, Junwei Lucas; Zhang, Xin; Truhlar, Donald G

2016-11-29

Bond dissociation is a fundamental chemical reaction, and the first principles modeling of the kinetics of dissociation reactions with a monotonically increasing potential energy along the dissociation coordinate presents a challenge not only for modern electronic structure methods but also for kinetics theory. In this work, we use multifaceted variable-reaction-coordinate variational transition-state theory (VRC-VTST) to compute the high-pressure limit dissociation rate constant of tetrafluoroethylene (C 2 F 4 ), in which the potential energies are computed by direct dynamics with the M08-HX exchange correlation functional. To treat the pressure dependence of the unimolecular rate constants, we use the recently developed system-specific quantum Rice-Ramsperger-Kassel theory. The calculations are carried out by direct dynamics using an exchange correlation functional validated against calculations that go beyond coupled-cluster theory with single, double, and triple excitations. Our computed dissociation rate constants agree well with the recent experimental measurements.

Calculations of atomic magnetic nuclear shielding constants based on the two-component normalized elimination of the small component method

NASA Astrophysics Data System (ADS)

Yoshizawa, Terutaka; Zou, Wenli; Cremer, Dieter

2017-04-01

A new method for calculating nuclear magnetic resonance shielding constants of relativistic atoms based on the two-component (2c), spin-orbit coupling including Dirac-exact NESC (Normalized Elimination of the Small Component) approach is developed where each term of the diamagnetic and paramagnetic contribution to the isotropic shielding constant σi s o is expressed in terms of analytical energy derivatives with regard to the magnetic field B and the nuclear magnetic moment 𝝁 . The picture change caused by renormalization of the wave function is correctly described. 2c-NESC/HF (Hartree-Fock) results for the σiso values of 13 atoms with a closed shell ground state reveal a deviation from 4c-DHF (Dirac-HF) values by 0.01%-0.76%. Since the 2-electron part is effectively calculated using a modified screened nuclear shielding approach, the calculation is efficient and based on a series of matrix manipulations scaling with (2M)3 (M: number of basis functions).

Moderate temperature-dependent surface and volume resistivity and low-frequency dielectric constant measurements of pure and multi-walled carbon nanotube (MWCNT) doped polyvinyl alcohol thin films

NASA Astrophysics Data System (ADS)

Edwards, Matthew; Guggilla, Padmaja; Reedy, Angela; Ijaz, Quratulann; Janen, Afef; Uba, Samuel; Curley, Michael

2017-08-01

Previously, we have reported measurements of temperature-dependent surface resistivity of pure and multi-walled carbon nanotube (MWNCT) doped amorphous Polyvinyl Alcohol (PVA) thin films. In the temperature range from 22 °C to 40 °C with humidity-controlled environment, we found the surface resistivity to decrease initially, but to rise steadily as the temperature continued to increase. Moreover, electric surface current density (Js) was measured on the surface of pure and MWCNT doped PVA thin films. In this regard, the surface current density and electric field relationship follow Ohm's law at low electric fields. Unlike Ohmic conduction in metals where free electrons exist, selected captive electrons are freed or provided from impurities and dopants to become conduction electrons from increased thermal vibration of constituent atoms in amorphous thin films. Additionally, a mechanism exists that seemingly decreases the surface resistivity at higher temperatures, suggesting a blocking effect for conducting electrons. Volume resistivity measurements also follow Ohm's law at low voltages (low electric fields), and they continue to decrease as temperatures increase in this temperature range, differing from surface resistivity behavior. Moreover, we report measurements of dielectric constant and dielectric loss as a function of temperature and frequency. Both the dielectric constant and dielectric loss were observed to be highest for MWCNT doped PVA compared to pure PVA and commercial paper, and with frequency and temperature for all samples.

Study of pressure variation effect on structural, opto-electronic, elastic, mechanical, and thermodynamic properties of SrLiF3

NASA Astrophysics Data System (ADS)

Erum, Nazia; Iqbal, Muhammad Azhar

2017-11-01

The structural, electronic, elastic, optical and thermodynamic properties of cubic fluoroperovskite SrLiF3 at ambient and high-pressure are investigated by using first-principles total energy calculations within the framework of Generalized Gradient Approximation (GGA), combined with Quasi-harmonic Debye model in which the phonon effects are considered. The pressure effects are determined in the range of 0-50 GPa, in which cubic stability of SrLiF3 fluoroperovskite remains valid. The computed lattice parameters agree well with experimental and previous theoretical results. Decrease in lattice constant and bonds length is observed with the increase in pressure from 0 to 50 GPa. The effect of increase in pressure on electronic band structure calculations with GGA and GGA plus Tran-Blaha modified Becke-Johnson (TB-mBJ) potential reveals a predominant characteristic associated with widening of bandgap. The influence of pressure on elastic constants and their related mechanical parameters have been discussed in detail. All the calculated optical properties such as the complex dielectric function Ԑ(ω), optical conductivity σ(ω), energy loss function L(ω), absorption coefficient α(w), refractive index n (ω), reflectivity R (ω), and effective number of electrons neff, via sum rules shift towards the higher energies under the application of pressure. Moreover, important thermodynamic properties heat capacities (Cp and Cv), volume expansion coefficient (α), and Debye temperature (θD) are predicted successfully in the wide temperature and pressure ranges.

First principles study of optical properties of molybdenum disulfide: From bulk to monolayer

NASA Astrophysics Data System (ADS)

Hieu, Nguyen N.; Ilyasov, Victor V.; Vu, Tuan V.; Poklonski, Nikolai A.; Phuc, Huynh V.; Phuong, Le T. T.; Hoi, Bui D.; Nguyen, Chuong V.

2018-03-01

In this paper, we theoretically study the optical properties of both bulk and monolayer MoS2 using first-principles calculations. The optical characters such as: dielectric function, optical reflectivity, and electron energy-loss spectrum of MoS2 are observed in the energy region from 0 to 15 eV. At equilibrium state the dielectric constant in the parallel E∥ x and perpendicular E∥ z directions are of 15.01 and 8.92 for bulk while they are 4.95 and 2.92 for monolayer MoS2, respectively. In the case of bulk MoS2, the obtained computational results for both real and imaginary parts of the dielectric constant are in good agreement with the previous experimental data. In the energy range from 0 to 6 eV, the dielectric functions have highly anisotropic, whereas they become isotropic when the energy is larger than 7 eV. For the adsorption spectra and optical reflectivity, both the collective plasmon resonance and (π + σ) electron plasmon peaks are observed, in which the transition in E∥ x direction is accordant with the experiment data more than the transition in E∥ z direction is. The refractive index, extinction index, and electron energy-loss spectrum are also investigated. The observed prominent peak at 23.1 eV in the energy-loss spectra is in good agreement with experiment value. Our results may provide a useful potential application for the MoS2 structures in electronic and optoelectronic devices.

Electronic and optical properties of antiferromagnetic iron doped NiO - A first principles study

NASA Astrophysics Data System (ADS)

Petersen, John E.; Twagirayezu, Fidele; Scolfaro, Luisa M.; Borges, Pablo D.; Geerts, Wilhelmus J.

2017-05-01

Antiferromagnetic NiO is a candidate for next generation high-speed and scaled RRAM devices. Here, electronic and optical properties of antiferromagnetic NiO: Fe 25% in the rock salt structure are studied and compared to intrinsic NiO. From density of states and complex dielectric function analysis, the first optical transition is found to be at lower frequency than intrinsic NiO due to an Fe impurity level being the valence band maximum. The resulting effects on refractive index, reflectivity, absorption, optical conductivity and loss function for Fe-doped NiO are compared to those of intrinsic NiO, and notable differences are analyzed. The electronic component of the static dielectric constant of NiO: Fe 25% is calculated to be about 2% less than that of intrinsic NiO.

Evidence for electron-based ion generation in radio-frequency ionization.

PubMed

Olaitan, Abayomi D; Zekavat, Behrooz; Solouki, Touradj

2016-01-01

Radio-frequency ionization (RFI) is a novel ionization method coupled to mass spectrometry (MS) for analysis of semi-volatile and volatile organic compounds (VOCs). Despite the demonstrated capabilities of RFI MS for VOC analysis in both positive- and negative-ion modes, mechanism of RFI is not completely understood. Improved understanding of the ion generation process in RFI should expand its utility in MS. Here, we studied the possibility of electron emission in RFI using both direct charged particle current measurements and indirect electron detection in a 9.4-T Fourier transform-ion cyclotron resonance (FT-ICR) mass spectrometer. We show that RF-generated electrons can be trapped in the ICR cell and, subsequently, reacted with neutral hexafluorobenzene (C6 F6 ) molecules to generate C6 F6 (●-) . Intensity of observed C6 F6 (●-) species correlated with the number of trapped electrons and decreased as a function of electron quenching period. We also measured the electron attachment rate constant of hexafluorobenzene using a post-RF electron trapping experiment. Measured electron attachment rate constant of hexafluorobenzene (1.19 (±0.53) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) for post-RF FT-ICR MS agreed with the previously reported value (1.60 (±0.30) × 10(-9)  cm(3)  molecule(-1)  s(-1) ) from low-pressure ICR MS measurements. Experimental results from direct and indirect electron measurements suggest that RFI process involves RF-generated electrons under ultrahigh vacuum conditions. Copyright © 2015 John Wiley & Sons, Ltd.

Dissipative NEGF methodology to treat short range Coulomb interaction: Current through a 1D nanostructure.

PubMed

Martinez, Antonio; Barker, John R; Di Prieto, Riccardo

2018-06-13

A methodology describing Coulomb blockade in the Non-equilibrium Green Function formalism is presented. We carried out ballistic and dissipative simulations through a 1D quantum dot using an Einstein phonon model. Inelastic phonons with different energies have been considered. The methodology incorporates the short-range Coulomb interaction between two electrons through the use of a two-particle Green's function. Unlike previous work, the quantum dot has spatial resolution i.e. it is not just parameterized by the energy level and coupling constants of the dot. Our method intends to describe the effect of electron localization while maintaining an open boundary or extended wave function. The formalism conserves the current through the nanostructure. A simple 1D model is used to explain the increase of mobility in semi-crystalline polymers as a function of the electron concentration. The mechanism suggested is based on the lifting of energy levels into the transmission window as a result of the local electron-electron repulsion inside a crystalline domain. The results are aligned with recent experimental findings. Finally, as a proof of concept, we present a simulation of a low temperature resonant structure showing the stability diagram in the Coulomb blockade regime. . © 2018 IOP Publishing Ltd.

Hyperfine structure of 2Σ molecules containing alkaline-earth-metal atoms

NASA Astrophysics Data System (ADS)

Aldegunde, Jesus; Hutson, Jeremy M.

2018-04-01

Ultracold molecules with both electron spin and an electric dipole moment offer new possibilities in quantum science. We use density-functional theory to calculate hyperfine coupling constants for a selection of molecules important in this area, including RbSr, LiYb, RbYb, CaF, and SrF. We find substantial hyperfine coupling constants for the fermionic isotopes of the alkaline-earth-metal and Yb atoms. We discuss the hyperfine level patterns and Zeeman splittings expected for these molecules. The results will be important both to experiments aimed at forming ultracold open-shell molecules and to their applications.

Effects of cation ordering on the elastic and electronic properties of Mg-Fe silicate phases at high pressures

NASA Astrophysics Data System (ADS)

Das, Pratik Kr.; Mandal, Nibir; Arya, A.

2017-12-01

Olivine [(Mg, Fe)2SiO4] and pyroxene [(Mg, Fe)Si2O6] are naturally occurring silicate phases. Both the phases crystallize with orthorhombic symmetry, displaying ordering of Mg2+ and Fe2+ in their non-equivalent octahedral lattice sites (M1, M2). We address two major issues: (1) how far an inversion of the cation ordering: type I (Mg2+ in M1; Fe2+ in M2) to type II (Mg2+ in M2; Fe2+in M1) can modify their elastic properties and (2) what are the effects of this inversion on their electronic properties? Using density functional theory, we calculate the elastic constant tensors (Cij) as a function of hydrostatic pressure for types I and II ordering. Our calculations suggest that the inversion (types I to II) in olivine significantly reduces the shear elastic constant C55 (˜25%). This has little effect on the Cij of pyroxene in ambient condition, but the effects become strong at elevated pressures (100 GPa), resulting in large variations (>40%) of all the shear elastic constants: C44, C55, and C66. We predict contrasting variations in compressional (VP) and shear (VS) wave velocities by 1% and 9% and by 2% and 11% for olivine and pyroxene, respectively, on types I to II switchover. Our Debye temperature (θD) calculations show that θD of olivine is less sensitive to ordering inversion, whereas that of pyroxene varies substantially (˜22%) under ambient condition. We evaluate the electronic DOS of pyroxene, and obtain a large difference in the magnetic moment between types I and II.

The first principle study of Ni{sub 2}ScGa and Ni{sub 2}TiGa

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

Özduran, Mustafa; Turgut, Kemal; Arikan, Nihat

2014-10-06

We computed the electronic structure, elastic moduli, vibrational properties, and Ni{sub 2}TiGa and Ni{sub 2}ScGa alloys in the cubic L2{sub 1} structure. The obtained equilibrium lattice constants of these alloys are in good agreement with available data. In cubic systems, there are three independent elastic constants, namely C{sub 11}, C{sub 12} and C{sub 44}. We calculated elastic constants in L2{sub 1} structure for Ni{sub 2}TiGa and Ni{sub 2}ScGa using the energy-strain method. The electronic band structure, total and partial density of states for these alloys were investigated within density functional theory using the plane-wave pseudopotential method implemented in Quantum-Espresso programmore » package. From band structure, total and projected density of states, we observed metallic characters of these compounds. The electronic calculation indicate that the predominant contributions of the density of states at Fermi level come from the Ni 3d states and Sc 3d states for Ni{sub 2}TiGa, Ni 3d states and Sc 3d states for Ni{sub 2}ScGa. The computed density of states at Fermi energy are 2.22 states/eV Cell for Ni{sub 2}TiGa, 0.76 states/eV Cell for Ni{sub 2}ScGa. The vibrational properties were obtained using a linear response in the framework at the density functional perturbation theory. For the alloys, the results show that the L2{sub 1} phase is unstable since the phonon calculations have imagine modes.« less

An Ab Initio Full Potential Fully Relativistic Study of the (0001) Surface of Double Hexagonal Close Packed Americium*

NASA Astrophysics Data System (ADS)

Gao, Da; Ray, Asok

2007-03-01

The electronic and geometric properties of bulk dhcp Am as well as quantum size effects in the surface energies and the work functions of the dhcp Am (0001) ultra thin films up to seven layers have been examined at nonmagnetic, ferromagnetic, and anti-ferromagnetic configurations via full-potential all-electron density-functional calculations with a mixed APW+lo/LAPW basis. The anti-ferromagnetic state including spin-orbit coupling is found to be the ground state of both bulk and the (0001) surface of dhcp Am with the 5f electrons primarily localized. Our results show that magnetic configurations and spin-orbit coupling play important roles in determining the equilibrium lattice constant, the bulk modulus as well as the localized feature of 5f electrons for dhcp Am. Quantum size effects are found to be more pronounced in work functions than in surface energies. *This work is supported by the Chemical Sciences, Geosciences and Biosciences Division, Office of Basic Energy Sciences, Office of Science, U. S. Department of Energy and the Welch Foundation, Houston, Texas.

Structure and function of NADPH-cytochrome P450 reductase and nitric oxide synthase reductase domain

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

Iyanagi, Takashi

2005-12-09

NADPH-cytochrome P450 reductase (CPR) and the nitric oxide synthase (NOS) reductase domains are members of the FAD-FMN family of proteins. The FAD accepts two reducing equivalents from NADPH (dehydrogenase flavin) and FMN acts as a one-electron carrier (flavodoxin-type flavin) for the transfer from NADPH to the heme protein, in which the FMNH {sup {center_dot}}/FMNH{sub 2} couple donates electrons to cytochrome P450 at constant oxidation-reduction potential. Although the interflavin electron transfer between FAD and FMN is not strictly regulated in CPR, electron transfer is activated in neuronal NOS reductase domain upon binding calmodulin (CaM), in which the CaM-bound activated form canmore » function by a similar mechanism to that of CPR. The oxygenated form and spin state of substrate-bound cytochrome P450 in perfused rat liver are also discussed in terms of stepwise one-electron transfer from CPR. This review provides a historical perspective of the microsomal mixed-function oxidases including CPR and P450. In addition, a new model for the redox-linked conformational changes during the catalytic cycle for both CPR and NOS reductase domain is also discussed.« less

Method and apparatus for controlling pitch and flap angles of a wind turbine

DOEpatents

Deering, Kenneth J [Seattle, WA; Wohlwend, Keith P [Issaquah, WA

2009-05-12

A wind turbine with improved response to wind conditions is provided. Blade flap angle motion is accompanied by a change in pitch angle by an amount defining a pitch/flap coupling ratio. The coupling ratio is non-constant as a function of a flap angle and is preferably a substantially continuous, non-linear function of flap angle. The non-constant coupling ratio can be provided by mechanical systems such as a series of linkages or by configuring electronic or other control systems and/or angle sensors. A link with a movable proximal end advantageously is part of the mechanical system. The system can provide relatively large coupling ratios and relatively large rates of coupling ratio changes especially for near-feather pitches and low flap angles.

Optical characteristics and parameters of gas-discharge plasma in a mixture of mercury dibromide vapor with argon

NASA Astrophysics Data System (ADS)

Malinina, A. A.; Malinin, A. N.

2015-03-01

Results are presented from studies of the optical characteristics and parameters of the plasma of a dielectric barrier discharge in a mixture of mercury dibromide vapor with argon—the working medium of an exciplex gas-discharge emitter. It is established that the partial pressures of mercury dibromide vapor and argon at which the average and pulsed emission intensities in the blue—green spectral region (λmax = 502 nm) reach their maximum values are 0.6 and 114.4 kPa, respectively. The electron energy distribution function, the transport characteristics, the specific power spent on the processes involving electrons, the electron density and temperature, and the rate constants for the processes of elastic and inelastic electron scattering from the molecules and atoms of the working mixture are determined by numerical simulation, and their dependences on the reduced electric field strength are analyzed. The rate constant of the process leading to the formation of exciplex mercury monobromide molecules for a reduced electric field of E/ N = 20 Td, at which the maximum emission intensity in the blue—green spectral region was observed in this experiment, is found to be 8.1 × 10-15 m3/s.

Direct electron transfer of glucose oxidase and biosensing for glucose based on PDDA-capped gold nanoparticle modified graphene/multi-walled carbon nanotubes electrode.

PubMed

Yu, Yanyan; Chen, Zuanguang; He, Sijing; Zhang, Beibei; Li, Xinchun; Yao, Meicun

2014-02-15

In this work, poly (diallyldimethylammonium chloride) (PDDA)-capped gold nanoparticles (AuNPs) functionalized graphene (G)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were fabricated. Based on the electrostatic attraction, the G/MWCNTs hybrid material can be decorated with AuNPs uniformly and densely. The new hierarchical nanostructure can provide a larger surface area and a more favorable microenvironment for electron transfer. The AuNPs/G/MWCNTs nanocomposite was used as a novel immobilization platform for glucose oxidase (GOD). Direct electron transfer (DET) was achieved between GOD and the electrode. Field emission scanning electron microscopy (FESEM), UV-vis spectroscopy and cyclic voltammetry (CV) were used to characterize the electrochemical biosensor. The glucose biosensor fabricated based on GOD electrode modified with AuNPs/G/MWCNTs demonstrated satisfactory analytical performance with high sensitivity (29.72mAM(-1)cm(-2)) and low limit of detection (4.8 µM). The heterogeneous electron transfer rate constant (ΚS) and the apparent Michaelis-Menten constant (Km) of GOD were calculated to be 11.18s(-1) and 2.09 mM, respectively. With satisfactory selectivity, reproducibility, and stability, the nanostructure we proposed offered an alternative for electrode fabricating and glucose biosensing. © 2013 Elsevier B.V. All rights reserved.

Properties of strong-coupling magneto-bipolaron qubit in quantum dot under magnetic field

NASA Astrophysics Data System (ADS)

Xu-Fang, Bai; Ying, Zhang; Wuyunqimuge; Eerdunchaolu

2016-07-01

Based on the variational method of Pekar type, we study the energies and the wave-functions of the ground and the first-excited states of magneto-bipolaron, which is strongly coupled to the LO phonon in a parabolic potential quantum dot under an applied magnetic field, thus built up a quantum dot magneto-bipolaron qubit. The results show that the oscillation period of the probability density of the two electrons in the qubit decreases with increasing electron-phonon coupling strength α, resonant frequency of the magnetic field ω c, confinement strength of the quantum dot ω 0, and dielectric constant ratio of the medium η the probability density of the two electrons in the qubit oscillates periodically with increasing time t, angular coordinate φ 2, and dielectric constant ratio of the medium η the probability of electron appearing near the center of the quantum dot is larger, and the probability of electron appearing away from the center of the quantum dot is much smaller. Project supported by the Natural Science Foundation of Hebei Province, China (Grant No. E2013407119) and the Items of Institution of Higher Education Scientific Research of Hebei Province and Inner Mongolia, China (Grant Nos. ZD20131008, Z2015149, Z2015219, and NJZY14189).

Lightning protection of aircraft

NASA Technical Reports Server (NTRS)

Fisher, F. A.; Plumer, J. A.

1977-01-01

The current knowledge concerning potential lightning effects on aircraft and the means that are available to designers and operators to protect against these effects are summarized. The increased use of nonmetallic materials in the structure of aircraft and the constant trend toward using electronic equipment to handle flight-critical control and navigation functions have served as impetus for this study.

Esr Spectra of Alkali-Metal Atoms on Helium Nanodroplets: a Theoretical Model for the Prediction of Helium Induced Hyperfine Structure Shifts

NASA Astrophysics Data System (ADS)

Hauser, Reas W.; Filatov, Michael; Ernst, Wolfgang E.

2013-06-01

We predict He-droplet-induced changes of the isotropic HFS constant a_{HFS} of the alkali-metal atoms M = Li, Na, K and Rb on the basis of a model description. Optically detected electron spin resonance spectroscopy has allowed high resolution measurements that show the influence of the helium droplet and its size on the unpaired electron spin density at the alkali nucleus. Our theoretical approach to describe this dependence is based on a combination of two well established techniques: Results of relativistic coupled-cluster calculations on the alkali-He dimers (energy and HFS constant as functions of the binding length) are mapped onto the doped-droplet-situation with the help of helium-density functional theory. We simulate doped droplets He_{N} with N ranging from 50 to 10000, using the diatomic alkali-He-potential energy curves as input. From the obtained density profiles we evaluate average distances between the dopant atom and its direct helium neighborhood. The distances are then set in relation to the variation of the HFS constant with binding length in the simplified alkali-He-dimer model picture. This method yields reliable relative shifts but involves a systematic absolute error. Hence, the absolute values of the shifts are tied to one experimentally determined HFS constant for ^{85}Rb-He_{N = 2000}. With this parameter choice we obtain results in good agreement with the available experimental data for Rb and K^{a,b} confirming the predicted 1/N trend of the functional dependence^{c}. M. Koch, G. Auböck, C. Callegari, and W. E. Ernst, Phys. Rev. Lett. 103, 035302-1-4 (2009) M. Koch, C. Callegari, and W. E. Ernst, Mol. Phys. 108 (7), 1005-1011 (2010) A. W. Hauser, T. Gruber, M. Filatov, and W. E. Ernst, ChemPhysChem (2013) online DOI: 10.1002/cphc.201200697

14N Quadrupole Coupling in the Microwave Spectra of N-Vinylformamide

NASA Astrophysics Data System (ADS)

Kannengießer, Raphaela; Stahl, Wolfgang; Nguyen, Ha Vinh Lam; Bailey, William C.

2016-06-01

The microwave spectra of two conformers, trans and cis, of the title compound were recorded using two molecular beam Fourier transform microwave spectrometers operating in the frequency range 2 GHz to 40 GHz, and aimed at analysis of their 14N quadrupole hyperfine structures. Rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants (NQCCs) χaa and χbb - χcc, were all determined with very high accuracy. Two fits including 176 and 117 hyperfine transitions were performed for the trans and cis conformers, respectively. Standard deviations of both fits are close to the measurement accuracy of 2 kHz. The NQCCs of the two conformers are almost exactly the same, and are compared with values found for other saturated and unsaturated formamides. Complementary quantum chemical calculations - MP2/6-311++G(d,p) rotational constants, MP2/cc-pVTZ centrifugal distortion constants, and B3PW91/6-311+G(d,p)//MP2/6-311++G(d,p) nuclear quadrupole coupling constants - give spectroscopic parameters in excellent agreement with the experimental parameters. B3PW91/6-311+G(d,p) calculated electric field gradients, in conjunction with eQ/h = 4.599(12) MHz/a.u., yields more reliable NQCCs for formamides possessing conjugated π-electron systems than does the B3PW91/6-311+G(df,pd) model recommended in Ref., whereas this latter performs better for aliphatic formamides. We conclude from this that f-polarization functions on heavy atoms hinder rather than help with modeling of conjugated π-electron systems. W. C. Bailey, Chem. Phys., 2000, 252, 57 W. C. Bailey, Calculation of Nuclear Quadrupole Coupling Constants in Gaseous State Molecules, http://nqcc.wcbailey.net/index.html.

Magnitude of finite-nucleus-size effects in relativistic density functional computations of indirect NMR nuclear spin-spin coupling constants.

PubMed

Autschbach, Jochen

2009-09-14

A spherical Gaussian nuclear charge distribution model has been implemented for spin-free (scalar) and two-component (spin-orbit) relativistic density functional calculations of indirect NMR nuclear spin-spin coupling (J-coupling) constants. The finite nuclear volume effects on the hyperfine integrals are quite pronounced and as a consequence they noticeably alter coupling constants involving heavy NMR nuclei such as W, Pt, Hg, Tl, and Pb. Typically, the isotropic J-couplings are reduced in magnitude by about 10 to 15 % for couplings between one of the heaviest NMR nuclei and a light atomic ligand, and even more so for couplings between two heavy atoms. For a subset of the systems studied, viz. the Hg atom, Hg(2) (2+), and Tl--X where X=Br, I, the basis set convergence of the hyperfine integrals and the coupling constants was monitored. For the Hg atom, numerical and basis set calculations of the electron density and the 1s and 6s orbital hyperfine integrals are directly compared. The coupling anisotropies of TlBr and TlI increase by about 2 % due to finite-nucleus effects.

Transient Dynamics of Double Quantum Dots Coupled to Two Reservoirs

NASA Astrophysics Data System (ADS)

Fukadai, Takahisa; Sasamoto, Tomohiro

2018-05-01

We study the time-dependent properties of double quantum dots coupled to two reservoirs using the nonequilibrium Green function method. For an arbitrary time-dependent bias, we derive an expression for the time-dependent electron density of a dot and several currents, including the current between the dots in the wide-band-limit approximation. For the special case of a constant bias, we calculate the electron density and the currents numerically. As a result, we find that these quantities oscillate and that the number of crests in a single period of the current from a dot changes with the bias voltage. We also obtain an analytical expression for the relaxation time, which expresses how fast the system converges to its steady state. From the expression, we find that the relaxation time becomes constant when the coupling strength between the dots is sufficiently large in comparison with the difference of coupling strength between the dots and the reservoirs.

Relaxation of ferroelectric states in 2D distributions of quantum dots: EELS simulation

NASA Astrophysics Data System (ADS)

Cortés, C. M.; Meza-Montes, L.; Moctezuma, R. E.; Carrillo, J. L.

2016-06-01

The relaxation time of collective electronic states in a 2D distribution of quantum dots is investigated theoretically by simulating EELS experiments. From the numerical calculation of the probability of energy loss of an electron beam, traveling parallel to the distribution, it is possible to estimate the damping time of ferroelectric-like states. We generate this collective response of the distribution by introducing a mean field interaction among the quantum dots, and then, the model is extended incorporating effects of long-range correlations through a Bragg-Williams approximation. The behavior of the dielectric function, the energy loss function, and the relaxation time of ferroelectric-like states is then investigated as a function of the temperature of the distribution and the damping constant of the electronic states in the single quantum dots. The robustness of the trends and tendencies of our results indicate that this scheme of analysis can guide experimentalists to develop tailored quantum dots distributions for specific applications.

A radially resolved kinetic model for nonlocal electron ripple diffusion losses in tokamaks

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

Robertson, Scott

A relatively simple radially resolved kinetic model is applied to the ripple diffusion problem for electrons in tokamaks. The distribution function f(r,v) is defined on a two-dimensional grid, where r is the radial coordinate and v is the velocity coordinate. Particle transport in the radial direction is from ripple and banana diffusion and transport in the velocity direction is described by the Fokker-Planck equation. Particles and energy are replaced by source functions that are adjusted to maintain a constant central density and temperature. The relaxed profiles of f(r,v) show that the electron distribution function at the wall contains suprathermal electronsmore » that have diffused from the interior that enhance ripple transport. The transport at the periphery is therefore nonlocal. The energy replacement times from the computational model are near to the experimental replacement times for tokamak discharges in the compilation by Pfeiffer and Waltz [Nucl. Fusion 19, 51 (1979)].« less

Boltzmann transport properties of ultra thin-layer of h-CX monolayers

NASA Astrophysics Data System (ADS)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh

2018-04-01

Structural, electronic and thermoelectric properties of monolayer h-CX (X= Al, As, B, Bi, Ga, In, P, N, Sb and Tl) have been computed using density functional theory (DFT). The structural, electronic band structure, phonon dispersion curves and thermoelectric properties have been investigated. h-CGa and h-CTl show the periodically lattice vibrations and h-CB and h-CIn show small imaginary ZA frequencies. Thermoelectric properties are obtained using BoltzTrap code with the constant relaxation time (τ) approximation such as electronic, thermal and electrical conductivity calculated for various temperatures. The results indicate that h-CGa, h-CIn, h-CTl and h-CAl have direct band gaps with minimum electronic thermal and electrical conductivity while h-CB and h-CN show the high electronic thermal and electrical conductivity with highest cohesive energy.

Theoretical Discussion of Electron Transport Rate Constant at TCNQ / Ge and TiO2 System

NASA Astrophysics Data System (ADS)

Al-agealy, Hadi J. M.; Alshafaay, B.; Hassooni, Mohsin A.; Ashwiekh, Ahmed M.; Sadoon, Abbas K.; Majeed, Raad H.; Ghadhban, Rawnaq Q.; Mahdi, Shatha H.

2018-05-01

We have been studying and estimation the electronic transport constant at TCNQ / Ge and Tio2 interface by means of tunneling potential (TP), transport energy reorientation (TER), driving transition energy DTE and coupling coefficient constant. A simple quantum model for the transition processes was adapted to estimation and analysis depending on the quantum state for donor state |α D > and acceptor stated |α A > and assuming continuum levels of the system. Evaluation results were performed for the surfaces of Ge and Tio2 as best as for multilayer TCNQ. The results show an electronic transfer feature for electronic TCNQ density of states and a semiconductor behavior. The electronic rate constant result for both systems shows a good tool to election system in applied devices. All these results indicate the

Electronic structure, magnetism, and exchange integrals in transition-metal oxides: Role of the spin polarization of the functional in DFT+U calculations

NASA Astrophysics Data System (ADS)

Keshavarz, Samara; Schött, Johan; Millis, Andrew J.; Kvashnin, Yaroslav O.

2018-05-01

Density functional theory augmented with Hubbard-U corrections (DFT+U ) is currently one of the most widely used methods for first-principles electronic structure modeling of insulating transition-metal oxides (TMOs). Since U is relatively large compared to bandwidths, the magnetic excitations in TMOs are expected to be well described by a Heisenberg model. However, in practice the calculated exchange parameters Ji j depend on the magnetic configuration from which they are extracted and on the functional used to compute them. In this work we investigate how the spin polarization dependence of the underlying exchange-correlation functional influences the calculated magnetic exchange constants of TMOs. We perform a systematic study of the predictions of calculations based on the local density approximation plus U (LDA+U ) and the local spin density approximation plus U (LSDA+U ) for the electronic structures, total energies, and magnetic exchange interactions Ji j extracted from ferromagnetic (FM) and antiferromagnetic (AFM) configurations of several transition-metal oxide materials. We report that for realistic choices of Hubbard U and Hund's J parameters, LSDA+U and LDA+U calculations result in different values of the magnetic exchange constants and band gap. The dependence of the band gap on the magnetic configuration is stronger in LDA+U than in LSDA+U and we argue that this is the main reason why the configuration dependence of Ji j is found to be systematically more pronounced in LDA+U than in LSDA+U calculations. We report a very good correspondence between the computed total energies and the parametrized Heisenberg model for LDA+U calculations, but not for LSDA+U , suggesting that LDA+U is a more appropriate method for estimating exchange interactions.

The vibrational dependence of dissociative recombination: Rate constants for N{sub 2}{sup +}

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

Guberman, Steven L., E-mail: slg@sci.org

Dissociative recombination rate constants are reported with electron temperature dependent uncertainties for the lowest 5 vibrational levels of the N{sub 2}{sup +} ground state. The rate constants are determined from ab initio calculations of potential curves, electronic widths, quantum defects, and cross sections. At 100 K electron temperature, the rate constants overlap with the exception of the third vibrational level. At and above 300 K, the rate constants for excited vibrational levels are significantly smaller than that for the ground level. It is shown that any experimentally determined total rate constant at 300 K electron temperature that is smaller thanmore » 2.0 × 10{sup −7} cm{sup 3}/s is likely to be for ions that have a substantially excited vibrational population. Using the vibrational level specific rate constants, the total rate constant is in very good agreement with that for an excited vibrational distribution found in a storage ring experiment. It is also shown that a prior analysis of a laser induced fluorescence experiment is quantitatively flawed due to the need to account for reactions with unknown rate constants. Two prior calculations of the dissociative recombination rate constant are shown to be inconsistent with the cross sections upon which they are based. The rate constants calculated here contribute to the resolution of a 30 year old disagreement between modeled and observed N{sub 2}{sup +} ionospheric densities.« less

Relativistic electromagnetic waves in an electron-ion plasma

NASA Technical Reports Server (NTRS)

Chian, Abraham C.-L.; Kennel, Charles F.

1987-01-01

High power laser beams can drive plasma particles to relativistic energies. An accurate description of strong waves requires the inclusion of ion dynamics in the analysis. The equations governing the propagation of relativistic electromagnetic waves in a cold electron-ion plasma can be reduced to two equations expressing conservation of energy-momentum of the system. The two conservation constants are functions of the plasma stream velocity, the wave velocity, the wave amplitude, and the electron-ion mass ratio. The dynamic parameter, expressing electron-ion momentum conversation in the laboratory frame, can be regarded as an adjustable quantity, a suitable choice of which will yield self-consistent solutions when other plasma parameters were specified. Circularly polarized electromagnetic waves and electrostatic plasma waves are used as illustrations.

Reverse process of usual optical analysis of boson-exchange superconductors: impurity effects on s- and d-wave superconductors.

PubMed

Hwang, Jungseek

2015-03-04

We performed a reverse process of the usual optical data analysis of boson-exchange superconductors. We calculated the optical self-energy from two (MMP and MMP+peak) input model electron-boson spectral density functions using Allen's formula for one normal and two (s- and d-wave) superconducting cases. We obtained the optical constants including the optical conductivity and the dynamic dielectric function from the optical self-energy using an extended Drude model, and finally calculated the reflectance spectrum. Furthermore, to investigate impurity effects on optical quantities we added various levels of impurities (from the clean to the dirty limit) in the optical self-energy and performed the same reverse process to obtain the optical conductivity, the dielectric function, and reflectance. From these optical constants obtained from the reverse process we extracted the impurity-dependent superfluid densities for two superconducting cases using two independent methods (the Ferrel-Glover-Tinkham sum rule and the extrapolation to zero frequency of -ϵ1(ω)ω(2)); we found that a certain level of impurities is necessary to get a good agreement on results obtained by the two methods. We observed that impurities give similar effects on various optical constants of s- and d-wave superconductors; the greater the impurities the more distinct the gap feature and the lower the superfluid density. However, the s-wave superconductor gives the superconducting gap feature more clearly than the d-wave superconductor because in the d-wave superconductors the optical quantities are averaged over the anisotropic Fermi surface. Our results supply helpful information to see how characteristic features of the electron-boson spectral function and the s- and d-wave superconducting gaps appear in various optical constants including raw reflectance spectrum. Our study may help with a thorough understanding of the usual optical analysis process. Further systematic study of experimental data collected at various conditions using the optical analysis process will help to reveal the origin of the mediated boson in the boson-exchange superconductors.

Rationally designed polyimides for high-energy density capacitor applications.

PubMed

Ma, Rui; Baldwin, Aaron F; Wang, Chenchen; Offenbach, Ido; Cakmak, Mukerrem; Ramprasad, Rampi; Sotzing, Gregory A

2014-07-09

Development of new dielectric materials is of great importance for a wide range of applications for modern electronics and electrical power systems. The state-of-the-art polymer dielectric is a biaxially oriented polypropylene (BOPP) film having a maximal energy density of 5 J/cm(3) and a high breakdown field of 700 MV/m, but with a limited dielectric constant (∼2.2) and a reduced breakdown strength above 85 °C. Great effort has been put into exploring other materials to fulfill the demand of continuous miniaturization and improved functionality. In this work, a series of polyimides were investigated as potential polymer materials for this application. Polyimide with high dielectric constants of up to 7.8 that exhibits low dissipation factors (<1%) and high energy density around 15 J/cm(3), which is 3 times that of BOPP, was prepared. Our syntheses were guided by high-throughput density functional theory calculations for rational design in terms of a high dielectric constant and band gap. Correlations of experimental and theoretical results through judicious variations of polyimide structures allowed for a clear demonstration of the relationship between chemical functionalities and dielectric properties.

A theoretical study on the electronic structures and equilibrium constants evaluation of Deferasirox iron complexes.

PubMed

Salehi, Samie; Saljooghi, Amir Shokooh; Izadyar, Mohammad

2016-10-01

Elemental iron is essential for cellular growth and homeostasis but it is potentially toxic to the cells and tissues. Excess iron can contribute in tumor initiation and tumor growth. Obviously, in iron overload issues using an iron chelator in order to reduce iron concentration seems to be vital. This study presents the density functional theory calculations of the electronic structure and equilibrium constant for iron-deferasirox (Fe-DFX) complexes in the gas phase, water and DMSO. A comprehensive study was performed to investigate the Deferasirox-iron complexes in chelation therapy. Calculation was performed in CAMB3LYP/6-31G(d,p) to get the optimized structures for iron complexes in high and low spin states. Natural bond orbital and quantum theory of atoms in molecules analyses was carried out with B3LYP/6-311G(d,p) to understand the nature of complex bond character and electronic transition in complexes. Electrostatic potential effects on the complexes were evaluated using the CHelpG calculations. The results indicated that higher affinity for Fe(III) is not strictly a function of bond length but also the degree of Fe-X (X=O,N) covalent bonding. Based on the quantum reactivity parameters which have been investigated here, it is possible reasonable design of the new chelators to improve the chelator abilities. Copyright © 2016 Elsevier Ltd. All rights reserved.

Optical properties of armchair (7, 7) single walled carbon nanotubes

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

Gharbavi, K.; Badehian, H., E-mail: hojatbadehian@gmail.com

2015-07-15

Full potential linearized augmented plane waves method with the generalized gradient approximation for the exchange-correlation potential was applied to calculate the optical properties of (7, 7) single walled carbon nanotubes. The both x and z directions of the incident photons were applied to estimate optical gaps, dielectric function, electron energy loss spectroscopies, optical conductivity, optical extinction, optical refractive index and optical absorption coefficient. The results predict that dielectric function, ε (ω), is anisotropic since it has higher peaks along z-direction than x-direction. The static optical refractive constant were calculated about 1.4 (z-direction) and 1.1 (x- direction). Moreover, the electron energymore » loss spectroscopy showed a sharp π electron plasmon peaks at about 6 eV and 5 eV for z and x-directions respectively. The calculated reflection spectra show that directions perpendicular to the tube axis have further optical reflection. Moreover, z-direction indicates higher peaks at absorption spectra in low range energies. Totally, increasing the diameter of armchair carbon nanotubes cause the optical band gap, static optical refractive constant and optical reflectivity to decrease. On the other hand, increasing the diameter cause the optical absorption and the optical conductivity to increase. Moreover, the sharp peaks being illustrated at optical spectrum are related to the 1D structure of CNTs which confirm the accuracy of the calculations.« less

Elastic and thermal properties of the layered thermoelectrics BiOCuSe and LaOCuSe

NASA Astrophysics Data System (ADS)

Saha, S. K.; Dutta, G.

2016-09-01

We determine the elastic properties of the layered thermoelectrics BiOCuSe and LaOCuSe using first-principles density functional theory calculations. To predict their stability, we calculate six distinct elastic constants, where all of them are positive, and suggest mechanically stable tetragonal crystals. As elastic properties relate to the nature and the strength of the chemical bond, the latter is analyzed by means of real-space descriptors, such as the electron localization function (ELF) and Bader charge. From elastic constants, a set of related properties, namely, bulk modulus, shear modulus, Young's modulus, sound velocity, Debye temperature, Grüneisen parameter, and thermal conductivity, are evaluated. Both materials are found to be ductile in nature and not brittle. We find BiOCuSe to have a smaller sound velocity and, hence, within the accuracy of the used Slack's model, a smaller thermal conductivity than LaOCuSe. Our calculations also reveal that the elastic properties and the related lattice thermal transport of both materials exhibit a much larger anisotropy than their electronic band properties that are known to be moderately anisotropic because of a moderate effective-electron-mass anisotropy. Finally, we determine the lattice dynamical properties, such as phonon dispersion, atomic displacement, and mode Grüneisen parameters, in order to correlate the elastic response, chemical bonding, and lattice dynamics.

Photochromic molecules as building blocks for molecular electronics.

PubMed

Peter, Belser

2010-01-01

Energy and electron transfer processes can be easily induced by a photonic excitation of a donor metal complex ([Ru(bpy)3]2), which is connected via a wire-type molecular fragment to an acceptor metal complex ([Os(bpy)3]2+). The rate constant for the transfer process can be determined by emission measurements of the two connected metal complexes. The system can be modified by incorporation of a switching unit or an interrupter into the wire, influencing the transfer process. Such a molecular device corresponds to an interrupter, mimic the same function applied in molecular electronics. We have used organic switches, which show photochromic properties. By irradiation with light of different wavelengths, the switch changes its functionality by a photochemical reaction from an OFF- to an ON-state and vice versa. The ON- respectively OFF-state is manifested by a color change but also in different conductivity properties for energy and electron transfer processes. Therefore, the mentioned molecular device can work as a simple interrupter, controlling the rate of the transfer processes.

Piezoelectric and dielectric characterization of corona and contact poled PZT-epoxy-MWCNT bulk composites

NASA Astrophysics Data System (ADS)

Banerjee, S.; Cook-Chennault, K. A.; Du, W.; Sundar, U.; Halim, H.; Tang, A.

2016-11-01

Three-phase lead zirconate titanate (PZT, PbZr0.52Ti0.48O3)-epoxy-multi-walled carbon nanotube (MWCNT) bulk composites were prepared, where the volume fraction of PZT was held constant at 30%, while the volume fraction of the MWCNTs was varied from 1.0%-10%. The samples were poled using either a parallel plate contact or contactless (corona) poling technique. The piezoelectric strain coefficient (d33), dielectric constant (ɛ), and dielectric loss tangent (tan δ) of the samples were measured at 110 Hz, and compared as a function of poling technique and volume fraction of MWCNTs. The highest values for dielectric constant and piezoelectric strain coefficients were 465.82 and 18.87 pC/N for MWCNT volume fractions of 10% and 6%, respectively. These values were obtained for samples that were poled using the corona contactless method. The impedance and dielectric spectra of the composites were recorded over a frequency range of 100 Hz-20 MHz. The impedance values observed for parallel-plate contact poled samples are higher than that of corona poled composites. The fractured surface morphology and distribution of the PZT particles and MWCNTs were observed with the aid of electron dispersion spectroscopy and a scanning electron microscope. The surface morphology of the MWCNTs was observed with the aid of a field emission transmission electron microscope.

Thermophysical properties of paramagnetic Fe from first principles

NASA Astrophysics Data System (ADS)

Ehteshami, Hossein; Korzhavyi, Pavel A.

2017-12-01

A computationally efficient, yet general, free-energy modeling scheme is developed based on first-principles calculations. Finite-temperature disorder associated with the fast (electronic and magnetic) degrees of freedom is directly included in the electronic structure calculations, whereas the vibrational free energy is evaluated by a proposed model that uses elastic constants to calculate average sound velocity of the quasiharmonic Debye model. The proposed scheme is tested by calculating the lattice parameter, heat capacity, and single-crystal elastic constants of α -, γ -, and δ -iron as functions of temperature in the range 1000-1800 K. The calculations accurately reproduce the well-established experimental data on thermal expansion and heat capacity of γ - and δ -iron. Electronic and magnetic excitations are shown to account for about 20% of the heat capacity for the two phases. Nonphonon contributions to thermal expansion are 12% and 10% for α - and δ -Fe and about 30% for γ -Fe. The elastic properties predicted by the model are in good agreement with those obtained in previous theoretical treatments of paramagnetic phases of iron, as well as with the bulk moduli derived from isothermal compressibility measurements [N. Tsujino et al., Earth Planet. Sci. Lett. 375, 244 (2013), 10.1016/j.epsl.2013.05.040]. Less agreement is found between theoretically calculated and experimentally derived single-crystal elastic constants of γ - and δ -iron.

A first principles study of the electronic structure, elastic and thermal properties of UB2

NASA Astrophysics Data System (ADS)

Jossou, Ericmoore; Malakkal, Linu; Szpunar, Barbara; Oladimeji, Dotun; Szpunar, Jerzy A.

2017-07-01

Uranium diboride (UB2) has been widely deployed for refractory use and is a proposed material for Accident Tolerant Fuel (ATF) due to its high thermal conductivity. However, the applicability of UB2 towards high temperature usage in a nuclear reactor requires the need to investigate the thermomechanical properties, and recent studies have failed in highlighting applicable properties. In this work, we present an in-depth theoretical outlook of the structural and thermophysical properties of UB2, including but not limited to elastic, electronic and thermal transport properties. These calculations were performed within the framework of Density Functional Theory (DFT) + U approach, using Quantum ESPRESSO (QE) code considering the addition of Coulomb correlations on the uranium atom. The phonon spectra and elastic constant analysis show the dynamic and mechanical stability of UB2 structure respectively. The electronic structure of UB2 was investigated using full potential linear augmented plane waves plus local orbitals method (FP-LAPW+lo) as implemented in WIEN2k code. The absence of a band gap in the total and partial density of states confirms the metallic nature while the valence electron density plot reveals the presence of covalent bond between adjacent B-B atoms. We predicted the lattice thermal conductivity (kL) by solving Boltzmann Transport Equation (BTE) using ShengBTE. The second order harmonic and third-order anharmonic interatomic force constants required as input to ShengBTE was calculated using the Density-functional perturbation theory (DFPT). However, we predicted the electronic thermal conductivity (kel) using Wiedemann-Franz law as implemented in Boltztrap code. We also show that the sound velocity along 'a' and 'c' axes exhibit high anisotropy, which accounts for the anisotropic thermal conductivity of UB2.

DFT-BASED AB INITIO STUDY OF THE ELECTRONIC AND OPTICAL PROPERTIES OF CESIUM BASED FLUORO-PEROVSKITE CsMF3 (M = Ca AND Sr)

NASA Astrophysics Data System (ADS)

Harmel, M.; Khachai, H.; Ameri, M.; Khenata, R.; Baki, N.; Haddou, A.; Abbar, B.; UǦUR, Ş.; Omran, S. Bin; Soyalp, F.

2012-12-01

Density functional theory (DFT) is performed to study the structural, electronic and optical properties of cubic fluoroperovskite AMF3 (A = Cs; M = Ca and Sr) compounds. The calculations are based on the total-energy calculations within the full-potential linearized augmented plane wave (FP-LAPW) method. The exchange-correlation potential is treated by local density approximation (LDA) and generalized gradient approximation (GGA). The structural properties, including lattice constants, bulk modulus and their pressure derivatives are in very good agreement with the available experimental and theoretical data. The calculations of the electronic band structure, density of states and charge density reveal that compounds are both ionic insulators. The optical properties (namely: the real and the imaginary parts of the dielectric function ɛ(ω), the refractive index n(ω) and the extinction coefficient k(ω)) were calculated for radiation up to 40.0 eV.

Revised model core potentials for third-row transition-metal atoms from Lu to Hg

NASA Astrophysics Data System (ADS)

Mori, Hirotoshi; Ueno-Noto, Kaori; Osanai, You; Noro, Takeshi; Fujiwara, Takayuki; Klobukowski, Mariusz; Miyoshi, Eisaku

2009-07-01

We have produced new relativistic model core potentials (spdsMCPs) for the third-row transition-metal atoms from Lu to Hg explicitly treating explicitly 5s and 5p electrons in addition to 5d and 6s electrons in the same manner for the first- and second-row transition-metal atoms given in the previous Letters [Y. Osanai, M.S. Mon, T. Noro, H. Mori, H. Nakashima, M. Klobukowski, E. Miyoshi, Chem. Phys. Lett. 452 (2008) 210; Y. Osanai, E. Soejima, T. Noro, H. Mori, M.S. Mon, M. Klobukowski, E. Miyoshi, Chem. Phys. Lett. 463 (2008) 230]. Using suitable correlating functions with the split-valence MCP functions, we demonstrate that the present MCP basis sets show reasonable performance in describing the electronic structures of atoms and molecules, bringing about accurate excitation energies for atoms and proper spectroscopic constants for Au 2, Hg 2, and AuH.

Influences of S, Se, Te and Po substitutions on structural, electronic and optical properties of hexagonal CuAlO2 using GGA and B3LYP functionals.

PubMed

Liu, Qi-Jun; Jiao, Zhen; Liu, Fu-Sheng; Liu, Zheng-Tang

2016-06-07

The effects of X-doping (X = S, Se, Te and Po) on the structural, electronic and optical properties of hexagonal CuAlO2 were studied using first-principles density functional theory. The calculated results showed the obtained lattice constants to increase with increasing atomic number, and the X-doping to be energetically more favorable under Al-rich conditions. The calculated electronic properties showed decreased bandgaps with increasing atomic number, which was due to the better covalent hybridizations after sulfuration doping. The enhanced covalency was further confirmed by calculating the Mulliken atomic populations and bond populations. The density of states indicated the increase of the contribution to antibonding from the X-p states to be a benefit for p-type conductivity. Moreover, the X-doping induced a red shift of the absorption edge.

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

DOE PAGES

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; ...

2016-09-09

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level

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

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing

In this paper, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesizedmore » by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated p-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. Finally, these four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.« less

Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.

PubMed

Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurélien; Blumberger, Jochen; Elstner, Marcus

2016-10-11

In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

Resonances in the cumulative reaction probability for a model electronically nonadiabatic reaction

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

Qi, J.; Bowman, J.M.

1996-05-01

The cumulative reaction probability, flux{endash}flux correlation function, and rate constant are calculated for a model, two-state, electronically nonadiabatic reaction, given by Shin and Light [S. Shin and J. C. Light, J. Chem. Phys. {bold 101}, 2836 (1994)]. We apply straightforward generalizations of the flux matrix/absorbing boundary condition approach of Miller and co-workers to obtain these quantities. The upper adiabatic electronic potential supports bound states, and these manifest themselves as {open_quote}{open_quote}recrossing{close_quote}{close_quote} resonances in the cumulative reaction probability, at total energies above the barrier to reaction on the lower adiabatic potential. At energies below the barrier, the cumulative reaction probability for themore » coupled system is shifted to higher energies relative to the one obtained for the ground state potential. This is due to the effect of an additional effective barrier caused by the nuclear kinetic operator acting on the ground state, adiabatic electronic wave function, as discussed earlier by Shin and Light. Calculations are reported for five sets of electronically nonadiabatic coupling parameters. {copyright} {ital 1996 American Institute of Physics.}« less

Characterization of sputter deposited thin film scandate cathodes for miniaturized thermionic converter applications

NASA Astrophysics Data System (ADS)

Zavadil, Kevin R.; Ruffner, Judith H.; King, Donald B.

1999-01-01

We have successfully developed a method for fabricating scandate-based thermionic emitters in thin film form. The primary goal of our effort is to develop thin film emitters that exhibit low work function, high intrinsic electron emissivity, minimum thermal activation properties and that can be readily incorporated into a microgap converter. Our approach has been to incorporate BaSrO into a Sc2O3 matrix using rf sputtering to produce thin films. Diode testing has shown the resulting films to be electron emissive at temperatures as low as 900 K with current densities of 0.1 mA.cm-2 at 1100 K and saturation voltages. We calculate an approximate maximum work function of 1.8 eV and an apparent emission constant (Richardson's constant, A*) of 36 mA.cm-2.K-2. Film compositional and structural analysis shows that a significant surface and subsurface alkaline earth hydroxide phase can form and probably explains the limited utilization and stability of Ba and its surface complexes. The flexibility inherent in sputter deposition suggests alternate strategies for eliminating undesirable phases and optimizing thin film emitter properties.

Signatures of van der Waals binding: A coupling-constant scaling analysis

NASA Astrophysics Data System (ADS)

Jiao, Yang; Schröder, Elsebeth; Hyldgaard, Per

2018-02-01

The van der Waals (vdW) density functional (vdW-DF) method [Rep. Prog. Phys. 78, 066501 (2015), 10.1088/0034-4885/78/6/066501] describes dispersion or vdW binding by tracking the effects of an electrodynamic coupling among pairs of electrons and their associated exchange-correlation holes. This is done in a nonlocal-correlation energy term Ecnl, which permits density functional theory calculation in the Kohn-Sham scheme. However, to map the nature of vdW forces in a fully interacting materials system, it is necessary to also account for associated kinetic-correlation energy effects. Here, we present a coupling-constant scaling analysis, which permits us to compute the kinetic-correlation energy Tcnl that is specific to the vdW-DF account of nonlocal correlations. We thus provide a more complete spatially resolved analysis of the electrodynamical-coupling nature of nonlocal-correlation binding, including vdW attraction, in both covalently and noncovalently bonded systems. We find that kinetic-correlation energy effects play a significant role in the account of vdW or dispersion interactions among molecules. Furthermore, our mapping shows that the total nonlocal-correlation binding is concentrated to pockets in the sparse electron distribution located between the material fragments.

Structural, Electronic and Dynamical Properties of Curium Monopnictides: Density Functional Calculations

NASA Astrophysics Data System (ADS)

Roondhe, Basant; Upadhyay, Deepak; Som, Narayan; Pillai, Sharad B.; Shinde, Satyam; Jha, Prafulla K.

2017-03-01

The structural, electronic, dynamical and thermodynamical properties of CmX (X = N, P, As, Sb, and Bi) compounds are studied using first principles calculations within density functional theory. The Perdew-Burke-Ernzerhof spin polarized generalized gradient approximation and Perdew-Wang (PW) spin polarized local density approximation as the exchange correlational functionals are used in these calculations. There is a good agreement between the present and previously reported data. The calculated electronic density of states suggests that the curium monopnictides are metallic in nature, which is consistent with earlier studies. The significant values of magnetic moment suggest their magnetic nature. The phonon dispersion curves and phonon density of states are also calculated, which depict the dynamical stability of these compounds. There is a significant separation between the optical and acoustical phonon branches. The temperature dependence of the thermodynamical functions are also calculated and discussed. Internal energy and vibrational contribution to the Helmholtz free energy increases and decreases, respectively, with temperature. The entropy increases with temperature. The specific heat at constant volume and Debye temperature obey Debye theory. The temperature variation of the considered thermodynamical functions is in line with those of other crystalline solids.

Ab Initio study on structural, electronic, magnetic and dielectric properties of LSNO within Density Functional Perturbation Theory

NASA Astrophysics Data System (ADS)

Petersen, John; Bechstedt, Friedhelm; Furthmüller, Jürgen; Scolfaro, Luisa

LSNO (La2-xSrxNiO4) is of great interest due to its colossal dielectric constant (CDC) and rich underlying physics. While being an antiferromagnetic insulator, localized holes are present in the form of stripes in the Ni-O planes which are commensurate with the inverse of the Sr concentration. The stripes are a manifestation of charge density waves with period approximately 1/x and spin density waves with period approximately 2/x. Here, the spin ground state is calculated via LSDA + U with the PAW method implemented in VASP. Crystal structure and the effective Hubbard U parameter are optimized before calculating ɛ∞ within the independent particle approximation. ɛ∞ and the full static dielectric constant (including the lattice polarizability) ɛ0 are calculated within Density Functional Perturbation Theory.

The optical properties of platinum and gold in the vacuum ultraviolet

NASA Technical Reports Server (NTRS)

Linton, R. C.

1972-01-01

The optical constants of platinum and gold thin films have been determined in the spectral region of 40 to 200 nm by reflection measurements. The highly polarized continuum of synchrotron radiation emitted by the 240-MeV electron storage ring at the Physical Sciences Laboratory of the University of Wisconsin was used as a light source for the spectrum below 120 nm, while a windowless discharge lamp coupled to a normal incidence monochromator provided a source for the longer wavelengths. Optical constants were determined by a computer program based on iterative solutions to the Fresnel equations for reflection as a function of the angle of incidence.

Glucose biosensing using glassy carbon electrode modified with polyhydroxy-C60, glucose oxidase and ionic-liquid.

PubMed

Yang, Tian; Yang, Xiao-Lu; Zhang, Yu-Shuai; Xiao, BaoLin; Hong, Jun

2014-01-01

Direct electrochemistry of glucose oxidase (GOD) was achieved when an ionic liquid/GOD-Polyhydroxy-C60 functional membrane was confined on a glassy carbon electrode (GCE). The cyclic voltammograms (CVs) of the modified GCE showed a pair of redox peaks with a formal potential (E°') of - 329 ± 2 mV. The heterogeneous electron transfer constant (k(s)) was 1.43 s-1. The modified GCE response to glucose was linear in the range from 0.02 to 2.0 mM. The detection limit was 1 μM. The apparent Michaelis-Menten constant (K(m)(app)) was 1.45 mM.

Structure and dynamics in self-organized C60 fullerenes.

PubMed

Patnaik, Archita

2007-01-01

This manuscript on 'structure and dynamics in self-organized C60 fullerenes' has three sections dealing with: (A) pristine C60 aggregate structure and geometry in solvents of varying dielectric constant. Here, using positronium (Ps) as a fundamental probe which maps changes in the local electron density of the microenvironment, the onset concentration for stable C60 aggregate formation and its phase behavior is deduced from the specific interactions of the Ps atom with the surrounding. (B) A novel methanofullerene dyad, based on a hydrophobic (acceptor C60 moiety)-hydrophilic (bridge with benzene and ester functionalities)-hydrophobic (donor didodecyloxybenzene) network is chosen for investigation of characteristic self-assembly it undergoes leading to supramolecular aggregates. The pi-electronic amphiphile, necessitating a critical dielectric constant epsilon > or = 30 in binary THF-water mixtures, dictated the formation of bilayer vesicles as precursors for spherical fractal aggregates upon complete dyad extraction into a more polar water phase. (C) While the molecular orientation is dependent on the packing density, the ordering of the molecular arrangement, indispensable for self-assembly depends on the balance between the structures demanded by inter-molecular and molecule-substrate interactions. The molecular orientation in a monolayer affects the orientation in a multilayer, formed on the monolayer, suggesting the possibility of the latter to act as a template for controlling the structure of the three dimensionally grown self-assembled molecular aggregation. A systematic study on the electronic structure and orientation associated with C60 functionalized aminothiol self-assembled monolayers on Au(111) surface is presented using surface sensitive Ultra-Violet Photoelectron Spectroscopy (UPS) and C-K edge Near-Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. The results revealed drastic modifications to d-band structure of Au(111) and the electronic structure was found sensitive towards the S-Au interface and the C60 end functional moiety with formation of localized sigma-(S-Au) and sigma(N-C) bonds, respectively. Upon binding C60 to the amine-terminated alkanethiol SAM, a drastically reduced HOMO-LUMO gap of 2.7 eV as compared to a large electronic gap of approximately 8 eV in alkanethiols enables the SAM to be a potential electron transport medium.

Study of electronic and magnetic properties of h-BN on Ni surfaces: A DFT approach

NASA Astrophysics Data System (ADS)

Sahoo, M. R.; Sahu, S.; Kushwaha, A. K.; Nayak, S.

2018-04-01

Hexagonal boron nitride (h-BN) is a promising material for implementation in spintronics due to large band gap, low spin-orbit coupling, and a small lattice mismatch to graphene and close-packedsurfaces of fcc-Ni(111). Electronic and magnetic properties of single layer hexagonal Boron Nitride (h-BN) on Ni (111) surface have been studied with density functional calculation. Since lattice constants of nickel surfaces are very close to that of h-BN, nickel acts as a good substrate. We found that the interaction between 2Pz - 3dz2 orbitals leads to change in electronic band structure as well as density of states which results spin polarization in h-BN.

Conduction band edge effective mass of La-doped BaSnO{sub 3}

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

James Allen, S., E-mail: allen@itst.ucsb.edu; Law, Ka-Ming; Raghavan, Santosh

2016-06-20

BaSnO{sub 3} has attracted attention as a promising material for applications requiring wide band gap, high electron mobility semiconductors, and moreover possesses the same perovskite crystal structure as many functional oxides. A key parameter for these applications and for the interpretation of its properties is the conduction band effective mass. We measure the plasma frequency of La-doped BaSnO{sub 3} thin films by glancing incidence, parallel-polarized resonant reflectivity. Using the known optical dielectric constant and measured electron density, the resonant frequency determines the band edge electron mass to be 0.19 ± 0.01. The results allow for testing band structure calculations and transport models.

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

Ianakiev, Kiril Dimitrov; Iliev, Metodi; Swinhoe, Martyn Thomas

The KM200 device is a versatile, configurable front-end electronics boards that can be used as a functional replacement for Canberra’s JAB-01 boards based on the Amptek A-111 hybrid chip, which continues to be the preferred choice of electronics for large number of the boards in junction boxes of multiplicity counters that process the signal from an array of 3He detectors. Unlike the A-111 chip’s fixed time constants and sensitivity range, the shaping time and sensitivity of the new KM200 can be optimized for demanding applications such as spent fuel, and thus could improve the safeguards measurements of existing systems wheremore » the A-111 or PDT electronics does not perform well.« less

Self-sustained criterion with photoionization for positive dc corona plasmas between coaxial cylinders

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

Zheng, Yuesheng, E-mail: yueshengzheng@fzu.edu.cn; Zhang, Bo, E-mail: shizbcn@tsinghua.edu.cn; He, Jinliang, E-mail: hejl@tsinghua.edu.cn

The positive dc corona plasmas between coaxial cylinders in air under the application of a self-sustained criterion with photoionization are investigated in this paper. A photon absorption function suitable for cylindrical electrode, which can characterize the total photons within the ionization region, is proposed on the basis of the classic corona onset criteria. Based on the general fluid model with the self-sustained criterion, the role of photoionization in the ionization region is clarified. It is found that the surface electric field keeps constant under a relatively low corona current, while it is slightly weakened with the increase of the coronamore » current. Similar tendencies can be found under different conductor radii and relative air densities. The small change of the surface electric field will become more significant for the electron density distribution as well as the ionization activity under a high corona current, compared with the results under the assumption of a constant surface field. The assumption that the surface electric field remains constant should be corrected with the increase of the corona current when the energetic electrons with a distance from the conductor surface are concerned.« less

Spin-polarized currents in a two-terminal double quantum ring driven by magnetic fields and Rashba spin-orbit interaction

NASA Astrophysics Data System (ADS)

Dehghan, E.; Khoshnoud, D. Sanavi; Naeimi, A. S.

2018-06-01

Aim of this study is to investigate spin transportation in double quantum ring (DQR). We developed an array of DQR to measure the transmission coefficient and analyze the spin transportation through this system in the presence of Rashba spin-orbit interaction (RSOI) and magnetic flux estimated using S-matrix method. In this article, we compute the spin transport and spin-current characteristics numerically as functions of electron energy, angles between the leads, coupling constant of the leads, RSOI, and magnetic flux. Our results suggest that, for typical values of the magnetic flux (ϕ /ϕ0) and Rashba constant (αR), such system can demonstrates many spintronic properties. It is possible to design a new geometry of DQR by incoming electrons polarization in a way to optimize the system to work as a spin-filtering and spin-inverting nano-device with very high efficiency. The results prove that the spin current will strongly modulate with an increase in the magnetic flux and Rashba constant. Moreover it is shown that, when the lead coupling is weak, the perfect spin-inverter does not occur.

Differential Mobility Spectrometry: Preliminary Findings on Determination of Fundamental Constants

NASA Technical Reports Server (NTRS)

Limero, Thomas; Cheng, Patti; Boyd, John

2007-01-01

The electron capture detector (ECD) has been used for 40+ years (1) to derive fundamental constants such as a compound's electron affinity. Given this historical perspective, it is not surprising that differential mobility spectrometry (DMS) might be used in a like manner. This paper will present data from a gas chromatography (GC)-DMS instrument that illustrates the potential capability of this device to derive fundamental constants for electron-capturing compounds. Potential energy curves will be used to provide possible explanation of the data.

Mechanical behavior, electronic and phonon properties of ZrB12 under pressure

NASA Astrophysics Data System (ADS)

Li, Xiao-Hong; Yong, Yong-Liang; Cui, Hong-Ling; Zhang, Rui-Zhou

2018-06-01

The mechanical, phonon and electronic properties of ZrB12 under pressure are investigated by first-principles calculations. The research shows that ZrB12 is mechanically and dynamically stable up to 100 GPa. The elastic constants, bulk modulus B, shear modulus G, hardness Hv, B/G ratio, Debye temperature under different pressures are systematically investigated. The calculation of electronic properties shows that ZrB12 has metallic character. The Zr-d states dominate the DOS at the Fermi level, and the total DOS and PDOS change slightly with the increasing pressure. DOS (Ef) first decreases, then increases with the increasing pressure. At 50 GPa, ZrB12 has less electron carriers. The analysis of electron localization function shows that the strong B-B and Zr-B covalent bonds may be responsible for the high hardness and stability.

On the Angular Dependence of the Vicinal Fluorine-Fluorine Coupling Constant in 1,2-Difluoroethane:  Deviation from a Karplus-like Shape.

PubMed

Provasi, Patricio F; Sauer, Stephan P A

2006-07-01

The angular dependence of the vicinal fluorine-fluorine coupling constant, (3)JFF, for 1,2-difluoroethane has been investigated with several polarization propagator methods. (3)JFF and its four Ramsey contributions were calculated using the random phase approximation (RPA), its multiconfigurational generalization, and both second-order polarization propagator approximations (SOPPA and SOPPA(CCSD)), using locally dense basis sets. The geometries were optimized for each dihedral angle at the level of density functional theory using the B3LYP functional and fourth-order Møller-Plesset perturbation theory. The resulting coupling constant curves were fitted to a cosine series with 8 coefficients. Our results are compared with those obtained previously and values estimated from experiment. It is found that the inclusion of electron correlation in the calculation of (3)JFF reduces the absolute values. This is mainly due to changes in the FC contribution, which for dihedral angles around the trans conformation even changes its sign. This sign change is responsible for the breakdown of the Karplus-like curve.

New constraints on time-dependent variations of fundamental constants using Planck data

NASA Astrophysics Data System (ADS)

Hart, Luke; Chluba, Jens

2018-02-01

Observations of the cosmic microwave background (CMB) today allow us to answer detailed questions about the properties of our Universe, targeting both standard and non-standard physics. In this paper, we study the effects of varying fundamental constants (i.e. the fine-structure constant, αEM, and electron rest mass, me) around last scattering using the recombination codes COSMOREC and RECFAST++. We approach the problem in a pedagogical manner, illustrating the importance of various effects on the free electron fraction, Thomson visibility function and CMB power spectra, highlighting various degeneracies. We demonstrate that the simpler RECFAST++ treatment (based on a three-level atom approach) can be used to accurately represent the full computation of COSMOREC. We also include explicit time-dependent variations using a phenomenological power-law description. We reproduce previous Planck 2013 results in our analysis. Assuming constant variations relative to the standard values, we find the improved constraints αEM/αEM, 0 = 0.9993 ± 0.0025 (CMB only) and me/me, 0 = 1.0039 ± 0.0074 (including BAO) using Planck 2015 data. For a redshift-dependent variation, αEM(z) = αEM(z0) [(1 + z)/1100]p with αEM(z0) ≡ αEM, 0 at z0 = 1100, we obtain p = 0.0008 ± 0.0025. Allowing simultaneous variations of αEM(z0) and p yields αEM(z0)/αEM, 0 = 0.9998 ± 0.0036 and p = 0.0006 ± 0.0036. We also discuss combined limits on αEM and me. Our analysis shows that existing data are not only sensitive to the value of the fundamental constants around recombination but also its first time derivative. This suggests that a wider class of varying fundamental constant models can be probed using the CMB.

Stability of Electrons in the Virtual Cathode Region of an IEC

NASA Astrophysics Data System (ADS)

Kim, Hyng-Jin; Miley, George; Momota, Hiromu

2003-04-01

In the Inertial Electrostatic Confinement (IEC) device, electrons are confined inside a virtual anode that in turn confines ions. Prior stability studies [1, 2] have considered systems in which one species is electrostatically confined by the other, and either or both species are out of local thermal equilibrium. In the present research, electron stability in the virtual cathode region of an ion injected IEC is being studied. The ion density in an IEC is non-uniform due to the radial electrostatic potential, and increases toward the center region. The potential near the virtual cathode is assumed to have a parabolic shape and is determined assuming that the net space charge density is constant in that region. The corresponding ion distribution function is assumed to have the form f = C [sigma] (H W) /L^0.5 and the electron response is taken to be diabatic. Then using a variational principle after linearizing the hydrodynamic equations, stability properties of the electron layer are determined. Results will be presented as a function of injected ion/electron current ratios. 1. L. Chacon and D. C. Barnes, Phys. Plasma 7, 4774 (2000). 2. D. C. Barnes, L. Chacon, and J. M. Finn, Phys. Plasmas 9, 4448 (2002).

Ultrasensitive Superconducting Transition Edge Sensors Based On Electron-Phonon Decoupling

NASA Technical Reports Server (NTRS)

Jethava, Nikhil; Chervenak, James; Brown, Ari-David; Benford, Dominic; Kletetschka, Gunther; Mikula, Vilem; U-yen, Kongpop

2011-01-01

We have successfully fabricated the superconducting transition edge sensor (TES), bolometer technology that centers on the use of electron-phonon decoupling (EPD) to thermally isolate the bolometer. Along with material characterization for large format antenna coupled bolometer arrays, we present the initial test results of bolometer based on EPD designed for THz detection. We have selected a design approach that separates the two functions of photon absorption and temperature measurement, allowing separate optimization of the performance of each element. We have integrated Molybdenum/Gold (Mo/Au) bilayer TES and ion assisted thermally evaporated (IAE) Bismuth (Bi) films as radiation absorber coupled to a low-loss microstripline from Niobium (Nb) ground plane to a twin-slot antenna structure. The thermal conductance and the time constant of these devices have been measured, and are consistent with our calculations. The device exhibits a single time constant at 0.1 K of approx.160 IlS, which is compatible with readout by a high-bandwidth single SQUID or a time domain SQUID multiplexer. The effects of thermal conductance and electrothermal feedback are major determinants of the time constant, but the electronic heat capacity also plays a major role. The NEP achieved in the device described above is 2.5x10(exp -17)W(gamma)Hz. Our plan is to demonstrate a reduction of the volume in the superconducting element to 5 microns x 5 microns in films of half the thickness at Tc = 60mK. By calculation, this new geometry corresponds to an NEP reduction of two orders of magnitude to 2.5x10(exp -19)W/(gamma)Hz, with a time constant of 130/ls.

Ab Initio Study of Electronic Structure, Elastic and Transport Properties of Fluoroperovskite LiBeF3

NASA Astrophysics Data System (ADS)

Benmhidi, H.; Rached, H.; Rached, D.; Benkabou, M.

2017-04-01

The aim of this work is to investigate the electronic, mechanical, and transport properties of the fluoroperovskite compound LiBeF3 by first-principles calculations using the full-potential linear muffin-tin orbital method based on density functional theory within the local density approximation. The independent elastic constants and related mechanical properties including the bulk modulus ( B), shear modulus ( G), Young's modulus ( E), and Poisson's ratio ( ν) have been studied, yielding the elastic moduli, shear wave velocities, and Debye temperature. According to the electronic properties, this compound is an indirect-bandgap material, in good agreement with available theoretical data. The electron effective mass, hole effective mass, and energy bandgaps with their volume and pressure dependence are investigated for the first time.

Millimeter-Wave Time Resolved Studies of the Formation and Decay of CO^+

NASA Astrophysics Data System (ADS)

Oesterling, Lee; Herbst, Eric; de Lucia, Frank

1998-04-01

Since the rate constants for ion-molecule interactions are typically much larger than neutral-neutral interactions, understanding ion-molecule interactions is essential to interpreting radio astronomical spectra from interstellar clouds and modeling the processes which lead to the formation of stars in these regions. We have developed a cell which allows us to study ion-molecule interactions in gases at low temperatures and pressures by using an electron gun technique to create ions. By centering our millimeter-wave source on a rotational resonance and gating the electron beam on and off, we are able to study the time-dependent rotational state distribution of the ion during its formation and decay, and so learn about excitation and relaxation processes as functions of temperature, pressure, electron beam energy, and electron beam current.

Coulomb Scattering in the Massless Nelson Model III: Ground State Wave Functions and Non-commutative Recurrence Relations

NASA Astrophysics Data System (ADS)

Dybalski, Wojciech; Pizzo, Alessandro

2018-02-01

Let $H_{P,\\sigma}$ be the single-electron fiber Hamiltonians of the massless Nelson model at total momentum $P$ and infrared cut-off $\\sigma>0$. We establish detailed regularity properties of the corresponding $n$-particle ground state wave functions $f^n_{P,\\sigma}$ as functions of $P$ and $\\sigma$. In particular, we show that \\[ |\\partial_{P^j}f^{n}_{P,\\sigma}(k_1,\\ldots, k_n)|, \\ \\ |\\partial_{P^j} \\partial_{P^{j'}} f^{n}_{P,\\sigma}(k_1,\\ldots, k_n)| \\leq \\frac{1}{\\sqrt{n!}} \\frac{(c\\lambda_0)^n}{\\sigma^{\\delta_{\\lambda_0}}} \\prod_{i=1}^n\\frac{ \\chi_{[\\sigma,\\kappa)}(k_i)}{|k_i|^{3/2}}, \\] where $c$ is a numerical constant, $\\lambda_0\\mapsto \\delta_{\\lambda_0}$ is a positive function of the maximal admissible coupling constant which satisfies $\\lim_{\\lambda_0\\to 0}\\delta_{\\lambda_0}=0$ and $\\chi_{[\\sigma,\\kappa)}$ is the (approximate) characteristic function of the energy region between the infrared cut-off $\\sigma$ and the ultraviolet cut-off $\\kappa$. While the analysis of the first derivative is relatively straightforward, the second derivative requires a new strategy. By solving a non-commutative recurrence relation we derive a novel formula for $f^n_{P,\\sigma}$ with improved infrared properties. In this representation $\\partial_{P^{j'}}\\partial_{P^{j}}f^n_{P,\\sigma}$ is amenable to sharp estimates obtained by iterative analytic perturbation theory in part II of this series of papers. The bounds stated above are instrumental for scattering theory of two electrons in the Nelson model, as explained in part I of this series.

Verification of the electron/proton coupled mechanism for phenolic H-atom transfer using a triplet π,π ∗ carbonyl

NASA Astrophysics Data System (ADS)

Yamaji, Minoru; Oshima, Juro; Hidaka, Motohiko

2009-06-01

Evidence for the coupled electron/proton transfer mechanism of the phenolic H-atom transfer between triplet π,π ∗ 3,3'-carbonylbis(7-diethylaminocoumarin) and phenol derivatives is obtained by using laser photolysis techniques. It was confirmed that the quenching rate constants of triplet CBC by phenols having positive Hammett constants do not follow the Rehm-Weller equation for electron transfer while those by phenols with negative Hammett constants do it. From the viewpoint of thermodynamic parameters for electron transfer, the crucial factors for phenolic H-atom transfer to π,π ∗ triplet are discussed.

Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

2018-03-01

We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

Distinguishing between deep trapping transients of electrons and holes in TiO2 nanotube arrays using planar microwave resonator sensor.

PubMed

Zarifi, Mohammad H; Wiltshire, Benjamin Daniel; Mahdi, Najia; Shankar, Karthik; Daneshmand, Mojgan

2018-05-16

A large signal DC bias and a small signal microwave bias were simultaneously applied to TiO2 nanotube membranes mounted on a planar microwave resonator. The DC bias modulated the electron concentration in the TiO2 nanotubes, and was varied between 0 and 120 V in this study. Transients immediately following the application and removal of DC bias were measured by monitoring the S-parameters of the resonator as a function of time. The DC bias stimulated Poole-Frenkel type trap-mediated electrical injection of excess carriers into TiO2 nanotubes which resulted in a near constant resonant frequency but a pronounced decrease in the microwave amplitude due to free electron absorption. When ultraviolet illumination and DC bias were both present and then step-wise removed, the resonant frequency shifted due to trapping -mediated change in the dielectric constant of the nanotube membranes. Characteristic lifetimes of 60-80 s, 300-800 s and ~3000 s were present regardless of whether light or bias was applied and are also observed in the presence of a hole scavenger, which we attribute to oxygen adsorption and deep electron traps while another characteristic lifetime > 9000 s was only present when illumination was applied, and is attributed to the presence of hole traps.

Compton profiles of NiO and TiO2 obtained from first principles GWA spectral function

NASA Astrophysics Data System (ADS)

S, M. Khidzir; M, F. M. Halid; W, A. T. Wan Abdullah

2016-06-01

In this work, we first use momentum density studies to understand strongly correlated electron behavior, which is typically seen in transition metal oxides. We observe that correlated electron behavior as seen in bulk NiO is due to the Fermi break located in the middle of overlapping spectral functions obtained from a GW (G is Green’s function and W is the screened Coulomb interaction) approximation (GWA) calculation while in the case of TiO2 we can see that the origin of the constant momentum distribution in lower momenta is due to a pile up of spectra before the Fermi energy. These observations are then used to compare our calculated Compton profiles with previous experimental studies of Fukamachi and Limandri. Our calculations for NiO are observed to follow the same trend as the experimental profile but it is seen to have a wide difference in the case of TiO2before the Fermi break. The ground state momentum densities differ significantly from the quasiparticle momentum density, thus stressing the importance of the quasiparticle wave function as the input for the study of charge density and the electron localization function. Finally we perform a calculation of the quasiparticle renormalization function, giving a quantitative description of the discontinuity of the GWA momentum density.

Direct measurement of electron transfer distance decay constants of single redox proteins by electrochemical tunneling spectroscopy.

PubMed

Artés, Juan M; Díez-Pérez, Ismael; Sanz, Fausto; Gorostiza, Pau

2011-03-22

We present a method to measure directly and at the single-molecule level the distance decay constant that characterizes the rate of electron transfer (ET) in redox proteins. Using an electrochemical tunneling microscope under bipotentiostatic control, we obtained current−distance spectroscopic recordings of individual redox proteins confined within a nanometric tunneling gap at a well-defined molecular orientation. The tunneling current decays exponentially, and the corresponding decay constant (β) strongly supports a two-step tunneling ET mechanism. Statistical analysis of decay constant measurements reveals differences between the reduced and oxidized states that may be relevant to the control of ET rates in enzymes and biological electron transport chains.

Application of constrained deconvolution technique for reconstruction of electron bunch profile with strongly non-Gaussian shape

NASA Astrophysics Data System (ADS)

Geloni, G.; Saldin, E. L.; Schneidmiller, E. A.; Yurkov, M. V.

2004-08-01

An effective and practical technique based on the detection of the coherent synchrotron radiation (CSR) spectrum can be used to characterize the profile function of ultra-short bunches. The CSR spectrum measurement has an important limitation: no spectral phase information is available, and the complete profile function cannot be obtained in general. In this paper we propose to use constrained deconvolution method for bunch profile reconstruction based on a priori-known information about formation of the electron bunch. Application of the method is illustrated with practically important example of a bunch formed in a single bunch-compressor. Downstream of the bunch compressor the bunch charge distribution is strongly non-Gaussian with a narrow leading peak and a long tail. The longitudinal bunch distribution is derived by measuring the bunch tail constant with a streak camera and by using a priory available information about profile function.

Triazine herbicide resistance in the photosynthetic bacterium Rhodopseudomonas sphaeroides

PubMed Central

Brown, Alfred E.; Gilbert, Carl W.; Guy, Rachel; Arntzen, Charles J.

1984-01-01

The photoaffinity herbicide azidoatrazine (2-azido-4-ethylamino-6-isopropylamino-s-triazine) selectively labels the L subunit of the reaction center of the photosynthetic bacterium Rhodopseudomonas sphaeroides. Herbicide-resistant mutants retain the L subunit and have altered binding properties for methylthio- and chloro-substituted triazines as well as altered equilibrium constants for electron transfer between primary and secondary electron acceptors. We suggest that a subtle alteration in the L subunit is responsible for herbicide resistance and that the L subunit is the functional analog of the 32-kDa QB protein of chloroplast membranes. Images PMID:16593520

Revisiting Wiedemann-Franz law through Boltzmann transport equations and ab-initio density functional theory

NASA Astrophysics Data System (ADS)

Nag, Abhinav; Kumari, Anuja; Kumar, Jagdish

2018-05-01

We have investigated structural, electronic and transport properties of the alkali metals using ab-initio density functional theory. The electron energy dispersions are found parabolic free electron like which is expected for alkali metals. The lattice constants for all the studied metals are also in good agreement within 98% with experiments. We have further computed their transport properties using semi-classical Boltzmann transport equations with special focus on electrical and thermal conductivity. Our objective was to obtain Wiedemann-Franz law and hence Lorenz number. The motivation to do these calculations is to see that how the incorporation of different interactions such as electron-lattice, electron-electron interaction affect the Wiedeman-Franz law. By solving Boltzmann transport equations, we have obtained electrical conductivity (σ/τ) and thermal conductivity (κ0 /τ) at different temperatures and then calculated Lorenz number using L = κ0 /(σT). The obtained value of Lorenz number has been found to match with value derived for free electron Fermi gas 2.44× 10-8 WΩK-2. Our results prove that the Wiedemann-Franz law as derived for free electron gas does not change much for alkali metals, even when one incorporates interaction of electrons with atomic nuclei and other electrons. However, at lower temperatures, the Lorenz number, was found to be deviating from its theoretical value.

Absolute NMR shielding scales and nuclear spin–rotation constants in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br and {sup 127}I)

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

Demissie, Taye B., E-mail: taye.b.demissie@uit.no; Komorovsky, Stanislav; Repisky, Michal

2015-10-28

We present nuclear spin–rotation constants, absolute nuclear magnetic resonance (NMR) shielding constants, and shielding spans of all the nuclei in {sup 175}LuX and {sup 197}AuX (X = {sup 19}F, {sup 35}Cl, {sup 79}Br, {sup 127}I), calculated using coupled-cluster singles-and-doubles with a perturbative triples (CCSD(T)) correction theory, four-component relativistic density functional theory (relativistic DFT), and non-relativistic DFT. The total nuclear spin–rotation constants determined by adding the relativistic corrections obtained from DFT calculations to the CCSD(T) values are in general in agreement with available experimental data, indicating that the computational approach followed in this study allows us to predict reliable results formore » the unknown spin–rotation constants in these molecules. The total NMR absolute shielding constants are determined for all the nuclei following the same approach as that applied for the nuclear spin–rotation constants. In most of the molecules, relativistic effects significantly change the computed shielding constants, demonstrating that straightforward application of the non-relativistic formula relating the electronic contribution to the nuclear spin–rotation constants and the paramagnetic contribution to the shielding constants does not yield correct results. We also analyze the origin of the unusually large absolute shielding constant and its relativistic correction of gold in AuF compared to the other gold monohalides.« less

Electronic polarizability of light crude oil from optical and dielectric studies

NASA Astrophysics Data System (ADS)

George, A. K.; Singh, R. N.

2017-07-01

In the present paper we report the temperature dependence of density, refractive indices and dielectric constant of three samples of crude oils. The API gravity number estimated from the temperature dependent density studies revealed that the three samples fall in the category of light oil. The measured data of refractive index and the density are used to evaluate the polarizability of these fluids. Molar refractive index and the molar volume are evaluated through Lorentz-Lorenz equation. The function of the refractive index, FRI , divided by the mass density ρ, is a constant approximately equal to one-third and is invariant with temperature for all the samples. The measured values of the dielectric constant decrease linearly with increasing temperature for all the samples. The dielectric constant estimated from the refractive index measurements using Lorentz-Lorentz equation agrees well with the measured values. The results are promising since all the three measured properties complement each other and offer a simple and reliable method for estimating crude oil properties, in the absence of sufficient data.

Influence of defects on the absorption edge of InN thin films: The band gap value

NASA Astrophysics Data System (ADS)

Thakur, J. S.; Danylyuk, Y. V.; Haddad, D.; Naik, V. M.; Naik, R.; Auner, G. W.

2007-07-01

We investigate the optical-absorption spectra of InN thin films whose electron density varies from ˜1017tõ1021cm-3 . The low-density films are grown by molecular-beam-epitaxy deposition while highly degenerate films are grown by plasma-source molecular-beam epitaxy. The optical-absorption edge is found to increase from 0.61to1.90eV as the carrier density of the films is increased from low to high density. Since films are polycrystalline and contain various types of defects, we discuss the band gap values by studying the influence of electron degeneracy, electron-electron, electron-ionized impurities, and electron-LO-phonon interaction self-energies on the spectral absorption coefficients of these films. The quasiparticle self-energies of the valence and conduction bands are calculated using dielectric screening within the random-phase approximation. Using one-particle Green’s function analysis, we self-consistently determine the chemical potential for films by coupling equations for the chemical potential and the single-particle scattering rate calculated within the effective-mass approximation for the electron scatterings from ionized impurities and LO phonons. By subtracting the influence of self-energies and chemical potential from the optical-absorption edge energy, we estimate the intrinsic band gap values for the films. We also determine the variations in the calculated band gap values due to the variations in the electron effective mass and static dielectric constant. For the lowest-density film, the estimated band gap energy is ˜0.59eV , while for the highest-density film, it varies from ˜0.60tõ0.68eV depending on the values of electron effective mass and dielectric constant.

Structure-Property Relationship of Phenylene-Based Self-Assembled-Monolayers for Record Low Work Function of Indium Tin Oxide.

PubMed

Benneckendorf, Frank S; Hillebrandt, Sabina; Ullrich, Florian; Rohnacher, Valentina; Hietzschold, Sebastian; Jänsch, Daniel; Freudenberg, Jan; Beck, Sebastian; Mankel, Eric; Jaegermann, Wolfram; Pucci, Annemarie; Bunz, Uwe H F; Müllen, Klaus

2018-06-20

Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids we report self-assembled monolayers with a significant decrease of the work function (WF) of indium-tin oxide (ITO) electrodes. While the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N,N dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease of ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

Structural and vibrational properties of solid nitromethane under high pressure by density functional theory.

PubMed

Liu, Hong; Zhao, Jijun; Wei, Dongqing; Gong, Zizheng

2006-03-28

The structural, vibrational, and electronic properties of solid nitromethane under hydrostatic pressure of up to 20 GPa have been studied using density functional theory. The changes of cell volume, the lattice constants, and the molecular geometry of solid nitromethane under hydrostatic loading are examined, and the bulk modulus B0 and its pressure derivative B0' are fitted from the volume-pressure relation. Our theoretical results are compared with available experiments. The change of electron band gap of nitromethane under high pressure is also discussed. Based on the optimized crystal structures, the vibrational frequencies for the internal and lattice modes of the nitromethane crystal at ambient and high pressures are computed, and the pressure-induced frequency shifts of these modes are discussed.

First principles study of pressure induced polymorphic phase transition in KNO3

NASA Astrophysics Data System (ADS)

Yedukondalu, N.; Vaitheeswaran, G.

2015-06-01

We report the structural, elastic, electronic, and vibrational properties of polymorphic phases II and III of KNO3 based on density functional theory (DFT). Using semi-empirical dispersion correction (DFT-D2) method, we predicted the correct thermodynamic ground state of KNO3 and the obtained ground state properties of the polymorphs are in good agreement with the experiments. We further used this method to calculate the elastic constants, IR and Raman spectra, vibrational frequencies and their assignment of these polymorphs. The calculated Tran Blaha-modified Becke Johnson (TB-mBJ) electronic structure shows that both the polymorphic phases are direct band gap insulators with mixed ionic and covalent bonding. Also the TB-mBJ band gaps are improved over standard DFT functionals which are comparable with the available experiments.

STEREO/SEPT particle observations during the CIR event on 2011 August 9

NASA Astrophysics Data System (ADS)

Dresing, N.; Heber, B.; Klassen, A.; Kühl, P.; Boettcher, S. I.; Gomez-Herrero, R.; Wraase, S.

2017-12-01

Among others, shocks are known to be accelerators of energetic charged particles. However, many questions regarding the acceleration efficiency and the required conditions are not fully understood. In particular, the acceleration of electrons by shocks is often questioned. Recurrent energetic particle events are caused by the passage of Corotating Interaction Regions (CIRs) that have been extensively analysed by different instrumentation close to Earth. Measurements of the Solar Electron and Proton Telescope aboard the Solar TErrestrial RElations Observatory are utilized in the solar heliospheric community to investigate electron events. Due to its measurement principle, the magnet foil technique, ions can contribute to the electron channel. This effect is well known. During recurrent energetic particle events the averaged helium to proton ration is enhanced to more than 10%. The energy per nucleon spectra are nearly the same for protons and helium. Although the electron intensity profile is influenced by an ion contamination during the shock crossings it is not obvious that electrons are not enhanced during such periods. Computation using a GEANT4 simulation of the SEPT instrument resulted in response function for ions and electrons. These response functions have been utilzed to analyze the recurrent energetic particle event that was was measured by STEREO B on August 9, 2011. Assuming a constant helium to proton ratio and energy spectra described by a Band function we found that electron and ion measurement can be explained by the contribution of helium and protons with an helium to proton ratio of about 16%. Thus no electron enhancements are needed to explain the SEPT measurements.

Dynamic Determination of Some Optical and Electrical Properties of Galena Natural Mineral: Potassium Ethyl Xanthate Solution Interface

NASA Astrophysics Data System (ADS)

Todoran, D.; Todoran, R.; Anitas, E. M.; Szakacs, Zs.

2017-12-01

This paper presents results concerning optical and electrical properties of galena natural mineral and of the interface layer formed between it and the potassium ethyl xanthate solution. The applied experimental method was differential optical reflectance spectroscopy over the UV-Vis/NIR spectral domain. Computations were made using the Kramers-Kronig formalism. Spectral dependencies of the electron loss functions, determined from the reflectance data obtained from the polished mineral surface, display van Hove singularities, leading to the determination of its valence band gap and electron plasma energy. Time dependent measurement of the spectral dispersion of the relative reflectance of the film formed at the interface, using the same computational formalism, leads to the dynamical determination of the spectral variation of its optical and electrical properties. We computed behaviors of the dielectric constant (dielectric permittivity), the dielectric loss function, refractive index and extinction coefficient, effective valence number and of the electron loss functions. The measurements tend to stabilize when the dynamic adsorption-desorption equilibrium is reached at the interface level.

CuPc/Au(1 1 0): Determination of the azimuthal alignment by a combination of angle-resolved photoemission and density functional theory

PubMed Central

Lüftner, Daniel; Milko, Matus; Huppmann, Sophia; Scholz, Markus; Ngyuen, Nam; Wießner, Michael; Schöll, Achim; Reinert, Friedrich; Puschnig, Peter

2014-01-01

Here we report on a combined experimental and theoretical study on the structural and electronic properties of a monolayer of Copper-Phthalocyanine (CuPc) on the Au(1 1 0) surface. Low-energy electron diffraction reveals a commensurate overlayer unit cell containing one adsorbate species. The azimuthal alignment of the CuPc molecule is revealed by comparing experimental constant binding energy (kxky)-maps using angle-resolved photoelectron spectroscopy with theoretical momentum maps of the free molecule's highest occupied molecular orbital (HOMO). This structural information is confirmed by total energy calculations within the framework of van-der-Waals corrected density functional theory. The electronic structure is further analyzed by computing the molecule-projected density of states, using both a semi-local and a hybrid exchange-correlation functional. In agreement with experiment, the HOMO is located about 1.2 eV below the Fermi-level, while there is no significant charge transfer into the molecule and the CuPc LUMO remains unoccupied on the Au(1 1 0) surface. PMID:25284953

Half-metallic ferromagnetism in Fe, Co and Ni doped BaS: First principles calculations

NASA Astrophysics Data System (ADS)

Maurya, Savita; Sharma, Ramesh; Bhamu, K. C.

2018-04-01

The first principle investigation of structural, electronic, magnetic and optical properties of Ba1-xTMxS (x = 0.25) have been done using FPLAW method within the density functional theory (DFT) using generalized gradient approximation (GGA) for exchange correlation potential using two different functionals which are the PBE-sol and the modified Becke and Johnson local (spin) density approximation (mBJLDA). It was found that mBJLDA functional offer better account for the electronic structure of the Fe, Co and Ni-doped BaS. It was also observed that Fe/Co/Ni d, S p and Ba d states play a major role in determining the electronic properties of this alloy system. Investigation results shows that Ba0.75(Fe/Co/Ni)0.25S is ferromagnetic with magnetic moment of 3.72 µB, 2.73908 µB and 1.74324 µB at Fe, Co and Ni sites respectively. Complex dielectric constant ɛ(ω) and normal incidence reflectivity R(ω) are also been investigate for broad range of photon energies. These results are compared with the some reported existing experimental values.

Competitive Energy and Electron Transfer in β-Functionalized Free-Base Porphyrin-Zinc Porphyrin Dimer Axially Coordinated to C60 : Synthesis, Supramolecular Formation and Excited-State Processes.

PubMed

Hu, Yi; Thomas, Michael B; Jinadasa, R G Waruna; Wang, Hong; D'Souza, Francis

2017-09-18

Simultaneous occurrence of energy and electron transfer events involving different acceptor sites in a newly assembled supramolecular triad comprised of covalently linked free-base porphyrin-zinc porphyrin dyad, H 2 P-ZnP axially coordinated to electron acceptor fullerene, has been successfully demonstrated. The dyad was connected through the β-pyrrole positions of the porphyrin macrocycle instead of the traditionally used meso-positions for better electronic communication. Interestingly, the β-pyrrole functionalization modulated the optical properties to such an extent that it was possible to almost exclusively excite the zinc porphyrin entity in the supramolecular triad. The measured binding constant for the complex with 1:1 molecular stoichiometry was in the order of 10 4  m -1 revealing moderately stable complex formation. An energy level diagram constructed using optical, electrochemical and computational results suggested that both the anticipated energy and electron events are thermodynamically feasible in the triad. Consequently, it was possible to demonstrate occurrence of excited state energy transfer to the covalently linked H 2 P, and electron transfer to the coordinated ImC 60 from studies involving steady-state and time-resolved emission, and femto- and nanosecond transient absorption studies. The estimated energy transfer was around 67 % in the dyad with a rate constant of 1.1×10 9  s -1 . In the supramolecular triad, the charge separated state was rather long-lived although it was difficult to arrive the exact lifetime of charge separated state from nanosecond transient spectral studies due to overlap of strong triplet excited signals of porphyrin in the monitoring wavelength window. Nevertheless, simultaneous occurrence of energy and electron transfer in the appropriately positioned energy and electron acceptor entities in a supramolecular triad was possible to demonstrate in the present study, a step forward to unraveling the complex photochemical events occurring in natural photosynthesis and its implications in building light energy harvesting devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Uncovering the nonadiabatic response of geosynchronous electrons to geomagnetic disturbance

USGS Publications Warehouse

Gannon, Jennifer; Elkington, Scot R.; Onsager, Terrance G.

2012-01-01

We describe an energy spectrum method for scaling electron integral flux, which is measured at a constant energy, to phase space density at a constant value of the first adiabatic invariant which removes much of the variation due to reversible adiabatic effects. Applying this method to nearly a solar cycle (1995 - 2006) of geosynchronous electron integral flux (E>2.0MeV) from the GOES satellites, we see that much of the diurnal variation in electron phase space density at constant energy can be removed by the transformation to phase space density at constant μ (4000 MeV/G). This allows us a clearer picture of underlying non-adiabatic electron population changes due to geomagnetic activity. Using scaled phase space density, we calculate the percentage of geomagnetic storms resulting in an increase, decrease or no change in geosynchronous electrons as 38%, 7%, and 55%, respectively. We also show examples of changes in the electron population that may be different than the unscaled fluxes alone suggest. These examples include sudden electron enhancements during storms which appear during the peak of negative Dst for μ-scaled phase space density, contrary to the slow increase seen during the recovery phase for unscaled phase space density for the same event.

Electronic structure and defect properties of selenophosphate Pb2P2Se6 for γ-ray detection

NASA Astrophysics Data System (ADS)

Kontsevoi, Oleg Y.; Im, Jino; Wessels, Bruce W.; Kanatzidis, Mercouri G.; Freeman, Arthur J.

Heavy metal chalco-phosphate Pb2P2Se6 has shown a significant promise as an X-ray and γ-ray detector material. To assess the fundamental physical properties important for its performance as detector, theoretical calculations were performed for the electronic structure, band gaps, electron and hole effective masses, and static dielectric constants. The calculations were based on first-principles density functional theory (DFT) and employ the highly precise full potential linearized augmented plane wave method and the projector augmented wave method and include nonlocal exchange-correlation functionals to overcome the band gap underestimation in DFT calculations. The calculations show that Pb2P2Se6 is an indirect band gap material with the calculated band gap of 2.0 eV, has small effective masses, which could result in a good carrier mobility-lifetime product μτ , and a very high static dielectric constant, which could lead to high mobility of carriers by screening of charged scattering centers. We further investigated a large set of native defects in Pb2P2Se6 to determine the optimal growth conditions for application as γ-ray detectors. The results suggest that the prevalent intrinsic defects are selenium vacancies, followed by lead vacancies, then phosphorus vacancies and antisite defects. The effect of various chemical environments on defect properties was examined and the optimal conditions for material synthesis were suggested. Supported by DHS (Grant No. 2014-DN-077-ARI086-01).

Anisotropic distribution function of minority tail ions generated by strong ion-cyclotron resonance heating

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

Chang, C.S.; Colestock, P.

1989-05-01

The highly anisotropic particle distribution function of minority tail ions driven by ion-cyclotron resonance heating at the fundamental harmonic is calculated in a two-dimensional velocity space. It is assumed that the heating is strong enough to drive most of the resonant ions above the in-electron critical slowing-down energy. Simple analytic expressions for the tail distribution are obtained fro the case when the Doppler effect is sufficiently large to flatten the sharp pitch angle dependence in the bounce averaged qualilinear heating coefficient, D/sub b/, and for the case when D/sub b/ is assumed to be constant in pitch angle and energy.more » It is found that a simple constant-D/sub b/ solution can be used instead of the more complicated sharp-D/sub b/ solution for many analytic purposes. 4 refs., 4 figs.« less

Graphene as a Promising Electrode for Low-Current Attenuation in Nonsymmetric Molecular Junctions.

PubMed

Zhang, Qian; Liu, Longlong; Tao, Shuhui; Wang, Congyi; Zhao, Cezhou; González, César; Dappe, Yannick J; Nichols, Richard J; Yang, Li

2016-10-12

We have measured the single-molecule conductance of 1,n-alkanedithiol molecular bridges (n = 4, 6, 8, 10, 12) on a graphene substrate using scanning tunneling microscopy (STM)-formed electrical junctions. The conductance values of this homologous series ranged from 2.3 nS (n = 12) to 53 nS (n = 4), with a decay constant β n of 0.40 per methylene (-CH 2 ) group. This result is explained by a combination of density functional theory (DFT) and Keldysh-Green function calculations. The obtained decay, which is much lower than the one obtained for symmetric gold junctions, is related to the weak coupling at the molecule-graphene interface and the electronic structure of graphene. As a consequence, we show that using graphene nonsymmetric junctions and appropriate anchoring groups may lead to a much-lower decay constant and more-conductive molecular junctions at longer lengths.

First-principles study of length dependence of conductance in alkanedithiols

NASA Astrophysics Data System (ADS)

Zhou, Y. X.; Jiang, F.; Chen, H.; Note, R.; Mizuseki, H.; Kawazoe, Y.

2008-01-01

Electronic transport properties of alkanedithiols are calculated by a first-principles method based on density functional theory and nonequilibrium Green's function formalism. At small bias, the I-V characteristics are linear and the resistances conform to the Magoga's exponential law. The calculated length-dependent decay constant γ which reflects the effect of internal molecular structure is in accordance with most experiments quantitatively. Also, the calculated effective contact resistance R0 is in good agreement with the results of repeatedly measuring molecule-electrode junctions [B. Xu and N. Tao, Science 301, 1221 (2003)].

Partition functions and equilibrium constants for diatomic molecules and atoms of astrophysical interest

NASA Astrophysics Data System (ADS)

Barklem, P. S.; Collet, R.

2016-04-01

Partition functions and dissociation equilibrium constants are presented for 291 diatomic molecules for temperatures in the range from near absolute zero to 10 000 K, thus providing data for many diatomic molecules of astrophysical interest at low temperature. The calculations are based on molecular spectroscopic data from the book of Huber & Herzberg (1979, Constants of Diatomic Molecules) with significant improvements from the literature, especially updated data for ground states of many of the most important molecules by Irikura (2007, J. Phys. Chem. Ref. Data, 36, 389). Dissociation energies are collated from compilations of experimental and theoretical values. Partition functions for 284 species of atoms for all elements from H to U are also presented based on data collected at NIST. The calculated data are expected to be useful for modelling a range of low density astrophysical environments, especially star-forming regions, protoplanetary disks, the interstellar medium, and planetary and cool stellar atmospheres. The input data, which will be made available electronically, also provides a possible foundation for future improvement by the community. Full Tables 1-8 are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/588/A96

Composition dependence of mechanical property changes in electron irradiated borosilicate glasses

NASA Astrophysics Data System (ADS)

Lv, P.; Chen, L.; Duan, B. H.; Zhang, D. F.; Wang, T. S.

2017-08-01

Mechanical properties evolution of three kinds of ternary Na2O-B2O3-SiO2 (labeled as NBS) glasses induced by 1.2 MeV electrons has been investigated by nano-indentation measurements. The glass samples were prepared with different values of the molar ratio R = [Na2O]/[B2O3] (0.4, 0.75 and 1.34), while the molar ratio K = [SiO2]/[B2O3] was kept constant as 4.04. The results indicated that both the mean hardness and the reduced Young modulus were decreased as a function of electron dose and the decrements are significantly related with the glass compositions. The toughness of all these three NBS glasses was slightly improved due to electron irradiation. The mechanical properties of glass samples with greater R value tend to be less affected under electron irradiation.

Theoretical electronic transition moments for the Ballik-Ramsay, Fox-Herzberg, and Swan systems of C2

NASA Technical Reports Server (NTRS)

Cooper, D. M.

1981-01-01

Electronic transition moments and their variation with internuclear separation are calculated for the Ballik-Ramsay (b 3 Sigma g - a 3 Pi u), Fox-Herzberg (e 3 Pi g-a 3 Pi u) and Swan (d 3 Pi g-a 3 Pi u) band systems of C2, which appear in a variety of terrestrial and astrophysical sources. Electronic wave functions of the a 3 Pi u, b 2 Sigma g -, d 3 Pi g and e 3 Pi g states of C2 are obtained by means of a self-consistent field plus configuration interaction calculation using an atomic basis of 46 Slater-type orbitals, and theoretical potential energy curves and spectroscopic constants for the four electronic states were computed. The results obtained for both the potential energy curves and electronic transition moments are found to be in good agreement with experimental data.

Hot Electrons from Two-Plasmon Decay

NASA Astrophysics Data System (ADS)

Russell, D. A.; Dubois, D. F.

2000-10-01

We solve, self-consistently, the relativistic quasilinear diffusion equation and Zakharov's model equations of Langmuir wave (LW) and ion acoustic wave (IAW) turbulence, in two dimensions, for saturated states of the Two-Plasmon Decay instability. Parameters are those of the shorter gradient scale-length (50 microns) high temperature (4 keV) inhomogeneous plasmas anticipated at LLE’s Omega laser facility. We calculate the fraction of incident laser power absorbed in hot electron production as a function of laser intensity for a plane-wave laser field propagating parallel to the background density gradient. Two distinct regimes are identified: In the strong-turbulent regime, hot electron bursts occur intermittently in time, well correlated with collapse in the LW and IAW fields. A significant fraction of the incident laser power ( ~10%) is absorbed by hot electrons during a single burst. In the weak or convective regime, relatively constant rates of hot electron production are observed at much reduced intensities.

First-principles investigation for some physical properties of some fluoroperovskites compounds ABF3 (A = K, Na; B = Mg, Zn)

NASA Astrophysics Data System (ADS)

Bakri, Badis; Driss, Zied; Berri, Saadi; Khenata, Rabah

2017-12-01

In this work, the structural, electronic and optical properties of fluoroperovskite ABF3 (A = K, Na; B = Mg, Zn) were studied using two different approaches: the full-potential linearized augmented plane wave method and the pseudo-potential plane wave scheme in the frame of generalized gradient approximation features such as the lattice constant, bulk modulus and its pressure derivative are reported. The ground state properties of these compounds such as the equilibrium lattice constant and the bulk modulus are in good agreement with the experimental results. The first principles calculations were performed to study the electronic structures of ABF3(A = K, Na; B = Mg, Zn) compounds and the results indicated that these four compounds are indirect band gap insulators. The optical properties are analysed and the source of some peaks in the spectra is discussed. Besides, the dielectric function, refractive index and extinction coefficient for radiation up to 25 eV have also been reported and discussed.

Development of Superconducting Transition Edge Sensors Based on Electron-Phonon Decoupling

NASA Technical Reports Server (NTRS)

Jethava, Nikhil; Chervenak, James; Brown, Ari-David; Benford, Dominic; Kletetschka, Gunther; Mikula, Vilem; U-yen, Kongpop

2010-01-01

We have successfully fabricated a superconducting transition edge sensor (TES), bolometer that centers on the use of electron-phonon decoupling (EPD) for thermal isolation. We have selected a design approach that separates the two functions of far-infrared and THz radiative power absorption and temperature measurement, allowing separate optimization of the performance of each element. We have integrated molybdenum/gold (Mo/Au) bilayer TES and ion assisted thermally evaporated (IAE) bismuth (Bi) films as radiation absorber coupled to a low-loss microstripline from niobium (Nb) ground plane to a twin-slot antenna structure. The thermal conductance (G) and the time constant for the different geometry device have been measured. For one such device, the measured G is 1.16 x 10(exp -10) W/K (plus or minus 0.61 x 10(exp- 10) W/K) at 60 mK, which corresponds to noise equivalent power (NEP) = 1.65 X 10(exp -18)W/vHz and time constant of approximately 5 microseconds.

Electron transfer by excited benzoquinone anions: slow rates for two-electron transitions.

PubMed

Zamadar, Matibur; Cook, Andrew R; Lewandowska-Andralojc, Anna; Holroyd, Richard; Jiang, Yan; Bikalis, Jin; Miller, John R

2013-09-05

Electron transfer (ET) rate constants from the lowest excited state of the radical anion of benzoquinone, BQ(-•)*, were measured in THF solution. Rate constants for bimolecular electron transfer reactions typically reach the diffusion-controlled limit when the free-energy change, ΔG°, reaches -0.3 eV. The rate constants for ET from BQ(-•)* are one-to-two decades smaller at this energy and do not reach the diffusion-controlled limit until -ΔG° is 1.5-2.0 eV. The rates are so slow probably because a second electron must also undergo a transition to make use of the energy of the excited state. Similarly, ET, from solvated electrons to neutral BQ to form the lowest excited state, is slow, while fast ET is observed at a higher excited state, which can be populated in a transition involving only one electron. A simple picture based on perturbation theory can roughly account for the control of electron transfer by the need for transition of a second electron. The picture also explains how extra driving force (-ΔG°) can restore fast rates of electron transfer.

Diazonium functionalized graphene: microstructure, electric, and magnetic properties.

PubMed

Huang, Ping; Jing, Long; Zhu, Huarui; Gao, Xueyun

2013-01-15

The unique honeycomb lattice structure of graphene gives rise to its outstanding electronic properties such as ultrahigh carrier mobility, ballistic transport, and more. However, a crucial obstacle to its use in the electronics industry is its lack of an energy bandgap. A covalent chemistry strategy could overcome this problem, and would have the benefits of being highly controllable and stable in the ambient environment. One possible approach is aryl diazonium functionalization. In this Account, we investigate the micromolecular/lattice structure, electronic structure, and electron-transport properties of nitrophenyl-diazonium-functionalized graphene. We find that nitrophenyl groups mainly adopt random and inhomogeneous configurations on the graphene basal plane, and that their bonding with graphene carbon atoms leads to slight elongation of the graphene lattice spacing. By contrast, hydrogenated graphene has a compressed lattice. Low levels of functionalization suppressed the electric conductivity of the resulting functionalized graphene, while highly functionalized graphene showed the opposite effect. This difference arises from the competition between the charge transfer effect and the scattering enhancement effect introduced by nitrophenyl groups bonding with graphene carbon atoms. Detailed electron transport measurements revealed that the nitrophenyl diazonium functionalization locally breaks the symmetry of graphene lattice, which leads to an increase in the density of state near the Fermi level, thus increasing the carrier density. On the other hand, the bonded nitrophenyl groups act as scattering centers, lowering the mean free path of the charge carriers and suppressing the carrier mobility. In rare cases, we observed ordered configurations of nitrophenyl groups in local domains on graphene flakes due to fluctuations in the reaction processes. We describe one example of such a superlattice, with a lattice constant nearly twice of that of pristine graphene. We performed comprehensive theoretical calculations to investigate the lattice and the electronic structure of the superlattice structure. Our results reveal that it is a thermodynamically stable, spin-polarized semiconductor with a bandgap of ∼0.5 eV. Our results demonstrate the possibility of controlling graphene's electronic properties using aryl diazonium functionalization. Asymmetric addition of aryl groups to different sublattices of graphene is a promising approach for producing ferromagnetic, semiconductive graphene, which will have broad applications in the electronic industry.

Nearly-free-electron system of monolayer Na on the surface of single-crystal HfSe 2

DOE PAGES

Eknapakul, T.; Fongkaew, I.; Siriroj, S.; ...

2016-11-15

Here, the electronic structure of a single Na monolayer on the surface of single-crystal HfSe 2 is investigated using angle-resolved photoemission spectroscopy. We find that this system exhibits an almost perfect "nearly-free-electron" behavior with an extracted effective mass of ~1m e, in contrast to heavier masses found previously for alkali-metal monolayers on other substrates. Our density-functional-theory calculations indicate that this is due to the large lattice constant, causing both exchange and correlation interactions to be suppressed, and to the weak hybridization between the overlayer and the substrate. This is therefore an ideal model system for understanding the properties of two-dimensionalmore » materials.« less

Mesoporous aluminium organophosphonates: a reusable chemsensor for the detection of explosives

NASA Astrophysics Data System (ADS)

Li, Dongdong; Yu, Xiang

2016-07-01

Rapid and sensitive detection of explosives is in high demand for homeland security and public safety. In this work, electron-rich of anthracene functionalized mesoporous aluminium organophosphonates (En-AlPs) were synthesized by a one-pot condensation process. The mesoporous structure and strong blue emission of En-AlPs were confirmed by the N2 adsorption-desorption isotherms, transmission electron microscopy images and fluorescence spectra. The materials En-AlPs can serve as sensitive chemosensors for various electron deficient nitroderivatives, with the quenching constant and the detection limit up to 1.5×106 M-1 and 0.3 ppm in water solution. More importantly, the materials can be recycled for many times by simply washed with ethanol, showing potential applications in explosives detection.

Characterization of hot dense plasma with plasma parameters

NASA Astrophysics Data System (ADS)

Singh, Narendra; Goyal, Arun; Chaurasia, S.

2018-05-01

Characterization of hot dense plasma (HDP) with its parameters temperature, electron density, skin depth, plasma frequency is demonstrated in this work. The dependence of HDP parameters on temperature and electron density is discussed. The ratio of the intensities of spectral lines within HDP is calculated as a function of electron temperature. The condition of weakly coupled for HDP is verified by calculating coupling constant. Additionally, atomic data such as transition wavelength, excitation energies, line strength, etc. are obtained for Be-like ions on the basis of MCDHF method. In atomic data calculations configuration interaction and relativistic effects QED and Breit corrections are newly included for HDP characterization and this is first result of HDP parameters from extreme ultraviolet (EUV) radiations.

Origins of the structural phase transitions in MoTe2 and WTe2

NASA Astrophysics Data System (ADS)

Kim, Hyun-Jung; Kang, Seoung-Hun; Hamada, Ikutaro; Son, Young-Woo

2017-05-01

Layered transition metal dichalcogenides MoTe2 and WTe2 share almost similar lattice constants as well as topological electronic properties except their structural phase transitions. While the former shows a first-order phase transition between monoclinic and orthorhombic structures, the latter does not. Using a recently proposed van der Waals density functional method, we investigate structural stability of the two materials and uncover that the disparate phase transitions originate from delicate differences between their interlayer bonding states near the Fermi energy. By exploiting the relation between the structural phase transitions and the low energy electronic properties, we show that a charge doping can control the transition substantially, thereby suggesting a way to stabilize or to eliminate their topological electronic energy bands.

Dielectric response of branched copper phthalocyanine

NASA Astrophysics Data System (ADS)

Hamam, Khalil J.; Al-Amar, Mohammad M.; Mezei, Gellert; Guda, Ramakrishna; Burns, Clement A.

2017-09-01

The dielectric constant of pressed pellets and thin films of branched copper phthalocyanine (CuPc) was investigated as a function of frequency from 0.1 kHz to 1 MHz and temperature from 20 °C to 100 °C. Surface morphology was studied using a scanning electron microscope. The high-frequency values of the dielectric constant of pellets and thin films are ~3.5 and ~5.8, respectively. The response was only weakly dependent on frequency and temperature. The branched structure of the CuPc molecules helped to cancel out the effects of low-frequency polarization mechanisms. A planar delocalized charge system with two-dimensional localization was found using time-resolved photoluminescence measurements.

The Analytical Solution of the Transient Radial Diffusion Equation with a Nonuniform Loss Term.

NASA Astrophysics Data System (ADS)

Loridan, V.; Ripoll, J. F.; De Vuyst, F.

2017-12-01

Many works have been done during the past 40 years to perform the analytical solution of the radial diffusion equation that models the transport and loss of electrons in the magnetosphere, considering a diffusion coefficient proportional to a power law in shell and a constant loss term. Here, we propose an original analytical method to address this challenge with a nonuniform loss term. The strategy is to match any L-dependent electron losses with a piecewise constant function on M subintervals, i.e., dealing with a constant lifetime on each subinterval. Applying an eigenfunction expansion method, the eigenvalue problem becomes presently a Sturm-Liouville problem with M interfaces. Assuming the continuity of both the distribution function and its first spatial derivatives, we are able to deal with a well-posed problem and to find the full analytical solution. We further show an excellent agreement between both the analytical solutions and the solutions obtained directly from numerical simulations for different loss terms of various shapes and with a diffusion coefficient DLL L6. We also give two expressions for the required number of eigenmodes N to get an accurate snapshot of the analytical solution, highlighting that N is proportional to 1/√t0, where t0 is a time of interest, and that N increases with the diffusion power. Finally, the equilibrium time, defined as the time to nearly reach the steady solution, is estimated by a closed-form expression and discussed. Applications to Earth and also Jupiter and Saturn are discussed.

Theoretical hyperfine structures of 19F i and 17O i

NASA Astrophysics Data System (ADS)

Aourir, Nouria; Nemouchi, Messaoud; Godefroid, Michel; Jönsson, Per

2018-03-01

Multiconfiguration Hartree-Fock (MCHF) and multiconfiguration Dirac-Hartree-Fock (MCDHF) calculations are performed for the 2 p5P2o , 2 p4(3P ) 3 s 4P , 2 p4(3P ) 3 s 2P , and 2 p4(3P ) 3 p 4So states of 19F i to determine their hyperfine constants. Several computing strategies are considered to investigate electron correlation and relativistic effects. High-order correlation contributions are included in MCHF calculations based on single and double multireference expansions. The largest components of the single reference MCHF wave functions are selected to define the multireference (MR) sets. In this scheme, relativistic corrections are evaluated in the Breit-Pauli approximation. A similar strategy is used for the calculation of MCDHF relativistic wave functions and hyperfine parameters. While correlation and relativistic corrections are found to be rather small for the ground state, we highlight large relativistic effects on the hyperfine constant A3 /2 of 2 p4(3P ) 3 p 4So and, to a lesser extent, on A1 /2 of 2 p4(3P ) 3 s 4P . As expected for such a light system, electron correlation effects dominate over relativity in the calculation of the hyperfine interaction of all other levels considered. We also revisit the hyperfine constants of 2 p3(4S ) 3 s S5o and 2 p3(4S ) 3 p 5P in 17O using similar strategies. The results are found to be in excellent agreement with experiment.

Full potential study of the elastic, electronic, and optical properties of spinels MgIn{sub 2}S{sub 4} and CdIn{sub 2}S{sub 4} under pressure effect

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

Semari, F.; Khenata, R.; Depatment of Physics and Astronomy, King Saud University, PO Box 2455, Riyadh 11451

2010-12-15

The structural, elastic, electronic, and optical properties of cubic spinel MgIn{sub 2}S{sub 4} and CdIn{sub 2}S{sub 4} compounds have been calculated using a full relativistic version of the full-potential linearized-augmented plane wave with the mixed basis FP/APW+lo method. The exchange and correlation potential is treated by the generalized-gradient approximation (GGA). Moreover, the Engel-Vosko GGA formalism is also applied to optimize the corresponding potential for band structure calculations. The ground state properties, including the lattice constants, the internal parameter, the bulk modulus, and the pressure derivative of the bulk modulus are in reasonable agreement with the available data. Using the totalmore » energy-strain technique, we have determined the full set of first-order elastic constants C{sub ij} and their pressure dependence, which have not been calculated or measured yet. The shear modulus, Young's modulus, and Poisson's ratio are calculated for polycrystalline XIn{sub 2}S{sub 4} aggregates. The Debye temperature is estimated from the average sound velocity. Electronic band structures show a direct band gap ({Gamma}-{Gamma}) for MgIn{sub 2}S{sub 4} and an indirect band gap (K-{Gamma}) for CdIn{sub 2}S{sub 4}. The calculated band gaps with EVGGA show a significant improvement over the GGA. The optical constants, including the dielectric function {epsilon}({omega}), the refractive index n({omega}), the reflectivity R({omega}), and the energy loss function L({omega}) were calculated for radiation up to 30 eV. -- Graphical abstract: Calculated total and partial densities of states for MgIn{sub 2}S{sub 4} and CdIn{sub 2}S{sub 4}« less

Electrochemical and theoretical analysis of the reactivity of shikonin derivatives: dissociative electron transfer in esterified compounds.

PubMed

Armendáriz-Vidales, Georgina; Frontana, Carlos

2014-09-07

An electrochemical and theoretical analysis of a series of shikonin derivatives in aprotic media is presented. Results showed that the first electrochemical reduction signal is a reversible monoelectronic transfer, generating a stable semiquinone intermediate; the corresponding E(I)⁰ values were correlated with calculated values of electroaccepting power (ω(+)) and adiabatic electron affinities (A(Ad)), obtained with BH and HLYP/6-311++G(2d,2p) and considering the solvent effect, revealing the influence of intramolecular hydrogen bonding and the substituting group at position C-2 in the experimental reduction potential. For the second reduction step, esterified compounds isobutyryl and isovalerylshikonin presented a coupled chemical reaction following dianion formation. Analysis of the variation of the dimensionless cathodic peak potential values (ξ(p)) as a function of the scan rate (v) functions and complementary experiments in benzonitrile suggested that this process follows a dissociative electron transfer, in which the rate of heterogeneous electron transfer is slow (~0.2 cm s(-1)), and the rate constant of the chemical process is at least 10(5) larger.

The order of three lowest-energy states of the six-electron harmonium at small force constant

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

Strasburger, Krzysztof

2016-06-21

The order of low-energy states of six-electron harmonium is uncertain in the case of strong correlation, which is not a desired situation for the model system being considered for future testing of approximate methods of quantum chemistry. The computational study of these states has been carried out at the frequency parameter ω = 0.01, using the variational method with the basis of symmetry-projected, explicitly correlated Gaussian (ECG) lobe functions. It has revealed that the six-electron harmonium at this confinement strength is an octahedral Wigner molecule, whose order of states is different than in the strong confinement regime and does notmore » agree with the earlier predictions. The results obtained for ω = 0.5 and 10 are consistent with the findings based on the Hund’s rules for the s{sup 2}p{sup 4} electron configuration. Substantial part of the computations has been carried out on the graphical processing units and the efficiency of these devices in calculation of the integrals over ECG functions has been compared with traditional processors.« less

Calculation of the electron wave function in a graded-channel double-heterojunction modulation-doped field-effect transistor

NASA Technical Reports Server (NTRS)

Mui, D. S. L.; Patil, M. B.; Morkoc, H.

1989-01-01

Three double-heterojunction modulation-doped field-effect transistor structures with different channel composition are investigated theoretically. All of these transistors have an In(x)Ga(1-x)As channel sandwiched between two doped Al(0.3)Ga(0.7)As barriers with undoped spacer layers. In one of the structures, x varies from 0 from either heterojunction to 0.15 at the center of the channel quadratically; in the other two, constant values of x of 0 and 0.15 are used. The Poisson and Schroedinger equations are solved self-consistently for the electron wave function in all three cases. The results showed that the two-dimensional electron gas (2DEG) concentration in the channel of the quadratically graded structure is higher than the x = 0 one and slightly lower than the x = 0.15 one, and the mean distance of the 2DEG is closer to the center of the channel for this transistor than the other two. These two effects have important implications on the electron mobility in the channel.

Long-range electron tunneling.

PubMed

Winkler, Jay R; Gray, Harry B

2014-02-26

Electrons have so little mass that in less than a second they can tunnel through potential energy barriers that are several electron-volts high and several nanometers wide. Electron tunneling is a critical functional element in a broad spectrum of applications, ranging from semiconductor diodes to the photosynthetic and respiratory charge transport chains. Prior to the 1970s, chemists generally believed that reactants had to collide in order to effect a transformation. Experimental demonstrations that electrons can transfer between reactants separated by several nanometers led to a revision of the chemical reaction paradigm. Experimental investigations of electron exchange between redox partners separated by molecular bridges have elucidated many fundamental properties of these reactions, particularly the variation of rate constants with distance. Theoretical work has provided critical insights into the superexchange mechanism of electronic coupling between distant redox centers. Kinetics measurements have shown that electrons can tunnel about 2.5 nm through proteins on biologically relevant time scales. Longer-distance biological charge flow requires multiple electron tunneling steps through chains of redox cofactors. The range of phenomena that depends on long-range electron tunneling continues to expand, providing new challenges for both theory and experiment.

Hydrodynamic limit of Wigner-Poisson kinetic theory: Revisited

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

Akbari-Moghanjoughi, M.; International Centre for Advanced Studies in Physical Sciences and Institute for Theoretical Physics, Ruhr University Bochum, D-44780 Bochum

2015-02-15

In this paper, we revisit the hydrodynamic limit of the Langmuir wave dispersion relation based on the Wigner-Poisson model in connection with that obtained directly from the original Lindhard dielectric function based on the random-phase-approximation. It is observed that the (fourth-order) expansion of the exact Lindhard dielectric constant correctly reduces to the hydrodynamic dispersion relation with an additional term of fourth-order, beside that caused by the quantum diffraction effect. It is also revealed that the generalized Lindhard dielectric theory accounts for the recently discovered Shukla-Eliasson attractive potential (SEAP). However, the expansion of the exact Lindhard static dielectric function leads tomore » a k{sup 4} term of different magnitude than that obtained from the linearized quantum hydrodynamics model. It is shown that a correction factor of 1/9 should be included in the term arising from the quantum Bohm potential of the momentum balance equation in fluid model in order for a correct plasma dielectric response treatment. Finally, it is observed that the long-range oscillatory screening potential (Friedel oscillations) of type cos(2k{sub F}r)/r{sup 3}, which is a consequence of the divergence of the dielectric function at point k = 2k{sub F} in a quantum plasma, arises due to the finiteness of the Fermi-wavenumber and is smeared out in the limit of very high electron number-densities, typical of white dwarfs and neutron stars. In the very low electron number-density regime, typical of semiconductors and metals, where the Friedel oscillation wavelength becomes much larger compared to the interparticle distances, the SEAP appears with a much deeper potential valley. It is remarked that the fourth-order approximate Lindhard dielectric constant approaches that of the linearized quantum hydrodynamic in the limit if very high electron number-density. By evaluation of the imaginary part of the Lindhard dielectric function, it is shown that the Landau-damping region in ω-k plane increases dramatically by increase of the electron number-density.« less

Large dielectric constant in zirconia polypyrrole hybrid nanocomposites.

PubMed

Dey, Ashis; De, S K

2007-06-01

Zirconia nanoparticles have been synthesized by a novel two-reverse emulsion technique and combined with polypyrrole (PPY) to form ZrO2-PPY nanocomposites. Complex impedance and dielectric permittivity of ZrO2-PPY nanocomposite have been investigated as a function of frequency and temperature for different compositions. The composite samples are characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning and transmission electron microscopy. The composites reveal ordered semiconducting behaviour. Polypyrrole is the major component in electrical transport process of the samples. A very large dielectric constant of about 12,000 at room temperature has been observed. The colossal dielectric constant is mainly dominated by interfacial polarization due to Maxwell-Wagner relaxation effect. Two completely separate groups of dielectric relaxation have been observed. The low frequency dielectric relaxation arises from surface defect states of zirconia nanoparticles. The broad peak at high frequency is due to Maxwell-Wagner type polarization.

Temperature-dependent ac conductivity and dielectric response of vanadium doped CaCu3Ti4O12 ceramic

NASA Astrophysics Data System (ADS)

Sen, A.; Maiti, U. N.; Thapa, R.; Chattopadhyay, K. K.

2011-09-01

Successful incorporation of vanadium dopant within the giant dielectric material CaCu 3Ti 4O12 (CCTO) through a conventional solid-state sintering process is achieved and its influence on the dielectric as well as electrical properties as a function of temperature and frequency is reported here. Proper crystalline phase formation together with dopant induced lattice constant shrinkage was confirmed through X-ray diffraction. The temperature dependence of the dielectric constant at different constant frequencies was investigated. We infer that the correlated barrier hopping (CBH) model is dominant in the conduction mechanism of the ceramic as per the temperature-dependent ac conductivity measurements. The electronic parameters such as density of the states at the Fermi level, N( E f) and hopping distance, R ω of the ceramic were also calculated using this model.

Elastic scattering of X-rays and gamma rays by 2S electrons in ions and neutral atoms

NASA Astrophysics Data System (ADS)

Costescu, A.; Spânulescu, S.; Stoica, C.

2012-08-01

The nonrelativistic limit of Rayleigh scattering amplitude on 2s electrons of neutral and partially ionized atoms is obtained by making use of the Green Function method. The result takes into consideration the retardation, relativistic kinematics and screening effects. The spurious singularities introduced by the retardation in a nonrelativistic approach are cancelled by the relativistic kinematics. For neutral and partially ionized atoms, a screening model is considered with an effective charge obtained by fitting the Hartree-Fock charge distribution with pure Coulombian wave functions corresponding to a central potential of a nucleus with Zeff as the atomic number. The total cross section of the photoeffect on the 2s electrons is also calculated from the imaginary part of the forward scattering amplitude by means of the optical theorem. The numerical results obtained are in a good agreement (10%) with the ones obtained by Kissell for the Rayleigh amplitude and by Scofield for the Photoeffect total cross section on the 2s electrons, for atoms with atomic number 18 ≤ Z ≤ 92 and photon energies ω≤αZm. (α=1/137,... is the fine structure constant, m is the electron mass).

Theoretical investigation of discharge parameters in magnetized radio frequency excited CO2 lasers

NASA Astrophysics Data System (ADS)

Tavassoli, H.; Sohbatzadeh, F.; Latifi, H.

2003-06-01

In the present paper the magnetic field effects on discharge parameters in rf excited CO2 lasers are calculated. A rf generated plasma imbedded in an external, constant, and homogeneous magnetic field is considered. The continuity equation is used to derive the electron density. Quasineutrality condition and ambipolar diffusion are used. Electron attachment coefficient is neglected. Local electric field, local electron density, and thickness of charge layers are derived as a function of distance from the electrodes and magnetic field. The thickness of charge layers in the presence of magnetic field is always smaller than one without the magnetic field. When the magnetic field increases, the electron density increases in all regions of discharge, and the electric field reduces in the charge layers but increases in the middle part of discharge.

Structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 phases from first-principles calculations

NASA Astrophysics Data System (ADS)

Li, X. D.; Li, K.; Wei, C. H.; Han, W. D.; Zhou, N. G.

2018-06-01

The structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 are systematically investigated by using first-principles calculations method based on density functional theory (DFT). The calculated formation enthalpies and cohesive energies show that CaSi2 possesses the greatest structural stability and CaSi has the strongest alloying ability. The structural stability of the three phases is compared according to electronic structures. Further analysis on electronic structures indicates that the bonding of these phases exhibits the combinations of metallic, covalent, and ionic bonds. The elastic constants are calculated, and the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and anisotropy factor of polycrystalline materials are deduced. Additionally, the thermodynamic properties were theoretically predicted and discussed.

Density functional theory study of hydrogen atom abstraction from a series of para-substituted phenols: why is the Hammett σ(p)+ constant able to represent radical reaction rates?

PubMed

Yoshida, Tatsusada; Hirozumi, Koji; Harada, Masataka; Hitaoka, Seiji; Chuman, Hiroshi

2011-06-03

The rate of hydrogen atom abstraction from phenolic compounds by a radical is known to be often linear with the Hammett substitution constant σ(+), defined using the S(N)1 solvolysis rates of substituted cumyl chlorides. Nevertheless, a physicochemical reason for the above "empirical fact" has not been fully revealed. The transition states of complexes between the 2,2-diphenyl-1-picrylhydrazyl radical (dpph·) and a series of para-substituted phenols were determined by DFT (Density Functional Theory) calculations, and then the activation energy as well as the homolytic bond dissociation energy of the O-H bond and charge distribution in the transition state were calculated. The heterolytic bond dissociation energy of the C-Cl bond and charge distribution in the corresponding para-substituted cumyl chlorides were calculated in parallel. Excellent correlations among σ(+), charge distribution, and activation and bond dissociation energies revealed quantitatively that there is a strong similarity between the two reactions, showing that the electron-deficiency of the π-electron system conjugated with a substituent plays a crucial role in determining rates of the two reactions. The results provide a new insight into and physicochemical understanding of σ(+) in the hydrogen abstraction from substituted phenols by a radical.

A computational study of photo-induced electron transfer rate constants in subphthalocyanine/C60 organic photovoltaic materials via Fermi's golden rule

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

We present a methodology to obtain the photo-induced electron transfer rate constant in organic photovoltaic (OPV) materials within the framework of Fermi's golden rule, using inputs obtained from first-principles electronic structure calculation. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided in contrast to the classical Marcus theory where these modes are treated classically within the high-temperature and short-time limits. We demonstrate our methodology on boron-subphthalocyanine-chloride/C60 OPV system to determine the rate constants of electron transfer and electron recombination processes upon photo-excitation. We consider two representative donor/acceptor interface configurations to investigate the effect of interface configuration on the charge transfer characteristics of OPV materials. In addition, we determine the time scale of excited states population by employing a master equation after obtaining the rate constants for all accessible electronic transitions. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

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.

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

Kappa and other nonequilibrium distributions from the Fokker-Planck equation and the relationship to Tsallis entropy.

PubMed

Shizgal, Bernie D

2018-05-01

This paper considers two nonequilibrium model systems described by linear Fokker-Planck equations for the time-dependent velocity distribution functions that yield steady state Kappa distributions for specific system parameters. The first system describes the time evolution of a charged test particle in a constant temperature heat bath of a second charged particle. The time dependence of the distribution function of the test particle is given by a Fokker-Planck equation with drift and diffusion coefficients for Coulomb collisions as well as a diffusion coefficient for wave-particle interactions. A second system involves the Fokker-Planck equation for electrons dilutely dispersed in a constant temperature heat bath of atoms or ions and subject to an external time-independent uniform electric field. The momentum transfer cross section for collisions between the two components is assumed to be a power law in reduced speed. The time-dependent Fokker-Planck equations for both model systems are solved with a numerical finite difference method and the approach to equilibrium is rationalized with the Kullback-Leibler relative entropy. For particular choices of the system parameters for both models, the steady distribution is found to be a Kappa distribution. Kappa distributions were introduced as an empirical fitting function that well describe the nonequilibrium features of the distribution functions of electrons and ions in space science as measured by satellite instruments. The calculation of the Kappa distribution from the Fokker-Planck equations provides a direct physically based dynamical approach in contrast to the nonextensive entropy formalism by Tsallis [J. Stat. Phys. 53, 479 (1988)JSTPBS0022-471510.1007/BF01016429].

Kappa and other nonequilibrium distributions from the Fokker-Planck equation and the relationship to Tsallis entropy

NASA Astrophysics Data System (ADS)

Shizgal, Bernie D.

2018-05-01

This paper considers two nonequilibrium model systems described by linear Fokker-Planck equations for the time-dependent velocity distribution functions that yield steady state Kappa distributions for specific system parameters. The first system describes the time evolution of a charged test particle in a constant temperature heat bath of a second charged particle. The time dependence of the distribution function of the test particle is given by a Fokker-Planck equation with drift and diffusion coefficients for Coulomb collisions as well as a diffusion coefficient for wave-particle interactions. A second system involves the Fokker-Planck equation for electrons dilutely dispersed in a constant temperature heat bath of atoms or ions and subject to an external time-independent uniform electric field. The momentum transfer cross section for collisions between the two components is assumed to be a power law in reduced speed. The time-dependent Fokker-Planck equations for both model systems are solved with a numerical finite difference method and the approach to equilibrium is rationalized with the Kullback-Leibler relative entropy. For particular choices of the system parameters for both models, the steady distribution is found to be a Kappa distribution. Kappa distributions were introduced as an empirical fitting function that well describe the nonequilibrium features of the distribution functions of electrons and ions in space science as measured by satellite instruments. The calculation of the Kappa distribution from the Fokker-Planck equations provides a direct physically based dynamical approach in contrast to the nonextensive entropy formalism by Tsallis [J. Stat. Phys. 53, 479 (1988), 10.1007/BF01016429].

Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical

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

Genova, Alessandro, E-mail: alessandro.genova@rutgers.edu; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu; Ceresoli, Davide, E-mail: davide.ceresoli@cnr.it

2016-06-21

In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange–correlation potentials that aremore » linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH{sup •} radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH{sup •} radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.« less

Avoiding fractional electrons in subsystem DFT based ab-initio molecular dynamics yields accurate models for liquid water and solvated OH radical.

PubMed

Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

2016-06-21

In this work we achieve three milestones: (1) we present a subsystem DFT method capable of running ab-initio molecular dynamics simulations accurately and efficiently. (2) In order to rid the simulations of inter-molecular self-interaction error, we exploit the ability of semilocal frozen density embedding formulation of subsystem DFT to represent the total electron density as a sum of localized subsystem electron densities that are constrained to integrate to a preset, constant number of electrons; the success of the method relies on the fact that employed semilocal nonadditive kinetic energy functionals effectively cancel out errors in semilocal exchange-correlation potentials that are linked to static correlation effects and self-interaction. (3) We demonstrate this concept by simulating liquid water and solvated OH(•) radical. While the bulk of our simulations have been performed on a periodic box containing 64 independent water molecules for 52 ps, we also simulated a box containing 256 water molecules for 22 ps. The results show that, provided one employs an accurate nonadditive kinetic energy functional, the dynamics of liquid water and OH(•) radical are in semiquantitative agreement with experimental results or higher-level electronic structure calculations. Our assessments are based upon comparisons of radial and angular distribution functions as well as the diffusion coefficient of the liquid.

Existence of ground state of an electron in the BDF approximation

NASA Astrophysics Data System (ADS)

Sok, Jérémy

2014-05-01

The Bogoliubov-Dirac-Fock (BDF) model allows us to describe relativistic electrons interacting with the Dirac sea. It can be seen as a mean-field approximation of Quantum Electrodynamics (QED) where photons are neglected. This paper treats the case of an electron together with the Dirac sea in the absence of any external field. Such a system is described by its one-body density matrix, an infinite rank, self-adjoint operator. The parameters of the model are the coupling constant α > 0 and the ultraviolet cut-off Λ > 0: we consider the subspace of squared integrable functions made of the functions whose Fourier transform vanishes outside the ball B(0, Λ). We prove the existence of minimizers of the BDF energy under the charge constraint of one electron and no external field provided that α, Λ-1 and α log(Λ) are sufficiently small. The interpretation is the following: in this regime the electron creates a polarization in the Dirac vacuum which allows it to bind. We then study the non-relativistic limit of such a system in which the speed of light tends to infinity (or equivalently α tends to zero) with αlog(Λ) fixed: after rescaling and translation the electronic solution tends to a Choquard-Pekar ground state.

Structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba)

NASA Astrophysics Data System (ADS)

Benahmed, A.; Bouhemadou, A.; Alqarni, B.; Guechi, N.; Al-Douri, Y.; Khenata, R.; Bin-Omran, S.

2018-05-01

First-principles calculations were performed to investigate the structural, elastic, electronic, optical and thermoelectric properties of the Zintl-phase Ae3AlAs3 (Ae = Sr, Ba) using two complementary approaches based on density functional theory. The pseudopotential plane-wave method was used to explore the structural and elastic properties whereas the full-potential linearised augmented plane wave approach was used to study the structural, electronic, optical and thermoelectric properties. The calculated structural parameters are in good consistency with the corresponding measured ones. The single-crystal and polycrystalline elastic constants and related properties were examined in details. The electronic properties, including energy band dispersions, density of states and charge-carrier effective masses, were computed using Tran-Blaha modified Becke-Johnson functional for the exchange-correlation potential. It is found that both studied compounds are direct band gap semiconductors. Frequency-dependence of the linear optical functions were predicted for a wide photon energy range up to 15 eV. Charge carrier concentration and temperature dependences of the basic parameters of the thermoelectric properties were explored using the semi-classical Boltzmann transport model. Our calculations unveil that the studied compounds are characterised by a high thermopower for both carriers, especially the p-type conduction is more favourable.

Dynamical properties of magnetized two-dimensional one-component plasma

NASA Astrophysics Data System (ADS)

Dubey, Girija S.; Gumbs, Godfrey; Fessatidis, Vassilios

2018-05-01

Molecular dynamics simulation are used to examine the effect of a uniform perpendicular magnetic field on a two-dimensional interacting electron system. In this simulation we include the effect of the magnetic field classically through the Lorentz force. Both the Coulomb and the magnetic forces are included directly in the electron dynamics to study their combined effect on the dynamical properties of the 2D system. Results are presented for the velocity autocorrelation function and the diffusion constants in the presence and absence of an external magnetic field. Our simulation results clearly show that the external magnetic field has an effect on the dynamical properties of the system.

Prediction of phonon-mediated superconductivity in hole-doped black phosphorus.

PubMed

Feng, Yanqing; Sun, Hongyi; Sun, Junhui; Lu, Zhibin; You, Yong

2018-01-10

We study the conventional electron-phonon mediated superconducting properties of hole-doped black phosphorus by density functional calculations and get quite a large electron-phonon coupling (EPC) constant λ ~ 1.0 with transition temperature T C ~ 10 K, which is comparable to MgB 2 when holes are doped into the degenerate and nearly flat energy bands around the Fermi level. We predict that the softening of low-frequency [Formula: see text] optical mode and its phonon displacement, which breaks the lattice nonsymmorphic symmetry of gliding plane and lifts the band double degeneracy, lead to a large EPC. These factors are favorable for BCS superconductivity.

Prediction of phonon-mediated superconductivity in hole-doped black phosphorus

NASA Astrophysics Data System (ADS)

Feng, Yanqing; Sun, Hongyi; Sun, Junhui; Lu, Zhibin; You, Yong

2018-01-01

We study the conventional electron-phonon mediated superconducting properties of hole-doped black phosphorus by density functional calculations and get quite a large electron-phonon coupling (EPC) constant λ ~ 1.0 with transition temperature T C ~ 10 K, which is comparable to MgB2 when holes are doped into the degenerate and nearly flat energy bands around the Fermi level. We predict that the softening of low-frequency B3g1 optical mode and its phonon displacement, which breaks the lattice nonsymmorphic symmetry of gliding plane and lifts the band double degeneracy, lead to a large EPC. These factors are favorable for BCS superconductivity.

Ab-initio calculations of structural, electronic, and optical properties of Zn3(VO4)2

NASA Astrophysics Data System (ADS)

Ahmed, Nisar; Mukhtar, S.; Gao, Wei; Zafar Ilyas, Syed

2018-03-01

The structural, electronic, and optical properties of Zn3(VO4)2 are investigated using full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory (DFT). Various approaches are adopted to treat the exchange and correlation potential energy such as generalized gradient approximation (GGA), GGA+U, and the Tran–Blaha modified Becke–Johnson (TB-mBJ) potential. The calculated band gap of 3.424 eV by TB-mBJ is found to be close to the experimental result (3.3 eV). The optical anisotropy is analyzed through optical constants, such as dielectric function and absorption coefficient along parallel and perpendicular crystal orientations. The absorption coefficient reveals high absorption (1.5× {10}6 {cm}}-1) of photons in the ultraviolet region.

Ab initio calculation of the electronic structures of the (7)Sigma+ ground and A (7)Pi and a (5)Sigma+ excited states of MnH.

PubMed

Tomonari, Mutsumi; Nagashima, Umpei; Hirano, Tsuneo

2009-04-21

Electronic structures and molecular constants of the ground (7)Sigma(+) and low-lying A (7)Pi and a (5)Sigma(+) electronic excited states of the MnH molecule were studied by multireference single and double excitation configuration interaction (MR-SDCI) with Davidson's correction (+Q) calculations under exact C(infinity v) symmetry using Slater-type basis sets. To correctly describe the (7)Sigma(+) electronic ground state, X (7)Sigma(+), at the MR-SDCI+Q calculation, we employed a large number of reference configurations in terms of the state-averaged complete active space self-consistent field (CASSCF) orbitals, taking into account the contribution from the B (7)Sigma(+) excited state. The A (7)Pi and a (5)Sigma(+) states can well be described by the MR-SDCI wave functions based on the CASSCF orbitals obtained for the lowest state only. In the MR-SDCI+Q, calculations of the X (7)Sigma(+), A (7)Pi, and a (5)Sigma(+) states required 16, 7, and 17 reference configurations, respectively. Molecular constants, i.e., r(e) and omega(e) of these states and excitation energy from the X (7)Sigma(+) state, obtained at the MR-SDCI+Q level, showed a good agreement with experimental values. The small remaining differences may be accounted for by taking relativistic effects into account.

Ab initio calculation of the electronic structures of the 7∑+ ground and A 7Π and a 5∑+ excited states of MnH

NASA Astrophysics Data System (ADS)

Tomonari, Mutsumi; Nagashima, Umpei; Hirano, Tsuneo

2009-04-01

Electronic structures and molecular constants of the ground ∑7+ and low-lying A 7Π and a ∑5+ electronic excited states of the MnH molecule were studied by multireference single and double excitation configuration interaction (MR-SDCI) with Davidson's correction (+Q) calculations under exact C∞v symmetry using Slater-type basis sets. To correctly describe the ∑7+ electronic ground state, X ∑7+, at the MR-SDCI+Q calculation, we employed a large number of reference configurations in terms of the state-averaged complete active space self-consistent field (CASSCF) orbitals, taking into account the contribution from the B ∑7+ excited state. The A 7Π and a ∑5+ states can well be described by the MR-SDCI wave functions based on the CASSCF orbitals obtained for the lowest state only. In the MR-SDCI+Q, calculations of the X ∑7+, A 7Π, and a ∑5+ states required 16, 7, and 17 reference configurations, respectively. Molecular constants, i.e., re and ωe of these states and excitation energy from the X ∑7+ state, obtained at the MR-SDCI+Q level, showed a good agreement with experimental values. The small remaining differences may be accounted for by taking relativistic effects into account.

Calculation of nuclear spin-spin coupling constants using frozen density embedding

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

Götz, Andreas W., E-mail: agoetz@sdsc.edu; Autschbach, Jochen; Visscher, Lucas, E-mail: visscher@chem.vu.nl

2014-03-14

We present a method for a subsystem-based calculation of indirect nuclear spin-spin coupling tensors within the framework of current-spin-density-functional theory. Our approach is based on the frozen-density embedding scheme within density-functional theory and extends a previously reported subsystem-based approach for the calculation of nuclear magnetic resonance shielding tensors to magnetic fields which couple not only to orbital but also spin degrees of freedom. This leads to a formulation in which the electron density, the induced paramagnetic current, and the induced spin-magnetization density are calculated separately for the individual subsystems. This is particularly useful for the inclusion of environmental effects inmore » the calculation of nuclear spin-spin coupling constants. Neglecting the induced paramagnetic current and spin-magnetization density in the environment due to the magnetic moments of the coupled nuclei leads to a very efficient method in which the computationally expensive response calculation has to be performed only for the subsystem of interest. We show that this approach leads to very good results for the calculation of solvent-induced shifts of nuclear spin-spin coupling constants in hydrogen-bonded systems. Also for systems with stronger interactions, frozen-density embedding performs remarkably well, given the approximate nature of currently available functionals for the non-additive kinetic energy. As an example we show results for methylmercury halides which exhibit an exceptionally large shift of the one-bond coupling constants between {sup 199}Hg and {sup 13}C upon coordination of dimethylsulfoxide solvent molecules.« less

Dynamics, magnetic properties, and electron binding energies of H2O2 in water.

PubMed

C Cabral, Benedito J

2017-06-21

Results for the magnetic properties and electron binding energies of H 2 O 2 in liquid water are presented. The adopted methodology relies on the combination of Born-Oppenheimer molecular dynamics and electronic structure calculations. The Keal-Tozer functional was applied for predicting magnetic shieldings and H 2 O 2 intramolecular spin-spin coupling constants. Electron binding energies were calculated with electron propagator theory. In water, H 2 O 2 is a better proton donor than proton acceptor, and the present results indicate that this feature is important for understanding magnetic properties in solution. In comparison with the gas-phase, H 2 O 2 atoms are deshielded in water. For oxygen atoms, the deshielding is mainly determined by structural/conformational changes. Hydrogen-bond interactions explain the deshielding of protons in water. The predicted chemical shift for the H 2 O 2 protons in water (δ∼11.8 ppm) is in good agreement with experimental information (δ=11.2 ppm). The two lowest electron binding energies of H 2 O 2 in water (10.7±0.5 and 11.2±0.5 eV) are in reasonable agreement with experiment. In keeping with data from photoelectron spectroscopy, an ∼1.6 eV red-shift of the two first ionisation energies relative to the gas-phase is observed in water. The strong dependence of magnetic properties on changes of the electronic density in the nuclei environment is illustrated by a correlation between the σ( 17 O) magnetic shielding constant and the energy gap between the [2a] lowest valence and [1a] core orbitals of H 2 O 2 .

Dielectric Properties of PMMA and its Composites with ZrO2

NASA Astrophysics Data System (ADS)

Sannakki, Basavaraja; Anita

The polymer films of PMMA with different thickness and its composites with ZrO2 at various weight percentages but of same thickness have been studied. The determination of its dielectric properties, dielectric loss, a.conductivity and dielectric modulus were carried out using capacitance measurements of the above samples as a function of frequency, over the range 50 Hz - 5 MHz at room temperature. The films of PMMA and its composites have been characterized using X-Ray Diffractometer. The dielectric permittivity of films of PMMA behaves nonlinearly as frequency increases over the range 50-300 Hz, where as above 300 Hz the values of dielectric constant remains constant. But it is observed that the dielectric constant of PMMA increases as thickness of the film increases. In case of composite films of PMMA with ZrO2 the values of dielectric permittivity decreases gradually up to frequency of around 1 KHz and at higher frequencies it remains constant for all the weight percentages of ZrO2. The complex form of dielectric modulus of PMMA is obtained from the experimentally measured data of dielectric constant and dielectric loss values. The relaxation time of the orientation of dipoles is obtained from the peak value of angular frequency through the plots of imaginary part of electrical modulus as function of frequency. The impedance of PMMA polymer increases as thickness of the films increases. The a c conductivity of PMMA film remains constant up to frequency of 1 MHz and above. It shows a nonlinear phenomenon with peak values at frequency 4 MHz. Shape and size of the nanoparticles of composite film of PMMA with ZrO2 was analyzed by Field Emission Scanning Electron Microscope (FESEM).

Electronic and optical properties of Fe2SiO4 under pressure effect: ab initio study

NASA Astrophysics Data System (ADS)

Xiao, Lingping; Li, Xiaobin; Yang, Xue

2018-05-01

We report first-principles studies the structural, electronic, and optical properties of the Fe2SiO4 fayalite in orthorhombic structure, including pressure dependence of structural parameters, band structures, density of states, and optical constants up to 30 GPa. The calculated results indicate that the linear compressibility along b axis is significantly higher than a and c axes, which is in agreement with earlier work. Meanwhile, the pressure dependence of the electronic band structure, density of states and partial density of states of Fe2SiO4 fayalite up to 30 GPa were presented. Moreover, the evolution of the dielectric function, absorption coefficient (α(ω)), reflectivity (R(ω)), and the real part of the refractive index (n(ω)) at high pressure are also presented.

Relativistic coupled-cluster calculations of the 173Yb nuclear quadrupole coupling constant for the YbF molecule

NASA Astrophysics Data System (ADS)

Pašteka, L. F.; Mawhorter, R. J.; Schwerdtfeger, P.

2016-04-01

We report calculations on the q(Yb) electric field gradient (EFG) for the X2Σ+ and A2Π1/2 electronic states of the ytterbium monofluoride (YbF) molecule at the molecular mean-field Dirac-Coulomb-Gaunt as well as scalar-relativistic coupled-cluster levels of theory using large uncontracted basis sets. Vibrational contributions are included in the final results. Our estimated nuclear quadrupole coupling constants of -3386(78) MHz and -2083(153) MHz for the X2Σ+ and A2Π1/2 states of 173YbF are in stark contrast to the only available experimental results (-2050(170) MHz and -1090(160) MHz) respectively, where the only similarity is the difference between the two values. Perturbative triple contributions in the coupled cluster treatment are significant and point towards the necessity to go to higher order in the coupled-cluster treatment in future calculations. We also present density functional calculations which show rather large variations for the Yb EFG with different functionals used; the best result was obtained using the CAM-B3LYP* functional.

A new quaternary semiconductor compound (Ba2Sb4GeS10): Ab initio study

NASA Astrophysics Data System (ADS)

Ozisik, Havva Bogaz; Ozisik, Haci; Deligoz, Engin

2017-03-01

The newly synthesised Ba2Sb4GeS10 compound is notable because of the interesting features of the quaternary Sb-containing materials. The first principle method has been used to determine the physical properties of this compound. In particular, the electronic structure has been analysed using both conventional GGA-PBE and HSE06 functional. The values of the band gap for PBE and HSE06 calculations were 1.324 and 1.84 eV, respectively. The calculated elastic constants were used to predict polycrystalline mechanical properties. The estimated Vickers hardness (2.7 GPa) values show that Ba2Sb4GeS10 is soft matter. Moreover, the vibrational properties of the compound have been studied. The calculation of the elastic constants and phonon dispersion curves indicates that the Ba2Sb4GeS10 compound is stable both mechanically and dynamically. Furthermore, the minimum thermal conductivity and optical properties, such as dielectric functions and energy loss function, have also been discussed in detail in this paper.

Numerical study of the defect adamantine compound CuGaGeSe4

NASA Astrophysics Data System (ADS)

Shen, Kesheng; Zhang, Xianzhou; Lu, Hai; Jiao, Zhaoyong

2018-06-01

The electronic structure, elastic and optical properties of the defect adamantine compound CuGaGeSe4 in ? structure are systematically investigated using first-principles calculations. Through detailed calculation and comparison, we obtain three independent atomic arrangements and predict the most stable atomic arrangement according to the lattice constants and enthalpy formation energies. The elastic constants are calculated, which can be used to predict the axial thermal expansion coefficients accurately. The optical properties of compound CuGaGeSe4, including the dielectric function, refractive index and absorption spectrum, are depicted for a more intuitive understanding. Our calculated zero-frequency limits ɛ1(0) and n(0) are very close to the other theoretical values, which proves that our calculations are reliable.

Electron Attachment to Radicals and Highly-Excited States in Laser-Irradiated CCl_2F_2*

NASA Astrophysics Data System (ADS)

Pinnaduwage, Lal; Datskos, Panos

1997-10-01

We have measured electron attachment rate constants for two species produced via ArF-excimer- laser irradiated CF_2Cl_2, i.e., the CF_2Cl radical and the highly-excited electronically-excited states of CF_2Cl_2. These measurements show that while electron attachment to the fragment radical has a rate constants about an order of magnitude higher compared to the ground states of CF_2Cl_2, electron attachment to the highly- excited states have many orders of magnitude larger rate constants. To our knowledge, only one other electron attachment measurement has been conducted on molecular fragments up to now. Implications of these measurements for plasma processing discharges will be discussed. Research supported by the National Science Foundation under contract No. ECS-9626217 with the University of Tennessee, Knoxville. The Oak Ridge National Laboratory is managed by Lockheed Martin Energy Research Corp. for the U. S. DOE under contract No. DE-AC05- 96OR22464.

Screening of a dust particle charge in a humid air plasma created by an electron beam

NASA Astrophysics Data System (ADS)

Filippov, A. V.; Derbenev, I. N.; Kurkin, S. A.

2018-01-01

A kinetic model has been developed for charged particle reactions in a humid air plasma produced by a fast electron beam. The model includes over 550 reactions with electrons, 33 positive ion species and 14 negative ion species. The model has been tested by solving 48 non-steady state equations for number densities of charged particles in humid air electron beam plasma, and by comparing with the available experimental data. The system of 48 steady state equations has been solved by iterative method in order to define the main ion species of the humid air plasma. A reduced kinetic model has been developed to describe the processes with the main ions and electrons. Screening constants have been calculated on the basis of the reduced system by means of Leverrier-Fadeev method. The dependencies of screening constants on gas ionization rates have been found for the rates from 10 to 1018 cm-3s-1 and the fraction of water molecules from 0 to 2%. The analysis of the constants has revealed that one of them is close to the inverse Debye length, and the other constants are defined by the inverse diffusion lengths passed by ions in the characteristic times of the attachment, recombination, and ion conversion. Pure imaginary screening constants appear at low rates of gas ionization.

Time-resolved study of the electron temperature and number density of argon metastable atoms in argon-based dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Desjardins, E.; Laurent, M.; Durocher-Jean, A.; Laroche, G.; Gherardi, N.; Naudé, N.; Stafford, L.

2018-01-01

A combination of optical emission spectroscopy and collisional-radiative modelling is used to determine the time-resolved electron temperature (assuming Maxwellian electron energy distribution function) and number density of Ar 1s states in atmospheric pressure Ar-based dielectric barrier discharges in presence of either NH3 or ethyl lactate. In both cases, T e values were higher early in the discharge cycle (around 0.8 eV), decreased down to about 0.35 eV with the rise of the discharge current, and then remained fairly constant during discharge extinction. The opposite behaviour was observed for Ar 1s states, with cycle-averaged values in the 1017 m-3 range. Based on these findings, a link was established between the discharge ionization kinetics (and thus the electron temperature) and the number density of Ar 1s state.

Basic electronic properties of iron selenide under variation of structural parameters

NASA Astrophysics Data System (ADS)

Guterding, Daniel; Jeschke, Harald O.; Valentí, Roser

2017-09-01

Since the discovery of high-temperature superconductivity in the thin-film FeSe /SrTiO3 system, iron selenide and its derivates have been intensively scrutinized. Using ab initio density functional theory calculations we review the electronic structures that could be realized in iron selenide if the structural parameters could be tuned at liberty. We calculate the momentum dependence of the susceptibility and investigate the symmetry of electron pairing within the random phase approximation. Both the susceptibility and the symmetry of electron pairing depend on the structural parameters in a nontrivial way. These results are consistent with the known experimental behavior of binary iron chalcogenides and, at the same time, reveal two promising ways of tuning superconducting transition temperatures in these materials: on one hand by expanding the iron lattice of FeSe at constant iron-selenium distance and, on the other hand, by increasing the iron-selenium distance with unchanged iron lattice.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander V.; Hammes-Schiffer, Sharon

2015-11-21

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency proton donor-acceptor vibrational modes. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term in the framework of the cumulant expansion framework may significantly impact the rate constants at highmore » temperatures for proton transfer interfaces with soft proton donor-acceptor modes that are associated with small force constants and weak hydrogen bonds. The effects of the quadratic term may also become significant in these regimes when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant. In this case, however, the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances sampled. The effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances. Additionally, the rigorous relation between the cumulant expansion and thermal averaging approaches is clarified. In particular, the cumulant expansion rate constant includes effects from dynamical interference between the proton donor-acceptor and solvent motions and becomes equivalent to the thermally averaged rate constant when these dynamical effects are neglected. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes.« less

On the truncation of the number of excited states in density functional theory sum-over-states calculations of indirect spin spin coupling constants

NASA Astrophysics Data System (ADS)

Zarycz, M. Natalia C.; Provasi, Patricio F.; Sauer, Stephan P. A.

2015-12-01

It is investigated, whether the number of excited (pseudo)states can be truncated in the sum-over-states expression for indirect spin-spin coupling constants (SSCCs), which is used in the Contributions from Localized Orbitals within the Polarization Propagator Approach and Inner Projections of the Polarization Propagator (IPPP-CLOPPA) approach to analyzing SSCCs in terms of localized orbitals. As a test set we have studied the nine simple compounds, CH4, NH3, H2O, SiH4, PH3, SH2, C2H2, C2H4, and C2H6. The excited (pseudo)states were obtained from time-dependent density functional theory (TD-DFT) calculations with the B3LYP exchange-correlation functional and the specialized core-property basis set, aug-cc-pVTZ-J. We investigated both how the calculated coupling constants depend on the number of (pseudo)states included in the summation and whether the summation can be truncated in a systematic way at a smaller number of states and extrapolated to the total number of (pseudo)states for the given one-electron basis set. We find that this is possible and that for some of the couplings it is sufficient to include only about 30% of the excited (pseudo)states.

Role of biaxial strain and microscopic ordering for structural and electronic properties of InxGa1 -xN

NASA Astrophysics Data System (ADS)

Cui, Ying; Lee, Sangheon; Freysoldt, Christoph; Neugebauer, Jörg

2015-08-01

The structural and electronic properties of InxGa1 -xN alloys are studied as a function of c -plane biaxial strain and In ordering by density functional theory with the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional. A nonlinear variation of the c lattice parameter with In content is observed in biaxial strain and should be taken into account when deducing In content from interplanar distances. From compressive to tensile strain, the character of the top valence-band state changes, leading to a nonlinear variation of the band gap in InxGa1 -xN . Interestingly, the well-known bowing of the InxGa1 -xN band gap is largely removed for alloys grown strictly coherently on GaN, while the actual values for band gaps at x <0.33 are hardly affected by strain. Ordering plays a minor role for lattice constants but may induce changes of the band gap up to 0.15 eV.

Measuring the Electron’s Charge and the Fine-Structure Constant by Counting Electrons on a Capacitor

PubMed Central

Williams, E. R.; Ghosh, Ruby N.; Martinis, John M.

1992-01-01

The charge of the electron can be determined by simply placing a known number of electrons on one electrode of a capacitor and measuring the voltage, Vs, across the capacitor. If Vs is measured in terms of the Josephson volt and the capacitor is measured in SI units then the fine-structure constant is the quantity determined. Recent developments involving single electron tunneling, SET, have shown bow to count the electrons as well as how to make an electrometer with sufficient sensitivity to measure the charge. PMID:28053434

Theoretical rate constants of super-exchange hole transfer and thermally induced hopping in DNA.

PubMed

Shimazaki, Tomomi; Asai, Yoshihiro; Yamashita, Koichi

2005-01-27

Recently, the electronic properties of DNA have been extensively studied, because its conductivity is important not only to the study of fundamental biological problems, but also in the development of molecular-sized electronics and biosensors. We have studied theoretically the reorganization energies, the activation energies, the electronic coupling matrix elements, and the rate constants of hole transfer in B-form double-helix DNA in water. To accommodate the effects of DNA nuclear motions, a subset of reaction coordinates for hole transfer was extracted from classical molecular dynamics (MD) trajectories of DNA in water and then used for ab initio quantum chemical calculations of electron coupling constants based on the generalized Mulliken-Hush model. A molecular mechanics (MM) method was used to determine the nuclear Franck-Condon factor. The rate constants for two types of mechanisms of hole transfer-the thermally induced hopping (TIH) and the super-exchange mechanisms-were determined based on Marcus theory. We found that the calculated matrix elements are strongly dependent on the conformations of the nucleobase pairs of hole-transferable DNA and extend over a wide range of values for the "rise" base-step parameter but cluster around a particular value for the "twist" parameter. The calculated activation energies are in good agreement with experimental results. Whereas the rate constant for the TIH mechanism is not dependent on the number of A-T nucleobase pairs that act as a bridge, the rate constant for the super-exchange process rapidly decreases when the length of the bridge increases. These characteristic trends in the calculated rate constants effectively reproduce those in the experimental data of Giese et al. [Nature 2001, 412, 318]. The calculated rate constants were also compared with the experimental results of Lewis et al. [Nature 2000, 406, 51].

Alternative analytical forms to model diatomic systems based on the deformed exponential function.

PubMed

da Fonsêca, José Erinaldo; de Oliveira, Heibbe Cristhian B; da Cunha, Wiliam Ferreira; Gargano, Ricardo

2014-07-01

Using a deformed exponential function and the molecular-orbital theory for the simplest molecular ion, two new analytical functions are proposed to represent the potential energy of ground-state diatomic systems. The quality of these new forms was tested by fitting the ab initio electronic energies of the system LiH, LiNa, NaH, RbH, KH, H2, Li2, K2, H 2 (+) , BeH(+) and Li 2 (+) . From these fits, it was verified that these new proposals are able to adequately describe homonuclear, heteronuclear and cationic diatomic systems with good accuracy. Vibrational spectroscopic constant results obtained from these two proposals are in good agreement with experimental data.

When Density Functional Approximations Meet Iron Oxides.

PubMed

Meng, Yu; Liu, Xing-Wu; Huo, Chun-Fang; Guo, Wen-Ping; Cao, Dong-Bo; Peng, Qing; Dearden, Albert; Gonze, Xavier; Yang, Yong; Wang, Jianguo; Jiao, Haijun; Li, Yongwang; Wen, Xiao-Dong

2016-10-11

Three density functional approximations (DFAs), PBE, PBE+U, and Heyd-Scuseria-Ernzerhof screened hybrid functional (HSE), were employed to investigate the geometric, electronic, magnetic, and thermodynamic properties of four iron oxides, namely, α-FeOOH, α-Fe 2 O 3 , Fe 3 O 4 , and FeO. Comparing our calculated results with available experimental data, we found that HSE (a = 0.15) (containing 15% "screened" Hartree-Fock exchange) can provide reliable values of lattice constants, Fe magnetic moments, band gaps, and formation energies of all four iron oxides, while standard HSE (a = 0.25) seriously overestimates the band gaps and formation energies. For PBE+U, a suitable U value can give quite good results for the electronic properties of each iron oxide, but it is challenging to accurately get other properties of the four iron oxides using the same U value. Subsequently, we calculated the Gibbs free energies of transformation reactions among iron oxides using the HSE (a = 0.15) functional and plotted the equilibrium phase diagrams of the iron oxide system under various conditions, which provide reliable theoretical insight into the phase transformations of iron oxides.

Systematic study of the effect of HSE functional internal parameters on the electronic structure and band gap of a representative set of metal oxides.

PubMed

Viñes, Francesc; Lamiel-García, Oriol; Chul Ko, Kyoung; Yong Lee, Jin; Illas, Francesc

2017-04-30

The effect of the amount of Hartree-Fock mixing parameter (α) and of the screening parameter (w) defining the range separated HSE type hybrid functional is systematically studied for a series of seven metal oxides: TiO 2 , ZrO 2 , CuO 2 , ZnO, MgO, SnO 2 , and SrTiO 3 . First, reliable band gap values were determined by comparing the optimal α reproducing the experiment with the inverse of the experimental dielectric constant. Then, the effect of the w in the HSE functional on the calculated band gap was explored in detail. Results evidence the existence of a virtually infinite number of combinations of the two parameters which are able to reproduce the experimental band gap, without a unique pair able to describe the full studied set of materials. Nevertheless, the results point out the possibility of describing the electronic structure of these materials through a functional including a screened HF exchange and an appropriate correlation contribution. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Pressure-Dependent Electronic and Transport Properties of Bulk Platinum Oxide by Density Functional Theory

NASA Astrophysics Data System (ADS)

Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh; Nekrasov, Kirill A.; Kichigina, Natalia V.

2018-02-01

The structural, electronic, and vibrational properties of bulk platinum oxide (PtO) at compressive pressures in the interval from 0 GPa to 35 GPa are investigated using the density functional theory. The calculated electronic band structure of PtO shows poor metallicity at very low density of states on the Fermi level. However, the hybrid pseudopotential calculation yielded 0.78 eV and 1.30 eV direct band and indirect gap, respectively. Importantly, our results predict that PtO has a direct band gap within the framework of HSE06, and it prefers equally zero magnetic order at different pressures. In the Raman spectra, peaks are slightly shifted towards higher frequency with the decrease in pressure. We have also calculated the thermoelectric properties, namely the electronic thermal conductivity and electrical conductivity, with respect to temperature and thermodynamic properties such as entropy, specific heat at constant volume, enthalpy and Gibbs free energy with respect to pressure. The result shows that PtO is a promising candidate for use as a catalyst, in sensors, as a photo-cathode in water electrolysis, for thermal decomposition of inorganic salt and fuel cells.

New determination of the fine structure constant from the electron value and QED.

PubMed

Gabrielse, G; Hanneke, D; Kinoshita, T; Nio, M; Odom, B

2006-07-21

Quantum electrodynamics (QED) predicts a relationship between the dimensionless magnetic moment of the electron (g) and the fine structure constant (alpha). A new measurement of g using a one-electron quantum cyclotron, together with a QED calculation involving 891 eighth-order Feynman diagrams, determine alpha(-1)=137.035 999 710 (96) [0.70 ppb]. The uncertainties are 10 times smaller than those of nearest rival methods that include atom-recoil measurements. Comparisons of measured and calculated g test QED most stringently, and set a limit on internal electron structure.

Alloy and heterostructure architectures as promising tools for controlling electronic properties of semiconductor quantum dots

NASA Astrophysics Data System (ADS)

Vaxenburg, Roman; Lifshitz, Efrat

2012-02-01

Tunability of energy levels and wavefunctions of carriers in colloidal quantum dots (CQDs) has a marked effect on numerous physical aspects, such as Coulomb interactions and charge separation, which in turn has a direct impact on the functioning of CQD-based opto-electronic devices. The electronic properties of CQDs are conventionally controlled by variation of their size. Here we demonstrate a theoretical approach to engineer the electronic properties of IV-VI CQDs by introducing an alloy composition in core and core/shell heterostructures, having the general chemical formula PbSexS1-x/PbSeyS1-y (0 ≤ x ≤ 1, 0 ≤ y ≤ 1), while maintaining a constant size. The theoretical model considered an effective mass anisotropy and smooth potential step at the core/shell interface. The model revealed the influence induced by variation of chemical composition and core-to-shell division on the band-gap energy, remote states’ density, internal charge separation, electron-hole Coulomb interaction, and optical transition oscillator strength.

Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy.

PubMed

Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling

2017-08-22

Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

Simulation-Based Approach to Determining Electron Transfer Rates Using Square-Wave Voltammetry.

PubMed

Dauphin-Ducharme, Philippe; Arroyo-Currás, Netzahualcóyotl; Kurnik, Martin; Ortega, Gabriel; Li, Hui; Plaxco, Kevin W

2017-05-09

The efficiency with which square-wave voltammetry differentiates faradic and charging currents makes it a particularly sensitive electroanalytical approach, as evidenced by its ability to measure nanomolar or even picomolar concentrations of electroactive analytes. Because of the relative complexity of the potential sweep it uses, however, the extraction of detailed kinetic and mechanistic information from square-wave data remains challenging. In response, we demonstrate here a numerical approach by which square-wave data can be used to determine electron transfer rates. Specifically, we have developed a numerical approach in which we model the height and the shape of voltammograms collected over a range of square-wave frequencies and amplitudes to simulated voltammograms as functions of the heterogeneous rate constant and the electron transfer coefficient. As validation of the approach, we have used it to determine electron transfer kinetics in both freely diffusing and diffusionless surface-tethered species, obtaining electron transfer kinetics in all cases in good agreement with values derived using non-square-wave methods.

Fluorescence and electron paramagnetic resonance studies of norfloxacin and N-donor mixed-ligand ternary copper(II) complexes: Stability and interaction with SDS micelles

NASA Astrophysics Data System (ADS)

Vignoli Muniz, Gabriel S.; Incio, Jimmy Llontop; Alves, Odivaldo C.; Krambrock, Klaus; Teixeira, Letícia R.; Louro, Sonia R. W.

2018-01-01

The stability of ternary copper(II) complexes of a heterocyclic ligand, L (L being 2,2‧-bipyridine (bipy) or 1,10-phenanthroline (phen)) and the fluorescent antibacterial agent norfloxacin (NFX) as the second ligand was studied at pH 7.4 and different ionic strengths. Fluorescence quenching upon titration of NFX with the binary complexes allowed to obtain stability constants for NFX binding, Kb, as a function of ionic strength. The Kb values vary by more than two orders of magnitude when buffer concentration varies from 0.5 to 100 mM. It was observed that previously synthesized ternary complexes dissociate in buffer according with the obtained stability constants. This shows that equimolar solutions of NFX and binary complexes are equivalent to solutions of synthesized ternary complexes. The interaction of the ternary copper complexes with anionic SDS (sodium dodecyl sulfate) micelles was studied by fluorescence and electron paramagnetic resonance (EPR). Titration of NFX-loaded SDS micelles with the complexes Cu:L allowed to determine the stability constants inside the micelles. Fluorescence quenching demonstrated that SDS micelles increase the stability constants by factors around 50. EPR spectra gave details of the copper(II) local environment, and demonstrated that the structure of the ternary complexes inside SDS micelles is different from that in buffer. Mononuclear ternary complexes formed inside the micelles, while in buffer most ternary complexes are binuclear. The results show that anionic membrane interfaces increase formation of copper fluoroquinolone complexes, which can influence bioavailability, membrane diffusion, and mechanism of action of the antibiotics.

Rates and equilibrium constants of the ligand-induced conformational transition of an HCN ion channel protein domain determined by DEER spectroscopy.

PubMed

Collauto, Alberto; DeBerg, Hannah A; Kaufmann, Royi; Zagotta, William N; Stoll, Stefan; Goldfarb, Daniella

2017-06-14

Ligand binding can induce significant conformational changes in proteins. The mechanism of this process couples equilibria associated with the ligand binding event and the conformational change. Here we show that by combining the application of W-band double electron-electron resonance (DEER) spectroscopy with microfluidic rapid freeze quench (μRFQ) it is possible to resolve these processes and obtain both equilibrium constants and reaction rates. We studied the conformational transition of the nitroxide labeled, isolated carboxy-terminal cyclic-nucleotide binding domain (CNBD) of the HCN2 ion channel upon binding of the ligand 3',5'-cyclic adenosine monophosphate (cAMP). Using model-based global analysis, the time-resolved data of the μRFQ DEER experiments directly provide fractional populations of the open and closed conformations as a function of time. We modeled the ligand-induced conformational change in the protein using a four-state model: apo/open (AO), apo/closed (AC), bound/open (BO), bound/closed (BC). These species interconvert according to AC + L ⇌ AO + L ⇌ BO ⇌ BC. By analyzing the concentration dependence of the relative contributions of the closed and open conformations at equilibrium, we estimated the equilibrium constants for the two conformational equilibria and the open-state ligand dissociation constant. Analysis of the time-resolved μRFQ DEER data gave estimates for the intrinsic rates of ligand binding and unbinding as well as the rates of the conformational change. This demonstrates that DEER can quantitatively resolve both the thermodynamics and the kinetics of ligand binding and the associated conformational change.

Ab-initio Density Functional Theory (DFT) Studies of Electronic, Transport, and Bulk Properties of Sodium Oxide (Na2O)

NASA Astrophysics Data System (ADS)

Polin, Daniel; Ziegler, Joshua; Malozovsky, Yuriy; Bagayoko, Diola

We present the findings of ab-initio calculations of electronic, transport, and structural properties of cubic sodium oxide (Na2O). These results were obtained using density functional theory (DFT), specifically a local density approximation (LDA) potential, and the linear combination of Gaussian orbitals (LCGO). Our implementation of LCGO followed the Bagayoko, Zhao, and Williams method as enhanced by the work of Ekuma and Franklin (BZW-EF). We describe the electronic band structure of Na2O with a direct band gap of 2.22 eV. Our results include predicted values for the electronic band structure and associated energy eigenvalues, the total and partial density of states (DOS and pDOS), the equilibrium lattice constant of Na2O, and the bulk modulus. We have also calculated the electron and holes effective masses in the Γ to L, Γ to X, and Γ to K directions. Acknowledgments: This work was funded in part by the National Science Foundation (NSF) and the Louisiana Board of Regents, through LASiGMA [Award Nos. EPS- 1003897, NSF (2010-15)-RII-SUBR] and NSF HRD-1002541, the US Department of Energy - National, Nuclear Security Administration (NNSA) (Award No. DE- NA0002630), LaSPACE, and LONI-SUBR.

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

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

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

The effect of cross linking density on the mechanical properties and structure of the epoxy polymers: molecular dynamics simulation.

PubMed

Shokuhfar, Ali; Arab, Behrouz

2013-09-01

Recently, great attention has been focused on using epoxy polymers in different fields such as aerospace, automotive, biotechnology, and electronics, owing to their superior properties. In this study, the classical molecular dynamics (MD) was used to simulate the cross linking of diglycidyl ether of bisphenol-A (DGEBA) with diethylenetriamine (DETA) curing agent, and to study the behavior of resulted epoxy polymer with different conversion rates. The constant-strain (static) approach was then applied to calculate the mechanical properties (Bulk, shear and Young's moduli, elastic stiffness constants, and Poisson's ratio) of the uncured and cross-linked systems. Estimated material properties were found to be in good agreement with experimental observations. Moreover, the dependency of mechanical properties on the cross linking density was investigated and revealed improvements in the mechanical properties with increasing the cross linking density. The radial distribution function (RDF) was also used to study the evolution of local structures of the simulated systems as a function of cross linking density.

Imaginary-frequency polarizability and van der Waals force constants of two-electron atoms, with rigorous bounds

NASA Technical Reports Server (NTRS)

Glover, R. M.; Weinhold, F.

1977-01-01

Variational functionals of Braunn and Rebane (1972) for the imagery-frequency polarizability (IFP) have been generalized by the method of Gramian inequalities to give rigorous upper and lower bounds, valid even when the true (but unknown) unperturbed wavefunction must be represented by a variational approximation. Using these formulas in conjunction with flexible variational trial functions, tight error bounds are computed for the IFP and the associated two- and three-body van der Waals interaction constants of the ground 1(1S) and metastable 2(1,3S) states of He and Li(+). These bounds generally establish the ground-state properties to within a fraction of a per cent and metastable properties to within a few per cent, permitting a comparative assessment of competing theoretical methods at this level of accuracy. Unlike previous 'error bounds' for these properties, the present results have a completely a priori theoretical character, with no empirical input data.

A Combined Density Functional Theory and Spectrophotometry Study of the Bonding Interactions of [NpO 2·M] 4+ Cation–Cation Complexes

DOE PAGES

Freiderich, John W.; Burn, Adam G.; Martin, Leigh R.; ...

2017-04-14

The equilibrium constants for [NpO 2M∙] 4+ (M = Al 3+, In 3+, Sc 3+, Fe 3+) in μ = 10 M nitric acid and [NpO 2∙Ga] 4+ in μ = 10 M hydrochloric acid media have been determined. The trend in the interaction strength follows: Fe 3+ > Sc 3+ In 3+ > Ga 3+ Al 3+. These equilibrium constants are compared to those of previously reported values for NpO 2 + complexes with Cr 3+ and Rh 3+ within the literature. Thermodynamic parameters and bonding modes are discussed, with density functional theory and natural bond orbital analysis indicatingmore » that the NpO 2 + dioxocation acts as a -donor with transition-metal cations and a sigma donor with group 13 cations. The small changes in electron-donating ability is modulated by the overlap with the coordinating metal ion's valence atomic orbitals.« less

Computational study of electronic, optical and thermoelectric properties of X3PbO (X = Ca, Sr, Ba) anti-perovskites

NASA Astrophysics Data System (ADS)

Hassan, M.; Arshad, I.; Mahmood, Q.

2017-11-01

We report the structural, electronic, optical and thermoelectric (TE) properties of X3PbO (X = Ca, Sr, Ba) anti-perovskites as a function of X cations belonging to the group IIA. The computations are done by using the most recently introduced modified Becke-Johnson potential. It has been observed that the cubic lattice constant increases as the cations change from Ca to Ba, consequently, the bulk modulus reduces. The bottom of conduction band shows strong hybridization between Pb-6p, O-2p and X-s states, in contrast, valence band maxima are mainly manufactured by Pb-6p states. The anti-perovskites exhibit narrow direct band gap that show an inverse relation to the static real dielectric constants that verifies Penn’s model. In addition, the X cations induced tuning of the absorption edge in the visible and the ultraviolet energy suggest optical device applications. The computed TE parameters have been found sensitive to the X cations and have been demonstrated to be best suited for the TE devices operating at high temperatures.

First-principles study of the structural, electronic and thermal properties of CaLiF3

NASA Astrophysics Data System (ADS)

Chouit, N.; Amara Korba, S.; Slimani, M.; Meradji, H.; Ghemid, S.; Khenata, R.

2013-09-01

Density functional theory calculations have been performed to study the structural, electronic and optical properties of CaLiF3 cubic fluoroperovskite. Our calculations were carried out by means of the full-potential linearized augmented plane-wave method. The exchange-correlation potential is treated by the local density approximation and the generalized gradient approximation (GGA) (Perdew, Burke and Ernzerhof). Moreover, the alternative form of GGA proposed by Engel and Vosko is also used for band structure calculations. The calculated total energy versus volume allows us to obtain structural properties such as the lattice constant (a0), bulk modulus (B0) and pressure derivative of the bulk modulus (B'0 ). Band structure, density of states and band gap pressure coefficients are also given. Our calculations show that CaLiF3 has an indirect band gap (R-Γ). Following the quasi-harmonic Debye model, in which the phononic effects are considered, the temperature and pressure effects on the lattice constant, bulk modulus, thermal expansion coefficient, Debye temperature and heat capacities are calculated.

Electronic and optical properties of the LiCdX (X = N, P, As and Sb) filled-tetrahedral compounds with the Tran–Blaha modified Becke–Johnson density functional

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

Bouhemadou, A., E-mail: a_bouhemadou@yahoo.fr; Bin-Omran, S.; Department of Physics, Faculty of Science & Humanitarian Studies, Salman Bin Abdalaziz University, Alkharj 11942

Highlights: • Electronic and optical properties of the LiCdX compounds have been predicted. • Tran–Blaha-modified Becke–Johnson functional significantly improves the band gap. • We predict a direct band gap in all of the considered LiCdX compounds. • Origin of the peaks in the optical spectra is determined. - Abstract: The structural, electronic and optical properties of the LiCdN, LiCdP, LiCdAs and LiCdSb filled-tetrahedral compounds have been explored from first-principles. The calculated structural parameters are consistent with the available experimental results. Since DFT with the common LDA and GGA underestimates the band gap, we use a new developed functional able tomore » accurately describe the electronic structure of semiconductors, namely the Tran–Blaha-modified Becke–Johnson potential. The four investigated compounds demonstrate semiconducting behavior with direct band gap ranging from about 0.32 to 1.65 eV. The charge-carrier effective masses are evaluated at the topmost valence band and at the bottommost conduction band. The evolution of the value and nature of the energy band gap under pressure effect is also investigated. The frequency-dependent complex dielectric function and some macroscopic optical constants are estimated. The microscopic origins of the structures in the optical spectra are determined in terms of the calculated energy band structures.« less

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2012 CFR

2012-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

40 CFR 91.421 - Dilute gaseous exhaust sampling and analytical system description.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Pump—Constant Volume Sampler (PDP-CVS) system with a heat exchanger, or a Critical Flow Venturi—Constant Volume Sampler (CFV-CVS) system with CVS sample probes and/or a heat exchanger or electronic flow... sampling point. (ii) For the CFV-CVS, either a heat exchanger or electronic flow compensation is required...

Symmetrical windowing for quantum states in quasi-classical trajectory simulations: Application to electron transfer

NASA Astrophysics Data System (ADS)

Cotton, Stephen J.; Igumenshchev, Kirill; Miller, William H.

2014-08-01

It has recently been shown [S. J. Cotton and W. H. Miller, J. Chem. Phys. 139, 234112 (2013)] that a symmetrical windowing quasi-classical (SQC) approach [S. J. Cotton and W. H. Miller, J. Phys. Chem. A 117, 7190 (2013)] applied to the Meyer-Miller model [H.-D. Meyer and W. H. Miller, J. Chem. Phys. 70, 3214 (1979)] for the electronic degrees of freedom in electronically non-adiabatic dynamics is capable of quantitatively reproducing quantum mechanical results for a variety of test applications, including cases where "quantum" coherence effects are significant. Here we apply this same SQC methodology, within a flux-side correlation function framework, to calculate thermal rate constants corresponding to several proposed models of electron transfer processes [P. Huo, T. F. Miller III, and D. F. Coker, J. Chem. Phys. 139, 151103 (2013); A. R. Menzeleev, N. Ananth, and T. F. Miller III, J. Chem. Phys. 135, 074106 (2011)]. Good quantitative agreement with Marcus Theory is obtained over several orders of magnitude variation in non-adiabatic coupling. Moreover, the "inverted regime" in thermal rate constants (with increasing bias) known from Marcus Theory is also reproduced with good accuracy by this very simple classical approach. The SQC treatment is also applied to a recent model of photoinduced proton coupled electron transfer [C. Venkataraman, A. V. Soudackov, and S. Hammes-Schiffer, J. Chem. Phys. 131, 154502 (2009)] and population decay of the photoexcited donor state is found to be in reasonable agreement with results calculated via reduced density matrix theory.

Connecting Fundamental Constants

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

Di Mario, D.

2008-05-29

A model for a black hole electron is built from three basic constants only: h, c and G. The result is a description of the electron with its mass and charge. The nature of this black hole seems to fit the properties of the Planck particle and new relationships among basic constants are possible. The time dilation factor in a black hole associated with a variable gravitational field would appear to us as a charge; on the other hand the Planck time is acting as a time gap drastically limiting what we are able to measure and its dimension willmore » appear in some quantities. This is why the Planck time is numerically very close to the gravitational/electric force ratio in an electron: its difference, disregarding a {pi}{radical}(2) factor, is only 0.2%. This is not a coincidence, it is always the same particle and the small difference is between a rotating and a non-rotating particle. The determination of its rotational speed yields accurate numbers for many quantities, including the fine structure constant and the electron magnetic moment.« less

The electronic structure, elastic and optical properties of Cu2ZnGe(SexS1 - x)4 alloys: density functional calculations

NASA Astrophysics Data System (ADS)

Shen, Kesheng; Jia, Guangrui; Zhang, Xianzhou; Jiao, Zhaoyong

2016-10-01

The electronic structure, elastic and optical properties of Cu2ZnGe(SexS1 - x)4 alloys are systematically analysed using first-principles calculations. The lattice parameters agree well with the theoretical and experimental values which are searched as complete as possible indicating our calculations are reliable. The elastic properties are investigated first and are compared with the similar compounds CZTS and CZTSe due to the unavailable experimental data currently. The variation of the optical properties caused by the increase of Se/S ratio is discussed. The static optical constants are calculated and the corrected values are also predicted according to the available experimental data.

One-range addition theorems for derivatives of Slater-type orbitals.

PubMed

Guseinov, Israfil

2004-06-01

Using addition theorems for STOs introduced by the author with the help of complete orthonormal sets of psi(alpha)-ETOs (Guseinov II (2003) J Mol Model 9:190-194), where alpha=1, 0, -1, -2, ..., a large number of one-range addition theorems for first and second derivatives of STOs are established. These addition theorems are especially useful for computation of multicenter-multielectron integrals over STOs that arise in the Hartree-Fock-Roothaan approximation and also in the Hylleraas function method, which play a significant role for the study of electronic structure and electron-nuclei interaction properties of atoms, molecules, and solids. The relationships obtained are valid for arbitrary quantum numbers, screening constants and location of STOs.

Effect of tellurium concentration on the structural, electronic and mechanical properties of beryllium sulphide: A DFT approach

NASA Astrophysics Data System (ADS)

Iyorzor, B. E.; Babalola, M. I.; Adetunji, B. I.; Bakare, F. O.

2018-05-01

The structural, electronic and mechanical properties of Be{S}1-xT{e}x are studied within the concentration range of 0≤slant x≤slant 1 using first-principles plane–wave Pseudopotential density functional theory (DFT) approach. We have used generalized gradient approximation (GGA) to treat the exchange-correlation potentials. The elastic constants, bulk, shear and Young’s moduli, Poisson’s ratio, and Zener’s anisotropic factors are calculated. The results were found to be in agreement with other available theoretical and experimental values. It was also observed that the existence and increase of Tellurium concentration decreases the hardness of the alloy.

Intraband Raman laser gain in a boron nitride coupled quantum well

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

Moorthy, N. Narayana; Peter, A. John, E-mail: a.john.peter@gmail.com

2016-05-23

On-centre impurity related electronic and optical properties are studied in a Boron nitride coupled quantum well. Confined energies for the intraband transition are investigated by studying differential cross section of electron Raman scattering taking into consideration of spatial confinement in a B{sub 0.3}Ga{sub 0.7}N/BN coupled quantum well. Raman gain as a function of incident optical pump intensity is computed for constant well width. The enhancement of Raman gain is observed with the application of pump power. The results can be applied for the potential applications for fabricating some optical devices such as optical switches, infrared photo-detectors and electro-optical modulator.

Effect of Pressure on Some Optical Properties of GaxIn1-xP Semiconductors

NASA Astrophysics Data System (ADS)

Vyas, P.; Gajjar, P.; Jani, A.

2013-06-01

A theoretical procedure is presented for the study of optical properties of ternary alloy GaxIn1-xP. The calculations are based on the pseudopotential formalism in which local potential coupled with the virtual crystal approximation (VCA) is applied to evaluate the effect of pressure on the optical properties like refractive index, electronic polarizability, plasmon energy, dielectric constant and equation of state for gallium concentration x = 0, 0.25, 0.50, 0.75 and 1 of the ternary alloy GaxIn1-xP. To incorporate the screening effect, local field correction functions due to Hartree, Taylor, Ichimaru et al. and Nagy are employed. The refractive index, electronic polarizability and dielectric constant computed for the parent binary compounds GaP and InP are found to be satisfactorily agreeing with the experimental report. It is seen that the refractive index of GaxIn1-xP decreases nonlinearly with the increase in pressure. The results obtained using Hartree's screening functions are not very close to the experimental data as it does not include any exchange and correlation effects. Overall good agreement with the experimental and other theoretical findings confirms the application. The author P. S. Vyas is thankful to UGC, New Delhi, India for providing financial support under minor research project No. F.: 47-651/08(WRO).

Defect of the well-known (classical) expression for the ionization rate in gas-discharge plasma and its modification

NASA Astrophysics Data System (ADS)

Litvinov, I. I.

2015-11-01

A critical analysis is given of the well-known expression for the electron-impact ionization rate constant α i of neutral atoms and ions, derived by linearization of the ionization cross section σ i (ɛ) as a function of the electron energy near the threshold I and containing the characteristic factor ( I + 2 kT). Using the classical Thomson expression for the ionization cross section, it is shown that in addition to the linear slope of σ i (ɛ), it is also necessary to take into account the large negative curvature of this function near the threshold. In this case, the second term in parentheses changes its sign, which means that the commonly used expression for α i (˜4 kT/I) already at moderate values of the temperature ( kT/I ˜ 0.1). The source of this error lies in a mathematical mistake in the original approach and is related to the incorrect choice of the sequential orders of terms small in the parameter kT/I. On the basis of a large amount of experimental data and considerations similar to the Gryzinski theory, a universal two-parameter modification of the Thomson formula (as well as the Bethe—Born formula) is proposed and a new simple expression for the ionization rate constant for arbitrary values of kT/I is derived.

Preparation, electronic structure, and chemical bonding of lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3 solid solution

NASA Astrophysics Data System (ADS)

Sasikumar, S.; Saravanan, R.; Saravanakumar, S.; Robert, M. Charles

2018-01-01

Polycrystalline lead-free (1 - x)(K0.5Bi0.5)TiO3- xBaTiO3, ((1 - x)KBT- xBT) ( x = 0.00, 0.08, 0.12) ceramics were synthesized via solid-state reaction method. The powder X-ray diffraction (PXRD) and structural refinement results confirm that a single-phase tetragonal structure with space group P4mm. Charge density distribution inside the unit cell of (1 - x)KBT- xBT was investigated by the maximum entropy method. Charge density analysis reveals the reduction in ionic nature along K/Bi-O bond and enhancement of covalent nature along Ti-O bond with the addition of BaTiO3. The charge density distribution studies done using maximum entropy method for (1 - x)KBT- xBT have not been done so far. The surface morphology study was done using scanning electron microscopy (SEM). Energy dispersive X-rays spectra (EDS) were used to investigate the elemental compositions present in the system. The dielectric constant and loss tangent were studied as a function of frequency. The dielectric constant and loss were decreased with increase of frequency. Room temperature dielectric constant ( ɛ) and loss (tan δ) were measured for x = 0.00 about 511 and 0.51, respectively, at a frequency of 10 kHz.

Site- and species-specific hydrolysis rates of heroin.

PubMed

Szöcs, Levente; Orgován, Gábor; Tóth, Gergő; Kraszni, Márta; Gergó, Lajos; Hosztafi, Sándor; Noszál, Béla

2016-06-30

The hydroxide-catalyzed non-enzymatic, simultaneous and consecutive hydrolyses of diacetylmorphine (DAM, heroin) are quantified in terms of 10 site- and species-specific rate constants in connection with also 10 site- and species-specific acid-base equilibrium constants, comprising all the 12 coexisting species in solution. This characterization involves the major and minor decomposition pathways via 6-acetylmorphine and 3-acetylmorphine, respectively, and morphine, the final product. Hydrolysis has been found to be 18-120 times faster at site 3 than at site 6, depending on the status of the amino group and the rest of the molecule. Nitrogen protonation accelerates the hydrolysis 5-6 times at site 3 and slightly less at site 6. Hydrolysis rate constants are interpreted in terms of intramolecular inductive effects and the concomitant local electron densities. Hydrolysis fraction, a new physico-chemical parameter is introduced and determined to quantify the contribution of the individual microspecies to the overall hydrolysis. Hydrolysis fractions are depicted as a function of pH. Copyright © 2016 Elsevier B.V. All rights reserved.

A simplified controller and detailed dynamics of constant off-time peak current control

NASA Astrophysics Data System (ADS)

Van den Bossche, Alex; Dimitrova, Ekaterina; Valchev, Vencislav; Feradov, Firgan

2017-09-01

A fast and reliable current control is often the base of power electronic converters. The traditional constant frequency peak control is unstable above 50 % duty ratio. In contrast, the constant off-time peak current control (COTCC) is unconditionally stable and fast, so it is worth analyzing it. Another feature of the COTCC is that one can combine a current control together with a current protection. The time dynamics show a zero-transient response, even when the inductor changes in a wide range. It can also be modeled as a special transfer function for all frequencies. The article shows also that it can be implemented in a simple analog circuit using a wide temperature range IC, such as the LM2903, which is compatible with PV conversion and automotive temperature range. Experiments are done using a 3 kW step-up converter. A drawback is still that the principle does not easily fit in usual digital controllers up to now.

Hyperfine field, electric field gradient, quadrupole coupling constant and magnetic properties of challenging actinide digallide

NASA Astrophysics Data System (ADS)

Khan, Sajid; Yazdani-Kachoei, M.; Jalali-Asadabadi, S.; Ahmad, Iftikhar

2017-12-01

In this paper, we explore the structural and magnetic properties as well as electric field gradient (EFG), hyperfine field (HFF) and quadrupole coupling constant in actinide digallide AcGa2 (Ac = U, Np, Pu) using LDA, GGA, LDA+U, GGA+U and hybrid functional with Wu-Cohen Generalized Gradient approximation HF-WC. Relativistic effects of the electrons are considered by including spin-orbit coupling. The comparison of the calculated structural parameters and magnetic properties with the available experimental results confirms the consistency and hence effectiveness of our theoretical tools. The calculated magnetic moments demonstrate that UGa2 and NpGa2 are ferromagnetic while PuGa2 is antiferromagnetic in nature. The EFG of AcGa2 is reported for the first time. The HFF, EFG and quadrupole coupling constant in AcGa2 (Ac = U, Np, Pu) are mainly originated from f-f and p-p contributions of Ac atom and p-p contribution of Ga atom.

Interpretation of increased energetic particle flux measurements by SEPT aboard the STEREO spacecraft and contamination

NASA Astrophysics Data System (ADS)

Wraase, S.; Heber, B.; Böttcher, S.; Bucik, R.; Dresing, N.; Gómez-Herrero, R.; Klassen, A.; Müller-Mellin, R.

2018-04-01

Context. Interplanetary (IP) shocks are known to be accelerators of energetic charged particles observed in-situ in the heliosphere. However, the acceleration of near-relativistic electrons by shocks in the interplanetary medium is often questioned. On 9 August 2011 a corotating interaction region (CIR) passed STEREO B (STB), which resulted in a flux increase in the electron and ion channels of the Solar Electron and Proton Telescope (SEPT). Because electron measurements in the few keV to several 100 keV range rely on the so-called magnet foil technique, which is utilized by SEPT, ions can contribute to the electron channels. Aim. We aim to investigate whether the flux increase in the electron channels of SEPT during the CIR event on 9 August 2011 is caused by ion contamination only. Methods: We compute the SEPT response functions for protons and helium utilizing an updated GEANT4 model of SEPT. The CIR energetic particle ion spectra for protons and helium are assumed to follow a Band function in energy per nucleon with a constant helium to proton ratio. Results: Our analysis leads to a helium to proton ratio of 16.9% and a proton flux following a Band function with the parameters I0 = 1.24 × 104 (cm2 s sr MeV nuc-1)-1, Ec = 79 keV nuc-1, and spectral indices of γ1 = -0.94 and γ2 = -3.80, which are in good agreement with measurements by the Suprathermal Ion Telescope (SIT) aboard STB. Conclusions: Since our results explain the SEPT measurements, we conclude that no significant amount of electrons were accelerated between 55 and 425 keV by the CIR.

Observation of autoionization in O 2 by an electron-electron coincidence method

NASA Astrophysics Data System (ADS)

Doering, J. P.; Yang, J.; Cooper, J. W.

1995-01-01

A strong transition to an autoionizing stata has been observed in O 2 at 16.83 ± 0.11 eV by means of a new electron-electron conincidence method. The method uses the fact that electrons arising from autoionizing states appear at a constant energy loss corresponding to the excitation energy of the autoionizing state rather than at a constant ionization potential as do electrons produced by direct ionization. Comparison of the present data with previous photoionization studies suggests that the autoionizing O 2 state is the same state deduced to be responsible for abnormal vibrational intensities in the O 2+X 2Πg ground state when 16.85 eV Ne(I) photons are used. These electron-electron coincidence experiments provide a direct new method for the study of autoionization produced by electron impact.

Potential energy curves of the Na2+ molecular ion from all-electron ab initio relativistic calculations

NASA Astrophysics Data System (ADS)

Bewicz, Anna; Musiał, Monika; Kucharski, Stanisław A.

2017-11-01

The equation-of-motion coupled-cluster method for electron affinity calculations has been used to study potential energy curves (PECs) for the Na+2 molecular ion. Although the studied molecule represents the open shell system the applied approach employs the closed shell Na+ 22 ion as the reference. In addition the Na+ 22 system dissociates into the closed shell fragments; hence, the restricted Hartree-Fock scheme can be used within the whole range of interatomic distances, from 2 to 45 Å. We used large basis set engaging 268 basis functions with all 21 electrons correlated. The relativistic effects are included via second-order Douglas-Kroll method. The computed PECs, spectroscopic molecular constants and vibrational energy levels agree well with experimental values if the latter are available or with other theoretical data.

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.

Self-interaction-corrected local-spin-density calculations for rare earth materials

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

Svane, A.; Temmerman, W.M.; Szotek, Z.

2000-04-20

The ab initio self-interaction-corrected (SIC) local-spin-density (LSD) approximation is discussed with emphasis on the ability to describe localized f-electron states in rare earth solids. Two methods for minimizing the SIC-LSD total energy functional are discussed, one using a unified Hamiltonian for all electron states, thus having the advantages of Bloch's theorem, the other one employing an iterative scheme in real space. Results for cerium and cerium compounds as well as other rare earths are presented. For the cerium compounds the onset of f-electron delocalization can be accurately described, including the intricate isostructural phase transitions in elemental cerium and CeP. Inmore » Pr and Sm the equilibrium lattice constant and zero temperature equation of state is greatly improved in comparison with the LSD results.« less

Diazonium-functionalized horseradish peroxidase immobilized via addressable electrodeposition: direct electron transfer and electrochemical detection.

PubMed

Polsky, Ronen; Harper, Jason C; Dirk, Shawn M; Arango, Dulce C; Wheeler, David R; Brozik, Susan M

2007-01-16

A simple one-step procedure is introduced for the preparation of diazonium-enzyme adducts. The direct electrically addressable deposition of diazonium-modified enzymes is examined for electrochemical sensor applications. The deposition of diazonium-horseradish peroxidase leads to the direct electron transfer between the enzyme and electrode exhibiting a heterogeneous rate constant, ks, of 10.3 +/- 0.7 s-1 and a DeltaEp of 8 mV (v = 150 mV/s). The large ks and low DeltaEp are attributed to the intimate contact between enzyme and electrode attached by one to three phenyl molecules. Such an electrode shows high nonmediated catalytic activity toward H2O2 reduction. Future generations of arrayed electrochemical sensors and studies of direct electron transfer of enzymes can benefit from protein electrodes prepared by this method.

Analysis of Blockade in Charge Transport Across Polymeric Heterojunctions as a Function of Thermal Annealing: A Different Perspective

NASA Astrophysics Data System (ADS)

Rathi, Sonika; Chauhan, Gayatri; Gupta, Saral K.; Srivastava, Ritu; Singh, Amarjeet

2017-02-01

A blend of poly(3-hexylthiophene-2,5diyl) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is popularly used as an active medium in polymeric solar devices. According to the most recent understanding, the blend is a three-phase system contrary to its earlier understanding of two-phase bicontinuous network. We have synthesized a P3HT-PCBM based layered heterostructure system by spin coating and thermal vacuum evaporations. Current density ( J) was measured as a function of applied electric field ( E) across the system bound between two metal electrodes. J- E relations were analyzed into the backdrop of space charge limited current model and Schottky model. The later was used to predict dc-dielectric constants from the linear slopes of ln ( J) versus E 1/2. The curves were not monotonously linear, but observe a knee-bend separating into two linear segments for each curve. Thermal annealing from 40°C to 80°C was used as an activation tool for driving changes in the internal morphology via inter-diffusion of polymers and current measurements were performed at room temperature after each annealing. At the last stage of annealing the two linear slopes were highly distinct. The presence of sharp knee-bend results in approximately 20 times jump in dielectric constant as a function of electric field. Such high jumps in dielectric constant illustrate the potential for switching applications and charge storage. The high dielectric constants can be understood in terms of space charge polarization due to isolated domains which hindrance to charge transport. The high dielectric constants were confirmed by another experiment of capacitance measurements of a different set of similar samples. A study of thermal evolution of internal morphology was also carried out using x-ray diffraction and scanning electron microscopy techniques to correlate the morphological changes with the transport properties.

A density-functional study on the electronic and vibrational properties of layered antimony telluride.

PubMed

Stoffel, Ralf P; Deringer, Volker L; Simon, Ronnie E; Hermann, Raphaël P; Dronskowski, Richard

2015-03-04

We present a comprehensive survey of electronic and lattice-dynamical properties of crystalline antimony telluride (Sb2Te3). In a first step, the electronic structure and chemical bonding have been investigated, followed by calculations of the atomic force constants, phonon dispersion relationships and densities of states. Then, (macroscopic) physical properties of Sb2Te3 have been computed, namely, the atomic thermal displacement parameters, the Grüneisen parameter γ, the volume expansion of the lattice, and finally the bulk modulus B. We compare theoretical results from three popular and economic density-functional theory (DFT) approaches: the local density approximation (LDA), the generalized gradient approximation (GGA), and a posteriori dispersion corrections to the latter. Despite its simplicity, the LDA shows excellent performance for all properties investigated-including the Grüneisen parameter, which only the LDA is able to recover with confidence. In the absence of computationally more demanding hybrid DFT methods, the LDA seems to be a good choice for further lattice dynamical studies of Sb2Te3 and related layered telluride materials.

Stable isomers and electronic, vibrational, and optical properties of WS2 nano-clusters: A first-principles study

NASA Astrophysics Data System (ADS)

Hafizi, Roohollah; Hashemifar, S. Javad; Alaei, Mojtaba; Jangrouei, MohammadReza; Akbarzadeh, Hadi

2016-12-01

In this paper, we employ an evolutionary algorithm along with the full-potential density functional theory (DFT) computations to perform a comprehensive search for the stable structures of stoichiometric (WS2)n nano-clusters (n = 1 - 9), within three different exchange-correlation functionals. Our results suggest that n = 5 and 8 are possible candidates for the low temperature magic sizes of WS2 nano-clusters while at temperatures above 500 Kelvin, n = 7 exhibits a comparable relative stability with n = 8. The electronic properties and energy gap of the lowest energy isomers were computed within several schemes, including semilocal Perdew-Burke-Ernzerhof and Becke-Lee-Yang-Parr functionals, hybrid B3LYP functional, many body based DFT+GW approach, ΔSCF method, and time dependent DFT calculations. Vibrational spectra of the lowest lying isomers, computed by the force constant method, are used to address IR spectra and thermal free energy of the clusters. Time dependent density functional calculation in a real time domain is applied to determine the full absorption spectra and optical gap of the lowest energy isomers of the WS2 nano-clusters.

Curvature and frontier orbital energies in density functional theory

NASA Astrophysics Data System (ADS)

Kronik, Leeor; Stein, Tamar; Autschbach, Jochen; Govind, Niranjan; Baer, Roi

2013-03-01

Perdew et al. [Phys. Rev. Lett 49, 1691 (1982)] discovered and proved two different properties of exact Kohn-Sham density functional theory (DFT): (i) The exact total energy versus particle number is a series of linear segments between integer electron points; (ii) Across an integer number of electrons, the exchange-correlation potential may ``jump'' by a constant, known as the derivative discontinuity (DD). Here, we show analytically that in both the original and the generalized Kohn-Sham formulation of DFT, the two are in fact two sides of the same coin. Absence of a derivative discontinuity necessitates deviation from piecewise linearity, and the latter can be used to correct for the former, thereby restoring the physical meaning of the orbital energies. Using selected small molecules, we show that this results in a simple correction scheme for any underlying functional, including semi-local and hybrid functionals as well as Hartree-Fock theory, suggesting a practical correction for the infamous gap problem of DFT. Moreover, we show that optimally-tuned range-separated hybrid functionals can inherently minimize both DD and curvature, thus requiring no correction, and show that this can be used as a sound theoretical basis for novel tuning strategies.

EPR studies of free radicals decay and survival in gamma irradiated aminoglycoside antibiotics: sisomicin, tobramycin and paromomycin.

PubMed

Wilczyński, Sławomir; Pilawa, Barbara; Koprowski, Robert; Wróbel, Zygmunt; Ptaszkiewicz, Marta; Swakoń, Jan; Olko, Paweł

2012-02-14

Radiation sterilization technology is more actively used now that any time because of its many advantages. Gamma radiation has high penetrating power, relatively low chemical reactivity and causes small temperature rise. But on the other hand radiosterilization can lead to radiolytic products appearing, in example free radicals. Free radicals in radiative sterilized sisomicin, tobramycin and paromomycin were studied by electron paramagnetic resonance (EPR) spectroscopy. Dose of gamma irradiation of 25kGy was used. Concentrations and properties of free radicals in irradiated antibiotics were studied. EPR spectra were recorded for samples stored in air and argon. For gamma irradiated antibiotics strong EPR lines were recorded. One- and two-exponential functions were fitted to experimental points during testing and researching of time influence of the antibiotics storage to studied parameters of EPR lines. Our study of free radicals in radiosterilized antibiotics indicates the need for characterization of medicinal substances prior to sterilization process using EPR values. We propose the concentration of free radicals and other spectroscopic parameters as useful factors to select the optimal type of sterilization for the individual drug. The important parameters are i.a. the τ time constants and K constants of exponential functions. Time constants τ give us information about the speed of free radicals concentration decrease in radiated medicinal substances. The constant K(0) shows the free radicals concentration in irradiated medicament after long time of storage. Copyright © 2011 Elsevier B.V. All rights reserved.

Acceleration of Relativistic Electrons: A Comparison of Two Models

NASA Astrophysics Data System (ADS)

Green, J. C.; Kivelson, M. G.

2001-12-01

Observations of relativistic electron fluxes show order of magnitude increases during some geomagnetic storms. Many electron acceleration models have been proposed to explain the flux enhancements but attempts to validate these models have yielded ambiguous results. Here we examine two models of electron acceleration, radial diffusion via enhanced ULF wave activity [Elkington et al.,1999] and acceleration by resonant interaction with whistler waves[Summers,1998; Roth et al.,1999]. Two methods are used to compare observations with features predicted by the models. First, the evolution of phase space density as a function of L during flux enhancement events is evaluated. The phase space density (PSD) is calculated at constant first, second and third adiabatic invariants using data obtained by the CEPPAD-HIST instrument and the MFE instrument onboard the Polar spacecraft. Liouville's theorem states that PSD calculated at constant adiabatic invariants does not change with time unless some mechanism violates one of the invariants. The radial diffusion model predicts that only the flux invariant will be violated during the acceleration process while acceleration by whistler waves violates the first invariant. Therefore, the two models predict a different evolution of the PSD as a function of time and L. Previous examinations of the evolution of PSD have yielded ambiguous results because PSD calculations are highly dependent on the global accuracy of magnetic field models. We examine the PSD versus L profiles for a series of geomagnetic storms and in addition determine how errors in the Tsyganenko 96 field model affect the results by comparing the measured magnetic field to the model magnetic field used in the calculations. Second, the evolution of the relativistic electron pitch angle distributions is evaluated. Previous studies of pitch angle distributions were limited because few spacecraft have the necessary instrumentation and global coverage. The CEPPAD-HIST instrument measures 16 look directions and along with measurements from the MFE experiment allows calculation of complete pitch angle distributions. The evolving orbit of the Polar spacecraft over the 6 years mission has given measurements over a wide range of L and local time. Using data extending over the entire mission we use superposed epoch analysis to examine the evolution of pitch angle distributions during flux enhancement events as a function of L, magnetic local time, and storm phase.

Van der Waals equation of state revisited: importance of the dispersion correction.

PubMed

de Visser, Sam P

2011-04-28

One of the most basic equations of state describing nonideal gases and liquids is the van der Waals equation of state, and as a consequence, it is generally taught in most first year undergraduate chemistry courses. In this work, we show that the constants a and b in the van der Waals equation of state are linearly proportional to the polarizability volume of the molecules in a gas or liquid. Using this information, a new thermodynamic one-parameter equation of state is derived that contains experimentally measurable variables and physics constants only. This is the first equation of state apart from the Ideal Gas Law that contains experimentally measurable variables and physics constants only, and as such, it may be a very useful and practical equation for the description of dilute gases and liquids. The modified van der Waals equation of state describes pV as the sum of repulsive and attractive intermolecular interaction energies that are represented by an exponential repulsion function between the electron clouds of the molecules and a London dispersion component, respectively. The newly derived equation of state is tested against experimental data for several gas and liquid examples, and the agreement is satisfactory. The description of the equation of state as a one-parameter function also has implications on other thermodynamic functions, such as critical parameters, virial coefficients, and isothermal compressibilities. Using our modified van der Waals equation of state, we show that all of these properties are a function of the molecular polarizability volume. Correlations of experimental data confirm the derived proportionalities.

Anatomical background and generalized detectability in tomosynthesis and cone-beam CT.

PubMed

Gang, G J; Tward, D J; Lee, J; Siewerdsen, J H

2010-05-01

Anatomical background presents a major impediment to detectability in 2D radiography as well as 3D tomosynthesis and cone-beam CT (CBCT). This article incorporates theoretical and experimental analysis of anatomical background "noise" in cascaded systems analysis of 2D and 3D imaging performance to yield "generalized" metrics of noise-equivalent quanta (NEQ) and detectability index as a function of the orbital extent of the (circular arc) source-detector orbit. A physical phantom was designed based on principles of fractal self-similarity to exhibit power-law spectral density (kappa/Fbeta) comparable to various anatomical sites (e.g., breast and lung). Background power spectra [S(B)(F)] were computed as a function of source-detector orbital extent, including tomosynthesis (approximately 10 degrees -180 degrees) and CBCT (180 degrees + fan to 360 degrees) under two acquisition schemes: (1) Constant angular separation between projections (variable dose) and (2) constant total number of projections (constant dose). The resulting S(B) was incorporated in the generalized NEQ, and detectability index was computed from 3D cascaded systems analysis for a variety of imaging tasks. The phantom yielded power-law spectra within the expected spatial frequency range, quantifying the dependence of clutter magnitude (kappa) and correlation (beta) with increasing tomosynthesis angle. Incorporation of S(B) in the 3D NEQ provided a useful framework for analyzing the tradeoffs among anatomical, quantum, and electronic noise with dose and orbital extent. Distinct implications are posed for breast and chest tomosynthesis imaging system design-applications varying significantly in kappa and beta, and imaging task and, therefore, in optimal selection of orbital extent, number of projections, and dose. For example, low-frequency tasks (e.g., soft-tissue masses or nodules) tend to benefit from larger orbital extent and more fully 3D tomographic imaging, whereas high-frequency tasks (e.g., microcalcifications) require careful, application-specific selection of orbital extent and number of projections to minimize negative effects of quantum and electronic noise. The complex tradeoffs among anatomical background, quantum noise, and electronic noise in projection imaging, tomosynthesis, and CBCT can be described by generalized cascaded systems analysis, providing a useful framework for system design and optimization.

Continuum and atomistic description of excess electrons in TiO2

NASA Astrophysics Data System (ADS)

Maggio, Emanuele; Martsinovich, Natalia; Troisi, Alessandro

2016-02-01

The modelling of an excess electron in a semiconductor in a prototypical dye sensitised solar cell is carried out using two complementary approaches: atomistic simulation of the TiO2 nanoparticle surface is complemented by a dielectric continuum model of the solvent-semiconductor interface. The two methods are employed to characterise the bound (excitonic) states formed by the interaction of the electron in the semiconductor with a positive charge opposite the interface. Density-functional theory (DFT) calculations show that the excess electron in TiO2 in the presence of a counterion is not fully localised but extends laterally over a large region, larger than system sizes accessible to DFT calculations. The numerical description of the excess electron at the semiconductor-electrolyte interface based on the continuum model shows that the exciton is also delocalised over a large area: the exciton radius can have values from tens to hundreds of Ångströms, depending on the nature of the semiconductor (characterised by the dielectric constant and the electron effective mass in our model).

Effect of spin-orbit and on-site Coulomb interactions on the electronic structure and lattice dynamics of uranium monocarbide

NASA Astrophysics Data System (ADS)

Wdowik, U. D.; Piekarz, P.; Legut, D.; Jagło, G.

2016-08-01

Uranium monocarbide, a potential fuel material for the generation IV reactors, is investigated within density functional theory. Its electronic, magnetic, elastic, and phonon properties are analyzed and discussed in terms of spin-orbit interaction and localized versus itinerant behavior of the 5 f electrons. The localization of the 5 f states is tuned by varying the local Coulomb repulsion interaction parameter. We demonstrate that the theoretical electronic structure, elastic constants, phonon dispersions, and their densities of states can reproduce accurately the results of x-ray photoemission and bremsstrahlung isochromat measurements as well as inelastic neutron scattering experiments only when the 5 f states experience the spin-orbit interaction and simultaneously remain partially localized. The partial localization of the 5 f electrons could be represented by a moderate value of the on-site Coulomb interaction parameter of about 2 eV. The results of the present studies indicate that both strong electron correlations and spin-orbit effects are crucial for realistic theoretical description of the ground-state properties of uranium carbide.

Kinetics of interprotein electron transfer between cytochrome c6 and the soluble CuA domain of cyanobacterial cytochrome c oxidase.

PubMed

Paumann, Martina; Feichtinger, Markus; Bernroitner, Margit; Goldfuhs, Judith; Jakopitsch, Christa; Furtmüller, Paul G; Regelsberger, Günther; Peschek, Günter A; Obinger, Christian

2004-10-08

Cytochrome c6 is a soluble metalloprotein located in the periplasmic space and the thylakoid lumen of many cyanobacteria and is known to carry electrons from cytochrome b6f to photosystem I. The CuA domain of cytochrome c oxidase, the terminal enzyme which catalyzes the four-electron reduction of molecular oxygen in the respiratory chains of mitochondria and many bacteria, also has a periplasmic location. In order to test whether cytochrome c6 could also function as a donor for cytochrome c oxidase, we investigated the kinetics of the electron transfer between recombinant cytochrome c6 (produced in high yield in Escherichia coli by coexpressing the maturation proteins encoded by the ccmA-H gene cluster) and the recombinant soluble CuA domain (i.e., the donor binding and electron entry site) of subunit II of cytochrome c oxidase from Synechocystis PCC 6803. The forward and the reverse electron transfer reactions were studied by the stopped-flow technique and yielded apparent bimolecular rate constants of (3.3 +/- 0.3) x 10(5) M(-1) s(-1) and (3.9 +/- 0.1) x 10(6) M(-1) s(-1), respectively, in 5 mM potassium phosphate buffer, pH 7, containing 20 mM potassium chloride and 25 degrees C. This corresponds to an equilibrium constant Keq of 0.085 in the physiological direction (DeltarG'0 = 6.1 kJ/mol). The reduction of the CuA fragment by cytochrome c6 is almost independent on ionic strength, which is in contrast to the reaction of the CuA domain with horse heart cytochrome c, which decreases with increasing ionic strength. The findings are discussed with respect to the potential role of cytochrome c6 as mobile electron carrier in both cyanobacterial electron transport pathways. Copyright 2004 Federation of European Biochemical Societies

An investigation of accelerating mode and decelerating mode constant-momentum mass spectrometry and their application to a residual gas analyzer

NASA Technical Reports Server (NTRS)

Ng, Y. S.

1977-01-01

A theoretical analysis of constant momentum mass spectrometry was made. A maximum resolving power for the decelerating mode constant momentum mass spectrometer was shown theoretically to exist for a beam of ions of known energy. A vacuum system and an electron beam ionization source was constructed. Supporting electronics for a residual gas analyzer were built. Experimental investigations of various types of accelerating and decelerating impulsive modes of a constant momentum mass spectrometer as applied to a residual gas analyzer were made. The data indicate that the resolving power for the decelerating mode is comparable to that of the accelerating mode.

The Sheath-less Planar Langmuir Probe

NASA Astrophysics Data System (ADS)

Cooke, D. L.

2017-12-01

The Langmuir probe is one of the oldest plasma diagnostics, provided the plasma density and species temperature from analysis of a current-voltage curve as the voltage is swept over a practically chosen range. The analysis depends on a knowledge or theory of the many factors that influence the current-voltage curve including, probe shape, size, nearby perturbations, and the voltage reference. For applications in Low Earth Orbit, the Planar Langmuir Probe, PLP, is an attractive geometry because the ram ion current is very constant over many Volts of a sweep, allowing the ion density and electron temperature to be determined independently with the same instrument, at different points on the sweep. However, when the physical voltage reference is itself small and electrically floating as with a small spacecraft, the spacecraft and probe system become a double probe where the current collection theory depends on the interaction of the spacecraft with the plasma which is generally not as simple as the probe itself. The Sheath-less PLP, SPLP, interlaces on a single ram facing surface, two variably biased probe elements, broken into many small and intertwined segments on a scale smaller than the plasma Debye length. The SPLP is electrically isolated from the rest of the spacecraft. For relative bias potentials of a few volts, the ion current to all segments of each element will be constant, while the electron currents will vary as a function of the element potential and the electron temperature. Because the segments are small, intertwined, and floating, the assembly will always present the same floating potential to the plasma, with minimal growth as a function of voltage, thus sheath-less and still planar. This concept has been modelled with Nascap, and tested with a physical model inserted into a Low Earth Orbit-like chamber plasma. Results will be presented.

Detailed modeling of the statistical uncertainty of Thomson scattering measurements

NASA Astrophysics Data System (ADS)

Morton, L. A.; Parke, E.; Den Hartog, D. J.

2013-11-01

The uncertainty of electron density and temperature fluctuation measurements is determined by statistical uncertainty introduced by multiple noise sources. In order to quantify these uncertainties precisely, a simple but comprehensive model was made of the noise sources in the MST Thomson scattering system and of the resulting variance in the integrated scattered signals. The model agrees well with experimental and simulated results. The signal uncertainties are then used by our existing Bayesian analysis routine to find the most likely electron temperature and density, with confidence intervals. In the model, photonic noise from scattered light and plasma background light is multiplied by the noise enhancement factor (F) of the avalanche photodiode (APD). Electronic noise from the amplifier and digitizer is added. The amplifier response function shapes the signal and induces correlation in the noise. The data analysis routine fits a characteristic pulse to the digitized signals from the amplifier, giving the integrated scattered signals. A finite digitization rate loses information and can cause numerical integration error. We find a formula for the variance of the scattered signals in terms of the background and pulse amplitudes, and three calibration constants. The constants are measured easily under operating conditions, resulting in accurate estimation of the scattered signals' uncertainty. We measure F ≈ 3 for our APDs, in agreement with other measurements for similar APDs. This value is wavelength-independent, simplifying analysis. The correlated noise we observe is reproduced well using a Gaussian response function. Numerical integration error can be made negligible by using an interpolated characteristic pulse, allowing digitization rates as low as the detector bandwidth. The effect of background noise is also determined.

Ultrafast electronic relaxation in superheated bismuth

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2013-01-01

Interaction of moving electrons with vibrating ions in the lattice forms the basis for many physical properties from electrical resistivity and electronic heat capacity to superconductivity. In ultrafast laser interaction with matter the electrons are heated much faster than the electron-ion energy equilibration, leading to a two-temperature state with electron temperature far above that of the lattice. The rate of temperature equilibration is governed by the strength of electron-phonon energy coupling, which is conventionally described by a coupling constant, neglecting the dependence on the electron and lattice temperature. The application of this constant to the observations of fast relaxation rate led to a controversial notion of ‘ultra-fast non-thermal melting’ under extreme electronic excitation. Here we provide theoretical grounds for a strong dependence of the electron-phonon relaxation time on the lattice temperature. We show, by taking proper account of temperature dependence, that the heating and restructuring of the lattice occurs much faster than were predicted on the assumption of a constant, temperature independent energy coupling. We applied the temperature-dependent momentum and energy transfer time to experiments on fs-laser excited bismuth to demonstrate that all the observed ultra-fast transformations of the transient state of bismuth are purely thermal in nature. The developed theory, when applied to ultrafast experiments on bismuth, provides interpretation of the whole variety of transient phase relaxation without the non-thermal melting conjecture.

Adler Function, Bjorken Sum Rule, and the Crewther Relation to Order {alpha}{sub s}{sup 4} in a General Gauge Theory

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

Baikov, P. A.; Chetyrkin, K. G.; Kuehn, J. H.

2010-04-02

We compute, for the first time, the order {alpha}{sub s}{sup 4} contributions to the Bjorken sum rule for polarized electron-nucleon scattering and to the (nonsinglet) Adler function for the case of a generic color gauge group. We confirm at the same order a (generalized) Crewther relation which provides a strong test of the correctness of our previously obtained results: the QCD Adler function and the five-loop {beta} function in quenched QED. In particular, the appearance of an irrational contribution proportional to {zeta}{sub 3} in the latter quantity is confirmed. We obtain the commensurate scale equation relating the effective strong couplingmore » constants as inferred from the Bjorken sum rule and from the Adler function at order {alpha}{sub s}{sup 4}.« less

A Spectral Algorithm for Solving the Relativistic Vlasov-Maxwell Equations

NASA Technical Reports Server (NTRS)

Shebalin, John V.

2001-01-01

A spectral method algorithm is developed for the numerical solution of the full six-dimensional Vlasov-Maxwell system of equations. Here, the focus is on the electron distribution function, with positive ions providing a constant background. The algorithm consists of a Jacobi polynomial-spherical harmonic formulation in velocity space and a trigonometric formulation in position space. A transform procedure is used to evaluate nonlinear terms. The algorithm is suitable for performing moderate resolution simulations on currently available supercomputers for both scientific and engineering applications.

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

Veklenko, B. A., E-mail: veklenkoba@yandex.ru

It is shown theoretically that the electromagnetic background of longitudinal zero oscillations of a temperature-degenerate electron–ion plasma in a thermodynamic equilibrium state resonantly distorts the wave functions of its electrons. This gives rise to a characteristic quantum frequency that nonanalytically depends on Planck’s constant ℏ. Vacuum phenomena in plasma attributed to zero oscillations turn out to be anomalously large. Quantum corrections to the transverse dielectric permittivity of a degenerate electron–ion plasma, which are nonanalytic with respect to ℏ and are attributed to the zero-point oscillations of the plasma, are determined.

Influence of Manufacturing Parameters on Microstructure and Hydrogen Sorption Behavior of Electron Beam Melted Titanium Ti-6Al-4V Alloy

PubMed Central

Pushilina, Natalia; Syrtanov, Maxim; Murashkina, Tatyana; Kudiiarov, Viktor; Lider, Andrey; Koptyug, Andrey

2018-01-01

Influence of manufacturing parameters (beam current from 13 to 17 mA, speed function 98 and 85) on microstructure and hydrogen sorption behavior of electron beam melted (EBM) Ti-6Al-4V parts was investigated. Optical and scanning electron microscopies as well as X-ray diffraction were used to investigate the microstructure and phase composition of EBM Ti-6Al-4V parts. The average α lath width decreases with the increase of the speed function at the fixed beam current (17 mA). Finer microstructure was formed at the beam current 17 mA and speed function 98. The hydrogenation of EBM Ti-6Al-4V parts was performed at the temperatures 500 and 650 °С at the constant pressure of 1 atm up to 0.3 wt %. The correlation between the microstructure and hydrogen sorption kinetics by EBM Ti-6Al-4V parts was demonstrated. Lower average hydrogen sorption rate at 500 °C was in the sample with coarser microstructure manufactured at the beam current 17 mA and speed function 85. The difference of hydrogen sorption kinetics between the manufactured samples at 650 °C was insignificant. The shape of the kinetics curves of hydrogen sorption indicates the phase transition αH + βH→βH. PMID:29747471

Influence of Manufacturing Parameters on Microstructure and Hydrogen Sorption Behavior of Electron Beam Melted Titanium Ti-6Al-4V Alloy.

PubMed

Pushilina, Natalia; Syrtanov, Maxim; Kashkarov, Egor; Murashkina, Tatyana; Kudiiarov, Viktor; Laptev, Roman; Lider, Andrey; Koptyug, Andrey

2018-05-10

Influence of manufacturing parameters (beam current from 13 to 17 mA, speed function 98 and 85) on microstructure and hydrogen sorption behavior of electron beam melted (EBM) Ti-6Al-4V parts was investigated. Optical and scanning electron microscopies as well as X-ray diffraction were used to investigate the microstructure and phase composition of EBM Ti-6Al-4V parts. The average α lath width decreases with the increase of the speed function at the fixed beam current (17 mA). Finer microstructure was formed at the beam current 17 mA and speed function 98. The hydrogenation of EBM Ti-6Al-4V parts was performed at the temperatures 500 and 650 °С at the constant pressure of 1 atm up to 0.3 wt %. The correlation between the microstructure and hydrogen sorption kinetics by EBM Ti-6Al-4V parts was demonstrated. Lower average hydrogen sorption rate at 500 °C was in the sample with coarser microstructure manufactured at the beam current 17 mA and speed function 85. The difference of hydrogen sorption kinetics between the manufactured samples at 650 °C was insignificant. The shape of the kinetics curves of hydrogen sorption indicates the phase transition α H + β H →β H .

The electronic and optical properties of quaternary GaAs1-x-y N x Bi y alloy lattice-matched to GaAs: a first-principles study.

PubMed

Ma, Xiaoyang; Li, Dechun; Zhao, Shengzhi; Li, Guiqiu; Yang, Kejian

2014-01-01

First-principles calculations based on density functional theory have been performed for the quaternary GaAs1-x-y N x Bi y alloy lattice-matched to GaAs. Using the state-of-the-art computational method with the Heyd-Scuseria-Ernzerhof (HSE) hybrid functional, electronic, and optical properties were obtained, including band structures, density of states (DOSs), dielectric function, absorption coefficient, refractive index, energy loss function, and reflectivity. It is found that the lattice constant of GaAs1-x-y N x Bi y alloy with y/x =1.718 can match to GaAs. With the incorporation of N and Bi into GaAs, the band gap of GaAs1-x-y N x Bi y becomes small and remains direct. The calculated optical properties indicate that GaAs1-x-y N x Bi y has higher optical efficiency as it has less energy loss than GaAs. In addition, it is also found that the electronic and optical properties of GaAs1-x-y N x Bi y alloy can be further controlled by tuning the N and Bi compositions in this alloy. These results suggest promising applications of GaAs1-x-y N x Bi y quaternary alloys in optoelectronic devices.

Temperature and size-dependent Hamaker constants for metal nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, K.; Pinchuk, P.

2016-08-01

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Temperature and size-dependent Hamaker constants for metal nanoparticles.

PubMed

Jiang, K; Pinchuk, P

2016-08-26

Theoretical values of the Hamaker constant have been calculated for metal nanoparticles using Lifshitz theory. The theory describes the Hamaker constant in terms of the permittivity of the interacting bodies. Metal nanoparticles exhibit an internal size effect that alters the dielectric permittivity of the particle when its size falls below the mean free path of the conducting electrons. This size dependence of the permittivity leads to size-dependence of the Hamaker constant for metal nanoparticles. Additionally, the electron damping and the plasma frequency used to model the permittivity of the particle exhibit temperature-dependence, which lead to temperature dependence of the Hamaker constant. In this work, both the size and temperature dependence for gold, silver, copper, and aluminum nanoparticles is demonstrated. The results of this study might be of interest for studying the colloidal stability of nanoparticles in solution.

Electrophoretically deposited reduced graphene oxide platform for food toxin detection

NASA Astrophysics Data System (ADS)

Srivastava, Saurabh; Kumar, Vinod; Ali, Md Azahar; Solanki, Pratima R.; Srivastava, Anchal; Sumana, Gajjala; Saxena, Preeti Suman; Joshi, Amish G.; Malhotra, B. D.

2013-03-01

Reduced graphene oxide (RGO) due to its excellent electrochemical properties and large surface area, has recently aroused much interest for electrochemical biosensing application. Here, the chemically active RGO has been synthesized and deposited onto an indium tin oxide (ITO) coated glass substrate by the electrophoretic deposition technique. This novel platform has been utilized for covalent attachment of the monoclonal antibodies of aflatoxin B1 (anti-AFB1) for food toxin (AFB1) detection. The electron microscopy, X-ray diffraction, and UV-visible studies reveal successful synthesis of reduced graphene oxide while the XPS and FTIR studies suggest its carboxylic functionalized nature. The electrochemical sensing results of the anti-AFB1/RGO/ITO based immunoelectrode obtained as a function of aflatoxin concentration show high sensitivity (68 μA ng-1 mL cm-2) and improved detection limit (0.12 ng mL-1). The association constant (ka) for antigen-antibody interaction obtained as 5 × 10-4 ng mL-1 indicates high affinity of antibodies toward the antigen (AFB1).Reduced graphene oxide (RGO) due to its excellent electrochemical properties and large surface area, has recently aroused much interest for electrochemical biosensing application. Here, the chemically active RGO has been synthesized and deposited onto an indium tin oxide (ITO) coated glass substrate by the electrophoretic deposition technique. This novel platform has been utilized for covalent attachment of the monoclonal antibodies of aflatoxin B1 (anti-AFB1) for food toxin (AFB1) detection. The electron microscopy, X-ray diffraction, and UV-visible studies reveal successful synthesis of reduced graphene oxide while the XPS and FTIR studies suggest its carboxylic functionalized nature. The electrochemical sensing results of the anti-AFB1/RGO/ITO based immunoelectrode obtained as a function of aflatoxin concentration show high sensitivity (68 μA ng-1 mL cm-2) and improved detection limit (0.12 ng mL-1). The association constant (ka) for antigen-antibody interaction obtained as 5 × 10-4 ng mL-1 indicates high affinity of antibodies toward the antigen (AFB1). Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr32242d

First-principles calculation of photo-induced electron transfer rate constants in phthalocyanine-C60 organic photovoltaic materials: Beyond Marcus theory

NASA Astrophysics Data System (ADS)

Lee, Myeong H.; Dunietz, Barry D.; Geva, Eitan

2014-03-01

Classical Marcus theory is commonly adopted in solvent-mediated charge transfer (CT) process to obtain the CT rate constant, but it can become questionable when the intramolecular vibrational modes dominate the CT process as in OPV devices because Marcus theory treats these modes classically and therefore nuclear tunneling is not accounted for. We present a computational scheme to obtain the electron transfer rate constant beyond classical Marcus theory. Within this approach, the nuclear vibrational modes are treated quantum-mechanically and a short-time approximation is avoided. Ab initio calculations are used to obtain the basic parameters needed for calculating the electron transfer rate constant. We apply our methodology to phthalocyanine(H2PC)-C60 organic photovoltaic system where one C60 acceptor and one or two H2PC donors are included to model the donor-acceptor interface configuration. We obtain the electron transfer and recombination rate constants for all accessible charge transfer (CT) states, from which the CT exciton dynamics is determined by employing a master equation. The role of higher lying excited states in CT exciton dynamics is discussed. This work is pursued as part of the Center for Solar and Thermal Energy Conversion, an Energy Frontier Research Center funded by the US Department of Energy Office of Science, Office of Basic Energy Sciences under 390 Award No. DE-SC0000957.

Density Functional O(N) Calculations

NASA Astrophysics Data System (ADS)

Ordejón, Pablo

1998-03-01

We have developed a scheme for performing Density Functional Theory calculations with O(N) scaling.(P. Ordejón, E. Artacho and J. M. Soler, Phys. Rev. B, 53), 10441 (1996) The method uses arbitrarily flexible and complete Atomic Orbitals (AO) basis sets. This gives a wide range of choice, from extremely fast calculations with minimal basis sets, to greatly accurate calculations with complete sets. The size-efficiency of AO bases, together with the O(N) scaling of the algorithm, allow the application of the method to systems with many hundreds of atoms, in single processor workstations. I will present the SIESTA code,(D. Sanchez-Portal, P. Ordejón, E. Artacho and J. M. Soler, Int. J. Quantum Chem., 65), 453 (1997) in which the method is implemented, with several LDA, LSD and GGA functionals available, and using norm-conserving, non-local pseudopotentials (in the Kleinman-Bylander form) to eliminate the core electrons. The calculation of static properties such as energies, forces, pressure, stress and magnetic moments, as well as molecular dynamics (MD) simulations capabilities (including variable cell shape, constant temperature and constant pressure MD) are fully implemented. I will also show examples of the accuracy of the method, and applications to large-scale materials and biomolecular systems.

Jahn-Teller transition in TiF3 investigated using density-functional theory

NASA Astrophysics Data System (ADS)

Perebeinos, Vasili; Vogt, Tom

2004-03-01

We use first-principles density-functional theory to calculate the electronic and magnetic properties of TiF3 using the full-potential-linearized augmented-plane-wave method. The local density approximation (LDA) predicts a fully saturated ferromagnetic metal and finds degenerate energy minima for high- and low-symmetry structures. The experimentally observed Jahn-Teller phase transition at Tc=370 K cannot be driven by the electron-phonon interaction alone, which is usually described accurately by the LDA. Electron correlations beyond the LDA are essential to lift the degeneracy of the singly occupied Ti t2g orbital. Although the on-site Coulomb correlations are important, the direction of the t2g-level splitting is determined by dipole-dipole interactions. The LDA+U functional predicts an aniferromagnetic insulator with an orbitally ordered ground state. The input parameters U=8.1 eV and J=0.9 eV for the Ti 3d orbital were found by varying the total charge on the TiF2-6 ion using the molecular NRLMOL code. We estimate the Heisenberg exchange constant for spin 1/2 on a cubic lattice to be approximately 24 K. The symmetry lowering energy in LDA+U is about 900 K per TiF3 formula unit.

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).

Counterion effects on the ultrafast dynamics of charge-transfer-to-solvent electrons.

PubMed

Rivas, N; Moriena, G; Domenianni, L; Hodak, J H; Marceca, E

2017-12-06

We performed femtosecond transient absorption (TA) experiments to monitor the solvation dynamics of charge-transfer-to-solvent (CTTS) electrons originating from UV photoexcitation of ammoniated iodide in close proximity to the counterions. Solutions of KI were prepared in liquid ammonia and TA experiments were carried out at different temperatures and densities, along the liquid-gas coexistence curve of the fluid. The results complement previous femtosecond TA work by P. Vöhringer's group in neat ammonia via multiphoton ionization. The dynamics of CTTS-detached electrons in ammonia was found to be strongly affected by ion pairing. Geminate recombination time constants as well as escape probabilities were determined from the measured temporal profiles and analysed as a function of the medium density. A fast unresolved (τ < 250 fs) increase of absorption related to the creation/thermalization of solvated electron species was followed by two decay components: one with a characteristic time around 10 ps, and a slower one that remains active for hundreds of picoseconds. While the first process is attributed to an early recombination of (I, e - ) pairs, the second decay and its asymptote reflects the effect of the K + counterion on the geminate recombination dynamics, rate and yield. The cation basically acts as an electron anchor that restricts the ejection distance, leading to solvent-separated counterion-electron species. The formation of (K + , NH 3 , e - ) pairs close to the parent iodine atom brings the electron escape probability to very low values. Transient spectra of the electron species have also been estimated as a function of time by probing the temporal profiles at different wavelengths.

Fine structure constant defines visual transparency of graphene.

PubMed

Nair, R R; Blake, P; Grigorenko, A N; Novoselov, K S; Booth, T J; Stauber, T; Peres, N M R; Geim, A K

2008-06-06

There are few phenomena in condensed matter physics that are defined only by the fundamental constants and do not depend on material parameters. Examples are the resistivity quantum, h/e2 (h is Planck's constant and e the electron charge), that appears in a variety of transport experiments and the magnetic flux quantum, h/e, playing an important role in the physics of superconductivity. By and large, sophisticated facilities and special measurement conditions are required to observe any of these phenomena. We show that the opacity of suspended graphene is defined solely by the fine structure constant, a = e2/hc feminine 1/137 (where c is the speed of light), the parameter that describes coupling between light and relativistic electrons and that is traditionally associated with quantum electrodynamics rather than materials science. Despite being only one atom thick, graphene is found to absorb a significant (pa = 2.3%) fraction of incident white light, a consequence of graphene's unique electronic structure.

Free Radical Chemistry of Disinfection Byproducts 2: Rate Constants and Degradation Mechanism of Trichloronitromethane (Chloropicrin)

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

B. J. Mincher; S. K. Cole; W. J. Cooper

2007-02-01

Absolute rate constants for the free-radical-induced degradation of trichloronitromethane (TCNM, chloropicrin) were determined using electron pulse radiolysis and transient absorption spectroscopy. Rate constants for hydroxyl radical, OH, and hydrated electron, eaq-, reactions were (4.97 ± 0.28) × 107 M-1 s-1 and (2.13 ± 0.03) × 1010 M-1 s-1, respectively. It appears that the OH adds to the nitro-group, while the eaq- reacts via dissociative electron attachment to give two carbon centered radicals. The mechanisms of these free radical reactions with TCNM were investigated, using 60Co gamma irradiation at various absorbed doses, measuring the disappearance of TCNM and the appearance ofmore » the product nitrate and chloride ions. The rate constants and mechanistic data were combined in a kinetic computer model that was used to describe the major free radical pathways for the destruction of TCNM in solution. These data are applicable to other advanced oxidation/reduction processes.« less

Rate constants measured for hydrated electron reactions with peptides and proteins

NASA Technical Reports Server (NTRS)

Braams, R.

1968-01-01

Effects of ionizing radiation on the amino acids of proteins and the reactivity of the protonated amino group depends upon the pK subscript a of the group. Estimates of the rate constants for reactions involving the amino acid side chains are presented. These rate constants gave an approximate rate constant for three different protein molecules.

Electron-transfer oxidation properties of DNA bases and DNA oligomers.

PubMed

Fukuzumi, Shunichi; Miyao, Hiroshi; Ohkubo, Kei; Suenobu, Tomoyoshi

2005-04-21

Kinetics for the thermal and photoinduced electron-transfer oxidation of a series of DNA bases with various oxidants having the known one-electron reduction potentials (E(red)) in an aqueous solution at 298 K were examined, and the resulting electron-transfer rate constants (k(et)) were evaluated in light of the free energy relationship of electron transfer to determine the one-electron oxidation potentials (E(ox)) of DNA bases and the intrinsic barrier of the electron transfer. Although the E(ox) value of GMP at pH 7 is the lowest (1.07 V vs SCE) among the four DNA bases, the highest E(ox) value (CMP) is only 0.19 V higher than that of GMP. The selective oxidation of GMP in the thermal electron-transfer oxidation of GMP results from a significant decrease in the pH dependent oxidation potential due to the deprotonation of GMP*+. The one-electron reduced species of the photosensitizer produced by photoinduced electron transfer are observed as the transient absorption spectra when the free energy change of electron transfer is negative. The rate constants of electron-transfer oxidation of the guanine moieties in DNA oligomers with Fe(bpy)3(3+) and Ru(bpy)3(3+) were also determined using DNA oligomers containing different guanine (G) sequences from 1 to 10 G. The rate constants of electron-transfer oxidation of the guanine moieties in single- and double-stranded DNA oligomers with Fe(bpy)3(2+) and Ru(bpy)3(3+) are dependent on the number of sequential guanine molecules as well as on pH.

An improved approach to identify irradiated spices using electronic nose, FTIR, and EPR spectroscopy.

PubMed

Sanyal, Bhaskar; Ahn, Jae-Jun; Maeng, Jeong-Hwan; Kyung, Hyun-Kyu; Lim, Ha-Kyeong; Sharma, Arun; Kwon, Joong-Ho

2014-09-01

Changes in cumin and chili powder from India resulting from electron-beam irradiation were investigated using 3 analytical methods: electronic nose (E-nose), Fourier transform infrared (FTIR) spectroscopy, and electron paramagnetic resonance (EPR) spectroscopy. The spices had been exposed to 6 to 14 kGy doses recommended for microbial decontamination. E-nose measured a clear difference in flavor patterns of the irradiated spices in comparison with the nonirradiated samples. Principal component analysis further showed a dose-dependent variation. FTIR spectra of the samples showed strong absorption bands at 3425, 3007 to 2854, and 1746 cm(-1). However, both nonirradiated and irradiated spice samples had comparable patterns without any noteworthy changes in functional groups. EPR spectroscopy of the irradiated samples showed a radiation-specific triplet signal at g = 2.006 with a hyper-fine coupling constant of 3 mT confirming the results obtained with the E-nose technique. Thus, E-nose was found to be a potential tool to identify irradiated spices. © 2014 Institute of Food Technologists®

Ab-initio study on electronic properties of rocksalt SnAs

NASA Astrophysics Data System (ADS)

Babariya, Bindiya; Vaghela, M. V.; Gajjar, P. N.

2018-05-01

Within the frame work of Local Density Approximation of Exchange and Correlation, ab-initio method of density functional theory with Abinit code is used to compute electronic energy band structure, density of States and charge density of SnAs in rocksalt phase. Our result after optimization for lattice constant agrees with experimental value within 0.59% deviation. The computed electronic energy bands in high symmetry directions Γ→K→X→Γ→L→X→W→L→U shown metallic nature. The lowest band in the electronic band structure is showing band-gap approximately 1.70 eV from next higher band and no crossing between lowest two bands are seen. The density of states revels p-p orbit hybridization between Sn and As atoms. The spherical contour around Sn and As in the charge density plot represent partly ionic and partly covalent bonding. Fermi surface topology is the resultant effect of the single band crossing along L direction at Ef.

FIRST PRINCIPLES STUDY ON ELECTRONIC AND OPTICAL PROPERTIES OF Al-DOPED γ-Ge3N4

NASA Astrophysics Data System (ADS)

Ding, Y. C.; Xiang, A. P.; Zhu, X. H.; Luo, J.; Hu, X. F.

2012-12-01

First principles study of the structural, electronic and optical properties of Al-doped γ-Ge3N4 with different concentration has been reported using the pseudo-potential plane wave method within the generalized gradient approximation (GGA). The binding energy and the formation energy suggest that Aluminum (Al) impurities prefer to substitute Ge at octahedral sites. Different doping concentrations are considered and the corresponding density of states (DOS) are analyzed. Calculated DOS indicates that there are holes in the top of the valance band after doping, meaning a p-type doping. We study the complex dielectric function, the absorption coefficient, and the electron energy loss spectra. It is demonstrated that for the low Al concentration, the material exhibits the dielectric behavior and for the high Al concentration, the material has possibilities to exhibit some metallic behavior. The γ-Ge3N4 doped with Al has a much higher static dielectric constant than undoped γ-Ge3N4, implying its potential applications in electronics and optics.

Electronic structure and magnetic properties of quaternary Heusler alloy Co2CrGa1-xGex (x=0-1)

NASA Astrophysics Data System (ADS)

Seema, K.; Kumar, Ranjan

2015-03-01

The electronic structure of Co-based quaternary Heusler compounds Co2CrGa1-xGex (x=0.00, 0.25, 0.50, 0.75, 1.00) are calculated by first-principles density functional theory. The substitution of Ga by Ge leads to increase in the number of valence electrons. With increasing concentration of Ge, lattice constant decreases linearly whereas bulk modulus and total magnetic moment increases. This shows that the magnetic properties of the compound are dependent on electron concentration of main group element. The calculations show that the alloys with x=0.00, 0.25, 0.50 are not true half-metallic materials whereas alloy with x=0.75, 1.00 exhibit 100% spin polarization at the Fermi level. It shows that the Fermi level can be shifted within the energy-gap to achieve 100% spin polarization. The effect of volumetric and tetragonal strain on magnetic properties is also studied.

Study of high field side/low field side asymmetry in the electron temperature profile with electron cyclotron emission

NASA Astrophysics Data System (ADS)

Gugliada, V. R.; Austin, M. E.; Brookman, M. W.

2017-10-01

Electron cyclotron emission (ECE) provides high resolution measurements of electron temperature profiles (Te(R , t)) in tokamaks. Calibration accuracy of this data can be improved using a sawtooth averaging technique. This improved calibration will then be utilized to determine the symmetry of Te profiles by comparing low field side (LFS) and high field side (HFS) measurements. Although Te is considered constant on flux surfaces, cases have been observed in which there are pronounced asymmetries about the magnetic axis, particularly with increased pressure. Trends in LFS/HFS overlap are examined as functions of plasma pressure, MHD mode presence, heating techniques, and other discharge conditions. This research will provide information on the accuracy of the current two-dimensional mapping of flux surfaces in the tokamak. Findings can be used to generate higher quality EFITs and inform ECE calibration. Work supported in part by US DoE under the Science Undergraduate Laboratory Internship (SULI) program and under DE-FC02-04ER549698.

Electron-beam-evaporated thin films of hafnium dioxide for fabricating electronic devices

DOE PAGES

Xiao, Zhigang; Kisslinger, Kim

2015-06-17

Thin films of hafnium dioxide (HfO 2) are widely used as the gate oxide in fabricating integrated circuits because of their high dielectric constants. In this paper, the authors report the growth of thin films of HfO 2 using e-beam evaporation, and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using this HfO 2 thin film as the gate oxide. The authors analyzed the thin films using high-resolution transmission electron microscopy and electron diffraction, thereby demonstrating that the e-beam-evaporation-grown HfO 2 film has a polycrystalline structure and forms an excellent interface with silicon. Accordingly, we fabricated 31-stage CMOS ringmore » oscillator to test the quality of the HfO 2 thin film as the gate oxide, and obtained excellent rail-to-rail oscillation waveforms from it, denoting that the HfO 2 thin film functioned very well as the gate oxide.« less

Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

PubMed

Lennox, J Christian; Dempsey, Jillian L

2017-11-22

A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

Electronic and Magnetic Structures, Magnetic Hyperfine Fields and Electric Field Gradients in UX3 (X = In, Tl, Pb) Intermetallic Compounds

NASA Astrophysics Data System (ADS)

Khan, Sajid; Yazdani-Kachoei, Majid; Jalali-Asadabadi, Saeid; Farooq, Muhammad Bilal; Ahmad, Iftikhar

2018-02-01

Cubic uranium compounds such as UX3 (X is a non-transition element of groups IIIA or IVA) exhibit highly diverse magnetic properties, including Pauli paramagnetism, spin fluctuation and anti-ferromagnetism. In the present paper, we explore the structural, electronic and magnetic properties as well as the hyperfine fields (HFFs) and electric field gradients (EFGs) with quadrupole coupling constant of UX3 (X = In, Tl, Pb) compounds using local density approximation, Perdew-Burke-Ernzerhof parametrization of generalized gradient approximation (PBE-GGA) including the Hubbard U parameter (GGA + U), a revised version of PBE-GGA that improves equilibrium properties of densely packed solids and their surfaces (PBEsol-GGA), and a hybrid functional (HF-PBEsol). The spin orbit-coupling calculations have been added to investigate the relativistic effect of electrons in these materials. The comparison between the experimental parameters and our calculated structural parameters we confirm the consistency and effectiveness of our theoretical tools. The computed magnetic moments show that magnetic moment increases from indium to lead in the UX3 family, and all these compounds are antiferromagnetic in nature. The EFGs and HFFs, as well as the quadrupole coupling constant of UX3 (X = In, Tl, Pb), are discussed in detail. These properties primarily originate from f and p states of uranium and post-transition sites.

Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra

NASA Astrophysics Data System (ADS)

Shimada, Toru; Hasegawa, Takeshi

2017-10-01

The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pKa‧. The determination of pKa‧ is performed for various ionic strengths, which reveals the thermodynamic acid constant (pKa = 7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of - 1 and the blue form that of - 2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed.

Ab-initio study of C15-type Laves phase superconductor LaRu2

NASA Astrophysics Data System (ADS)

Kholil, Md. Ibrahim; Islam, Md. Shahinur; Rahman, Md. Atikur

2017-01-01

Structural, elastic, electronic, optical, thermodynamic, and superconducting properties of the Laves phase superconductor LaRu2 with Tc 1.63 K were investigated using the first-principles calculations for the first time. The corresponding evaluated structural parameters are in good agreement with the available theoretical values. The different elastic properties like as, elastic constants, bulk modulus B, shear modulus G, Young's modulus E, and Poisson ratio ν were calculated using the Voigt-Reuss-Hill approximation. The ductility nature appears in both values of Cauchy pressure and Pugh's ratio. The band structure and Cauchy pressure shows that the material behaves metallic nature. The calculated total density of state is 6.80 (electrons/eV) of LaRu2. The optical properties such as reflectivity, absorption spectrum, refractive index, dielectric function, conductivity, and energy loss spectrum are also calculated. The photoconductivity reveals the metallic nature of LaRu2 and absorption coefficient is good in the infrared region. The evaluated density and Debye temperature are 9.55 gm/cm3 and 110.51 K, respectively. In addition, the study of thermodynamic properties like as minimum thermal conductivity, melting temperature, and Dulong-Petit limit are 0.26 (Wm-1 K-1), 1,471.65 K, and 74.80 (J/mole K), respectively. Finally, the investigated electron-phonon coupling constant is 0.66 of LaRu2 superconductor.

Determination of equilibrium structures of bromothymol blue revealed by using quantum chemistry with an aid of multivariate analysis of electronic absorption spectra.

PubMed

Shimada, Toru; Hasegawa, Takeshi

2017-10-05

The pH dependent chemical structures of bromothymol blue (BTB), which have long been under controversy, are determined by employing a combined technique of multivariate analysis of electronic absorption spectra and quantum chemistry. Principle component analysis (PCA) of the pH dependent spectra apparently reveals that only two chemical species are adequate to fully account for the color changes, with which the spectral decomposition is readily performed by using augmented alternative least-squares (ALS) regression analysis. The quantity variation by the ALS analysis also reveals the practical acid dissociation constant, pK a '. The determination of pK a ' is performed for various ionic strengths, which reveals the thermodynamic acid constant (pK a =7.5) and the number of charge on each chemical species; the yellow form is negatively charged species of -1 and the blue form that of -2. On this chemical information, the quantum chemical calculation is carried out to find that BTB molecules take the pure quinoid form in an acid solution and the quinoid-phenolate form in an alkaline solution. The time-dependent density functional theory (TD-DFT) calculations for the theoretically determined chemical structures account for the peak shift of the electronic spectra. In this manner, the structures of all the chemical species appeared in equilibrium have finally been confirmed. Copyright © 2017 Elsevier B.V. All rights reserved.

Superconductivity in Doped sp3 Semiconductors: The Case of the Clathrates

NASA Astrophysics Data System (ADS)

Connétable, D.; Timoshevskii, V.; Masenelli, B.; Beille, J.; Marcus, J.; Barbara, B.; Saitta, A. M.; Rignanese, G.-M.; Mélinon, P.; Yamanaka, S.; Blase, X.

2003-12-01

We present a joint experimental and theoretical study of the superconductivity in doped silicon clathrates. The critical temperature in Ba8@Si-46 is shown to strongly decrease with applied pressure. These results are corroborated by ab initio calculations using MacMillan's formulation of the BCS theory with the electron-phonon coupling constant λ calculated from perturbative density functional theory. Further, the study of I8@Si-46 and of gedanken pure silicon diamond and clathrate phases doped within a rigid-band approach show that the superconductivity is an intrinsic property of the sp3 silicon network. As a consequence, carbon clathrates are predicted to yield large critical temperatures with an effective electron-phonon interaction much larger than in C60.

Near-infrared radiation absorption properties of covellite (CuS) using first-principles calculations

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

Xiao, Lihua, E-mail: xiaolihua@git.edu.cn; College of Physics and Information Science, Hunan Normal University, Changsha 410081; Guizhou Special Functional Materials 2011 Collaborative Innovation Center, Guizhou Institute of Technology, Guiyang 550003

2016-08-15

First-principles density functional theory was used to investigate the electronic structure, optical properties and the origin of the near-infrared (NIR) absorption of covellite (CuS). The calculated lattice constant and optical properties are found to be in reasonable agreement with experimental and theoretical findings. The electronic structure reveals that the valence and conduction bands of covellite are determined by the Cu 3d and S 3p states. By analyzing its optical properties, we can fully understand the potential of covellite (CuS) as a NIR absorbing material. Our results show that covellite (CuS) exhibits NIR absorption due to its metal-like plasma oscillation inmore » the NIR range.« less

K-shell Photoionization of Na-like to Cl-like Ions of Mg, Si, S, Ar, and Ca

NASA Technical Reports Server (NTRS)

Witthoeft, M. C.; Garcia, J.; Kallman, T. R.; Bautista, M. A.; Mendoza, C.; Palmeri, P.; Quinet, P.

2010-01-01

We present R-matrix calculations of photoabsorption and photoionization cross sections across the K edge of Mg, Si, S, Ar, and Ca ions with more than 10 electrons. The calculations include the effects of radiative and Auger damping by means of an optical potential. The wave functions are constructed from single-electron. orbital bases obtained using a Thomas-Fermi-Dirac statistical model potential. Configuration interaction is considered among all states up to n = 3. The damping processes affect the resonances converging to the K-thresholds causing them to display symmetric profiles of constant width that smear the otherwise sharp edge at the photoionization threshold. These data are important for the modeling of features found in photoionized plasmas.

Energy dependence of the response of lithium fluoride TLD rods in high energy electron fields.

PubMed

Holt, J G; Edelstein, G R; Clark, T E

1975-07-01

The energy dependence of lithium fluoride dosemeters is a complicated function of energy as well as of cavity size. In the application of TLD to charged particle dosimetry, a cavity perturbation effect may exist even though the ratios of the mass stopping powers are constant over the energies encountered. This effect was investigated for lithium fluoride rods in electron fields ranging in energy from 2-5 to 20 MeV. A 13% change of TL response per unit of absorbed dose was measured over that energy range. A semi-empirical theory was developed to account for the cavity effect, using Burlin cavity theory as a starting point. The agreement between theory and measurement is satisfactory.

Pressure induced phase transition in CdTe nanowire: A DFT study

NASA Astrophysics Data System (ADS)

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

2018-05-01

We have studied structural phase transition and electronic properties of CdTe nanowires in their wurtzite (B4) to rocksalt (B1) phase by first principles density functional calculations using SIESTA code. Nanowires are derived from wurtzite and rocksalt phase of bulk CdTe with growth direction along 100 planes. We observed structural phase transition from B4→B1 at 4.79 GPa. Wurtzite structure is found to have band gap 2.30 eV while rocksalt is metallic in nature. Our calculated lattice constant (4.55 Å for B4 and 5.84 Å for B1), transition pressure (4.79 GPa) and electronic structure results are in close agreement with the previous calculations on bulk and nanostructures.

Structural, Electronic and Elastic Properties of Half-Heusler Alloys CrNiZ (Z = Al, Si, Ge and As)

NASA Astrophysics Data System (ADS)

Zitouni, A.; Benstaali, W.; Abbad, A.; Lantri, T.; Bouadjemi, B.; Aziz, Z.

2018-06-01

In the present work, a self-consistent ab-initio calculation using the full- potential linearized augmented plane wave (FP-LAPW) method within the framework of the spin-polarized density functional theory (DFT) was used to study the structural, electronic, magnetic and elastic properties of the half Heusler alloys CrNiZ (Z = Al, Si, Ge and As) in three phases ( α, β and γ phases). The generalized gradient approximation (GGA) described by Perdew-Burke-Ernzerhof (PBE) was used. The results obtained for the spin-polarized band structure and the density of states show a halfmetallic behavior for the four compounds. The elastic constants ( C ij ) show that our compounds are ductile, stiff and anisotropic.

Spectroscopic Constants of the Known Electronic States of Lead Monofluoride

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

McRaven, C.P.; Sivakumar, P.; Shafer-Ray, N.E.

2010-08-01

Based on measurements made by mass-resolved 1 + 1{prime} + 1{double_prime} resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant {sup 208}Pb{sup 19}F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues {sup 206}Pb{sup 19}F and {sup 207}Pb{sup 19}F have also been determined. The symmetry of the D-state is found to be {sup 2}{pi}{sub 1/2}, and the F-state is found to be an {Omega} = 3/2more » state.« less

Electronic structure and spectra of the RbHe van der Waals system including spin orbit interaction

NASA Astrophysics Data System (ADS)

Dhiflaoui, Jamila; Bejaoui, Mohamed; Berriche, Hamid

2017-12-01

The potential energy interaction, the spectroscopic properties and dipole functions of the RbHe van der Waals dimer have been investigated. We used a one-electron pseudopotential approach and large Gaussian basis sets to represent the two atoms Rb and He. The Rb+ core and the electron-He interactions were replaced by semi-local pseudopotentials and a core-core interaction is included. Therefore, the number of active electrons of RbHe is reduced to only one electron. Consequently, the potential energy curves and dipole moments for many electronic states dissociating into Rb(5s,5p,4d,6s,6p,5d,7s)+He are performed at the SCF level. In addition, the spin-orbit coupling is included in the calculation. The Rb+He interaction, in its ground state, is taken from accurate CCSD (T) calculations and fitted to an analytical expression for a better description of the potential in all internuclear ranges. The spectroscopic properties of the RbHe electronic states are extracted. The comparison of these constants has shown a very good agreement for the ground state as well as for the lower excited states when compared with existing theoretical and experimental studies.

Thermoelectric properties of 2H-CuGaO2 for device applications: A first principle TB-mBJ potential study

NASA Astrophysics Data System (ADS)

Bhamu, K. C.; Praveen, C. S.

2017-12-01

Here we report the structural, electronic, optical, and thermoelectric properties of delafossite type 2H-CuGaO2 using first principles calculations. The present calculation predict an indirect band gap of 1.20 eV and a direct band gap of 3.48 eV. A detailed analysis of the electronic structure is provided based on atom and orbital projected density of states. Frequency dependent dielectric functions, refractive index, and absorption coefficient as a function of photon energy are discussed. The thermoelectric properties with power factor, and the figure of merit are reported as a function of chemical potential in the region ± 0.195 (μ -EF) eV at constant temperature of 300 and 800 K. The thermoelectric properties shows that 2H-CuGaO2 could be potential candidate for engineering devises operating at high temperature for the chemical potential in the range of ± 0.055 (μ -EF) eV and beyond this range the thermoelectric performance of 2H-CuGaO2 get reduced.

Gedanken densities and exact constraints in density functional theory.

PubMed

Perdew, John P; Ruzsinszky, Adrienn; Sun, Jianwei; Burke, Kieron

2014-05-14

Approximations to the exact density functional for the exchange-correlation energy of a many-electron ground state can be constructed by satisfying constraints that are universal, i.e., valid for all electron densities. Gedanken densities are designed for the purpose of this construction, but need not be realistic. The uniform electron gas is an old gedanken density. Here, we propose a spherical two-electron gedanken density in which the dimensionless density gradient can be an arbitrary positive constant wherever the density is non-zero. The Lieb-Oxford lower bound on the exchange energy can be satisfied within a generalized gradient approximation (GGA) by bounding its enhancement factor or simplest GGA exchange-energy density. This enhancement-factor bound is well known to be sufficient, but our gedanken density shows that it is also necessary. The conventional exact exchange-energy density satisfies no such local bound, but energy densities are not unique, and the simplest GGA exchange-energy density is not an approximation to it. We further derive a strongly and optimally tightened bound on the exchange enhancement factor of a two-electron density, which is satisfied by the local density approximation but is violated by all published GGA's or meta-GGA's. Finally, some consequences of the non-uniform density-scaling behavior for the asymptotics of the exchange enhancement factor of a GGA or meta-GGA are given.

Density of Trap States and Auger-mediated Electron Trapping in CdTe Quantum-Dot Solids.

PubMed

Boehme, Simon C; Azpiroz, Jon Mikel; Aulin, Yaroslav V; Grozema, Ferdinand C; Vanmaekelbergh, Daniël; Siebbeles, Laurens D A; Infante, Ivan; Houtepen, Arjan J

2015-05-13

Charge trapping is an ubiquitous process in colloidal quantum-dot solids and a major limitation to the efficiency of quantum dot based devices such as solar cells, LEDs, and thermoelectrics. Although empirical approaches led to a reduction of trapping and thereby efficiency enhancements, the exact chemical nature of the trapping mechanism remains largely unidentified. In this study, we determine the density of trap states in CdTe quantum-dot solids both experimentally, using a combination of electrochemical control of the Fermi level with ultrafast transient absorption and time-resolved photoluminescence spectroscopy, and theoretically, via density functional theory calculations. We find a high density of very efficient electron traps centered ∼0.42 eV above the valence band. Electrochemical filling of these traps increases the electron lifetime and the photoluminescence quantum yield by more than an order of magnitude. The trapping rate constant for holes is an order of magnitude lower that for electrons. These observations can be explained by Auger-mediated electron trapping. From density functional theory calculations we infer that the traps are formed by dicoordinated Te atoms at the quantum dot surface. The combination of our unique experimental determination of the density of trap states with the theoretical modeling of the quantum dot surface allows us to identify the trapping mechanism and chemical reaction at play during charge trapping in these quantum dots.

Microwave emulations and tight-binding calculations of transport in polyacetylene

NASA Astrophysics Data System (ADS)

Stegmann, Thomas; Franco-Villafañe, John A.; Ortiz, Yenni P.; Kuhl, Ulrich; Mortessagne, Fabrice; Seligman, Thomas H.

2017-01-01

A novel approach to investigate the electron transport of cis- and trans-polyacetylene chains in the single-electron approximation is presented by using microwave emulation measurements and tight-binding calculations. In the emulation we take into account the different electronic couplings due to the double bonds leading to coupled dimer chains. The relative coupling constants are adjusted by DFT calculations. For sufficiently long chains a transport band gap is observed if the double bonds are present, whereas for identical couplings no band gap opens. The band gap can be observed also in relatively short chains, if additional edge atoms are absent, which cause strong resonance peaks within the band gap. The experimental results are in agreement with our tight-binding calculations using the nonequilibrium Green's function method. The tight-binding calculations show that it is crucial to include third nearest neighbor couplings to obtain the gap in the cis-polyacetylene.

First-principles investigation of mechanical and electronic properties of tetragonal NbAl3 under tension

NASA Astrophysics Data System (ADS)

Jiao, Zhen; Liu, Qi-Jun; Liu, Fu-Sheng; Tang, Bin

2018-06-01

Using the density functional theory calculations, the mechanical and electronic properties of NbAl3 under different tensile loads were investigated. The calculated lattice parameters, elastic constants and mechanical properties (bulk modulus, shear modulus, Young's modulus, Poisson's ratio, Pugh's criterion and Cauchy's pressure) indicated that our results were in agreement with the published experimental and theoretical data at zero tension. With respect to NbAl3 under tension in this paper, the crystal structure was changed from tetragonal to orthorhombic under tension along the [100] and [101] directions. The NbAl3 crystal has been classified as brittle material under tension from 0 to 20 GPa. The obtained Young's modulus and Debye temperature monotonically decreased with increasing tension stress. Combining with mechanical and electronic properties in detail, the decreased mechanical properties were mainly due to the weakening of covalency.

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.

Neutron investigation of Nd 2- x- yCe xLa yCuO 4 (0 ⩽ x ⩽ 0.2; y = 0.5, 1)

NASA Astrophysics Data System (ADS)

Gutmann, M.; Allenspach, P.; Fauth, F.; Furrer, A.; Zolliker, M.; Rosenkranz, S.; Eccleston, R. S.

1997-02-01

We present neutron diffraction and crystal field (CF) spectroscopy results obtained for the electron-doped superconductor precursor material Nd 2- x- yCe xLa yCuO 4 (0 ⩽ x ⩽ 0.2; y = 0.5, 1). Samples were prepared via a sol-gel methods. The lattice constants as a function of Ce-doping show the well-known behavior common to this class of compounds, i.e. the a parameter increases while the c parameter decreases with increasing Ce amount. The presence of La expands the unit cell in all directions compared to the mother compound Nd 2CuO 4 while preserving the T‧-structure for the above mentioned range. The CF spectra clearly show the presence of electronic inhomogeneities associated with electron doping from Ce 4+ on one Cu-site in the CuO 2-planes.

Atropisomerization of di-para-substituted propyl-bridged biphenyl cyclophanes.

PubMed

Rotzler, Jürgen; Gsellinger, Heiko; Bihlmeier, Angela; Gantenbein, Markus; Vonlanthen, David; Häussinger, Daniel; Klopper, Wim; Mayor, Marcel

2013-01-07

The influence of electron donors and electron acceptors of variable strength in the 4 and 4' position of 2 and 2' propyl-bridged axial chiral biphenyl cyclophanes on their atropisomerization process was studied. Estimated free energies ΔG(‡)(T) of the rotation around the central biphenyl bond which were obtained from (1)H-NMR coalescence measurements were correlated to the Hammett parameters σ(p) as a measure for electron donor and acceptor strength. It is demonstrated that the resulting nice linear correlation is mainly based on the influence of the different substituents on the π-system of the biphenyl cyclophanes. By lineshape analysis the rate constants were calculated and by the use of the Eyring equation the enthalpic and entropic contributions were evaluated. Density functional theory calculations show a planar transition state of the isomerization process and the calculated energy barriers based on this reaction mechanism are in good agreement with the experimentally obtained free energies.

Kinetic studies on the oxidation of cytochrome b(5) Phe35 mutants with cytochrome c, plastocyanin and inorganic complexes.

PubMed

Yao, Ping; Wang, Yun-Hua; Sun, Bing-Yun; Xie, Yi; Hirota, Shun; Yamauchi, Osamu; Huang, Zhong-Xian

2002-04-01

To illustrate the functions of the aromatic residue Phe35 of cytochrome b(5) and to give further insight into the roles of the Phe35-containing hydrophobic patch and/or aromatic channel of cytochrome b(5), we studied electron transfer reactions of cytochrome b(5) and its Phe35Tyr and Phe35Leu variants with cytochrome c, with the wild-type and Tyr83Phe and Tyr83Leu variants of plastocyanin, and with the inorganic complexes [Fe(EDTA)](-), [Fe(CDTA)](-) and [Ru(NH(3))(6)](3+). The changes at Phe35 of cytochrome b(5) and Tyr83 of plastocyanin do not affect the second-order rate constants for the electron transfer reactions. These results show that the invariant aromatic residues and aromatic patch/channel are not essential for electron transfer in these systems.

Pump and Flow Control Subassembly of Thermal Control Subsystem for Photovoltaic Power Module

NASA Technical Reports Server (NTRS)

Motil, Brian; Santen, Mark A.

1993-01-01

The pump and flow control subassembly (PFCS) is an orbital replacement unit (ORU) on the Space Station Freedom photovoltaic power module (PVM). The PFCS pumps liquid ammonia at a constant rate of approximately 1170 kg/hr while providing temperature control by flow regulation between the radiator and the bypass loop. Also, housed within the ORU is an accumulator to compensate for fluid volumetric changes as well as the electronics and firmware for monitoring and control of the photovoltaic thermal control system (PVTCS). Major electronic functions include signal conditioning, data interfacing and motor control. This paper will provide a description of each major component within the PFCS along with performance test data. In addition, this paper will discuss the flow control algorithm and describe how the nickel hydrogen batteries and associated power electronics will be thermally controlled through regulation of coolant flow to the radiator.

Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes.

PubMed

Travia, Nicholas E; Xu, Zhenggang; Keith, Jason M; Ison, Elon A; Fanwick, Phillip E; Hall, Michael B; Abu-Omar, Mahdi M

2011-10-17

The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(‡)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(‡) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(‡) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.

Measurement of Rate Constants for Homodimer Subunit Exchange Using Double Electron-Electron Resonance and Paramagnetic Relaxation Enhancements

PubMed Central

Yang, Yunhuang; Ramelot, Theresa A.; Ni, Shuisong; McCarrick, Robert M.; Kennedy, Michael A.

2013-01-01

Here, we report novel methods to measure rate constants for homodimer subunit exchange using double electron-electron resonance (DEER) electron paramagnetic resonance spectroscopy measurements and nuclear magnetic resonance spectroscopy based paramagnetic relaxation enhancement (PRE) measurements. The techniques were demonstrated using the homodimeric protein Dsy0195 from the strictly anaerobic bacterium Desulfitobacterium hafniense Y51. At specific times following mixing site-specific MTSL-labeled Dsy0195 with uniformly 15N-labeled Dsy0195, the extent of exchange was determined either by monitoring the decrease of MTSL-labeled homodimer from the decay of the DEER modulation depth or by quantifying the increase of MTSL-labeled/15N-labeled heterodimer using PREs. Repeated measurements at several time points following mixing enabled determination of the homodimer subunit dissociation rate constant, k−1;, which was 0.037 ± 0.005 min−1 derived from DEER experiments with a corresponding half-life time of 18.7 minutes. These numbers agreed with independent measurements obtained from PRE experiments. These methods can be broadly applied to protein-protein and protein-DNA complex studies. PMID:23180051

Density functional theory determination of structural and electronic properties of struvite.

PubMed

Romanowski, Zbigniew; Kempisty, Paweł; Prywer, Jolanta; Krukowski, Stanisław; Torzewska, Agnieszka

2010-07-29

Crystallographic structure, total energy, electronic structure, and the most important elastic properties of struvite, NH(4)MgPO(4).6H(2)O, the main component of infectious urinary stones, are presented. The calculations were performed using ab initio full-electron calculations within the density functional theory-generalized gradient approximation (DFT-GGA) framework. The obtained crystallographic symmetry and the calculated lattice parameters and also the elastic constants are in good agreement with the experimental data. The elastic properties are essential for establishing an optimal response of urinary stones during shock-wave lithotripsy. The calculated electronic charge distribution confirms the layered structure of the struvite crystals. The polar character of the crystal, well-known from crystal growth experiments, was also confirmed by the magnitude of spontaneous polarization which was obtained from direct determination of the electrical dipole density. The calculated value of spontaneous polarization is equal to -8.8 microC cm(-2). This feature may play a key role in struvite crystallization, electrically binding the charged active impurities and other active species, and consequently determining urinary stone formation. We also present the results of our own experiment of the mineralization of struvite induced to growth by Proteus bacteria which are mainly isolated from infectious urinary stones.

THE ENVIRONMENT AND DISTRIBUTION OF EMITTING ELECTRONS AS A FUNCTION OF SOURCE ACTIVITY IN MARKARIAN 421

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

Mankuzhiyil, Nijil; Ansoldi, Stefano; Persic, Massimo

2011-05-20

For the high-frequency-peaked BL Lac object Mrk 421, we study the variation of the spectral energy distribution (SED) as a function of source activity, from quiescent to active. We use a fully automatized {chi}{sup 2}-minimization procedure, instead of the 'eyeball' procedure more commonly used in the literature, to model nine SED data sets with a one-zone synchrotron self-Compton (SSC) model and examine how the model parameters vary with source activity. The latter issue can finally be addressed now, because simultaneous broadband SEDs (spanning from optical to very high energy photon) have finally become available. Our results suggest that in Mrkmore » 421 the magnetic field (B) decreases with source activity, whereas the electron spectrum's break energy ({gamma}{sub br}) and the Doppler factor ({delta}) increase-the other SSC parameters turn out to be uncorrelated with source activity. In the SSC framework, these results are interpreted in a picture where the synchrotron power and peak frequency remain constant with varying source activity, through a combination of decreasing magnetic field and increasing number density of {gamma} {<=} {gamma}{sub br} electrons: since this leads to an increased electron-photon scattering efficiency, the resulting Compton power increases, and so does the total (= synchrotron plus Compton) emission.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

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

Osborne, David; Lawson, Patrick; Adams, Nigel, E-mail: ngadams@uga.edu

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible,more » using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.« less

Electron-ion dissociative recombination rate constants relevant to the Titan atmosphere and the Interstellar Medium

NASA Astrophysics Data System (ADS)

Osborne, David; Lawson, Patrick; Adams, Nigel

2014-01-01

Following the arrival of Cassini at Titan in 2004, the Titan atmosphere has been shown to contain large complex polycyclic-aromatic hydrocarbons. Since Cassini has provided a great deal of data, there exists a need for kinetic rate data to help with modeling this atmosphere. One type of kinetic data needed is electron-ion dissociative recombination (e-IDR) rate constants. These data are not readily available for larger compounds, such as naphthalene, or oxygen containing compounds, such as 1,4 dioxane or furan. Here, the rate constants for naphthalene, 1,4 dioxane, and furan have been measured and their temperature dependencies are determined when possible, using the University of Georgia's Variable Temperature Flowing Afterglow. The rate constants are compared with those previously published for other compounds; these show trends which illustrate the effects which multi-rings and oxygen heteroatoms substitutions have upon e-IDR rate constants.

Large Quantum Probability Backflow and the Azimuthal Angle-Angular Momentum Uncertainty Relation for an Electron in a Constant Magnetic Field

ERIC Educational Resources Information Center

Strange, P.

2012-01-01

In this paper we demonstrate a surprising aspect of quantum mechanics that is accessible to an undergraduate student. We discuss probability backflow for an electron in a constant magnetic field. It is shown that even for a wavepacket composed entirely of states with negative angular momentum the effective angular momentum can take on positive…

dParFit: A computer program for fitting diatomic molecule spectral data to parameterized level energy expressions

NASA Astrophysics Data System (ADS)

Le Roy, Robert J.

2017-01-01

This paper describes FORTRAN program dParFit, which performs least-squares fits of diatomic molecule spectroscopic data involving one or more electronic states and one or more isotopologues, to parameterized expressions for the level energies. The data may consist of any combination of microwave, infrared or electronic vibrotational bands, fluorescence series or binding energies (from photo-association spectroscopy). The level energies for each electronic state may be described by one of: (i) band constants {Gv ,Bv ,Dv , … } for each vibrational level, (ii) generalized Dunham expansions, (iii) pure near-dissociation expansions (NDEs), (iv) mixed Dunham/NDE expressions, or (v) individual term values for each distinct level of each isotopologue. Different representations may be used for different electronic states and/or for different types of constants in a given fit (e.g., Gv and Bv may be represented one way and centrifugal distortion constants another). The effect of Λ-doubling or 2Σ splittings may be represented either by band constants (qvB or γvB, qvD or γvD, etc.) for each vibrational level of each isotopologue, or by using power series expansions in (v + 1/2) to represent those constants. Fits to Dunham or NDE expressions automatically incorporate normal first-order semiclassical mass scaling to allow combined analyses of multi-isotopologue data. In addition, dParFit may fit to determine atomic-mass-dependent terms required to account for breakdown of the Born-Oppenheimer and first-order semiclassical approximations. In any of these types of fits, one or more subsets of these parameters for one or more of the electronic states may be held fixed, while a limited parameter set is varied. The program can also use a set of read-in constants to make predictions and calculate deviations [ycalc -yobs ] for any chosen input data set, or to generate predictions of arbitrary data sets.

Substitution and protonation effects on spin-spin coupling constants in prototypical aromatic rings: C6H6, C5H5N and C5H5P.

PubMed

Del Bene, Janet E; Elguero, José

2006-08-01

Ab initio equation-of-motion coupled cluster calculations have been carried out to evaluate one-, two-, and three-bond 13C-13C, 15N-13C, 31P-13C coupling constants in benzene, pyridine, pyridinium, phosphinine, and phosphininium. The introduction of N or P heteroatoms into the aromatic ring not only changes the magnitudes of the corresponding X-C coupling constants (J, for X = C, N, or P) but also the signs and magnitudes of corresponding reduced coupling constants (K). Protonation of the heteroatoms also produces dramatic changes in coupling constants and, by removing the lone pair of electrons from the sigma-electron framework, leads to the same signs for corresponding reduced coupling constants for benzene, pyridinium, and phosphininium. C-C coupling constants are rather insensitive to the presence of the heteroatoms and protonation. All terms that contribute to the total coupling constant (except for the diamagnetic spin-orbit (DSO) term) must be computed if good agreement with experimental data is to be obtained. Copyright 2006 John Wiley & Sons, Ltd.

Enhanced dielectric properties of Fe-substituted TiO2 nanoparticles

NASA Astrophysics Data System (ADS)

Ali, T.; Ahmed, Ateeq; Naseem siddique, M.; Tripathi, P.

2018-04-01

We report the structural and dielectric properties Ti1-xFexO2 (0.00 < x < 0.10) nanoparticles (NPs) synthesized by sol-gel method. The synthesized material has been characterized by soft X-ray absorption spectroscopy (SXAS) in order to investigate the fine structure and electronic valence state. SXAS analysis reveals that Fe-ions exist only in 3+ valance state in all the samples. The dielectric properties were studied by the use of LCR impedance spectroscopy. The dielectric constants, dielectric loss and A.C. conductivity have been determined as a function of frequency and composition of iron. At higher frequencies, the materials exhibited high AC Conductivity and low dielectric constant. The above theory could be explained by 'Maxwell Wagner Model' and may provide a new insight to fabricate nanomaterials having possible electrical application.

Nuclear spin noise in the central spin model

NASA Astrophysics Data System (ADS)

Fröhling, Nina; Anders, Frithjof B.; Glazov, Mikhail

2018-05-01

We study theoretically the fluctuations of the nuclear spins in quantum dots employing the central spin model which accounts for the hyperfine interaction of the nuclei with the electron spin. These fluctuations are calculated both with an analytical approach using homogeneous hyperfine couplings (box model) and with a numerical simulation using a distribution of hyperfine coupling constants. The approaches are in good agreement. The box model serves as a benchmark with low computational cost that explains the basic features of the nuclear spin noise well. We also demonstrate that the nuclear spin noise spectra comprise a two-peak structure centered at the nuclear Zeeman frequency in high magnetic fields with the shape of the spectrum controlled by the distribution of the hyperfine constants. This allows for direct access to this distribution function through nuclear spin noise spectroscopy.

SmB6 electron-phonon coupling constant from time- and angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Sterzi, A.; Crepaldi, A.; Cilento, F.; Manzoni, G.; Frantzeskakis, E.; Zacchigna, M.; van Heumen, E.; Huang, Y. K.; Golden, M. S.; Parmigiani, F.

2016-08-01

SmB6 is a mixed valence Kondo system resulting from the hybridization between localized f electrons and delocalized d electrons. We have investigated its out-of-equilibrium electron dynamics by means of time- and angle-resolved photoelectron spectroscopy. The transient electronic population above the Fermi level can be described by a time-dependent Fermi-Dirac distribution. By solving a two-temperature model that well reproduces the relaxation dynamics of the effective electronic temperature, we estimate the electron-phonon coupling constant λ to range from 0.13 ±0.03 to 0.04 ±0.01 . These extremes are obtained assuming a coupling of the electrons with either a phonon mode at 10 or 19 meV. A realistic value of the average phonon energy will give an actual value of λ within this range. Our results provide an experimental report on the material electron-phonon coupling, contributing to both the electronic transport and the macroscopic thermodynamic properties of SmB6.

Electronic couplings for molecular charge transfer: Benchmarking CDFT, FODFT, and FODFTB against high-level ab initio calculations

NASA Astrophysics Data System (ADS)

Kubas, Adam; Hoffmann, Felix; Heck, Alexander; Oberhofer, Harald; Elstner, Marcus; Blumberger, Jochen

2014-03-01

We introduce a database (HAB11) of electronic coupling matrix elements (Hab) for electron transfer in 11 π-conjugated organic homo-dimer cations. High-level ab inito calculations at the multireference configuration interaction MRCI+Q level of theory, n-electron valence state perturbation theory NEVPT2, and (spin-component scaled) approximate coupled cluster model (SCS)-CC2 are reported for this database to assess the performance of three DFT methods of decreasing computational cost, including constrained density functional theory (CDFT), fragment-orbital DFT (FODFT), and self-consistent charge density functional tight-binding (FODFTB). We find that the CDFT approach in combination with a modified PBE functional containing 50% Hartree-Fock exchange gives best results for absolute Hab values (mean relative unsigned error = 5.3%) and exponential distance decay constants β (4.3%). CDFT in combination with pure PBE overestimates couplings by 38.7% due to a too diffuse excess charge distribution, whereas the economic FODFT and highly cost-effective FODFTB methods underestimate couplings by 37.6% and 42.4%, respectively, due to neglect of interaction between donor and acceptor. The errors are systematic, however, and can be significantly reduced by applying a uniform scaling factor for each method. Applications to dimers outside the database, specifically rotated thiophene dimers and larger acenes up to pentacene, suggests that the same scaling procedure significantly improves the FODFT and FODFTB results for larger π-conjugated systems relevant to organic semiconductors and DNA.

The effects of temperature on optical properties of InGaN/GaN multiple quantum well light-emitting diodes

NASA Astrophysics Data System (ADS)

Li, Yi; Zhu, Youhua; Huang, Jing; Deng, Honghai; Wang, Meiyu; Yin, HaiHong

2017-02-01

The effects of temperature on the optical properties of InGaN/GaN quantum well (QW) light-emitting diodes have been investigated by using the six-by-six K-P method taking into account the temperature dependence of band gaps, lattice constants, and elastic constants. The numerical results indicate that the increase of temperature leads to the decrease of the spontaneous emission rate at the same injection current density due to the redistribution of carrier density and the increase of the non-radiative recombination rate. The product of Fermi-Dirac distribution functions of electron fc n and hole ( 1 - fv U m ) for the transitions between the three lowest conduction subbands (c1-c3) and the top six valence subbands (v1-v6) is larger at the lower temperature, which indicates that there are more electron-hole pairs distributed on the energy levels. It should be noted that the optical matrix elements of the inter-band transitions slightly increase at the higher temperature. In addition, the internal quantum efficiency of the InGaN/GaN QW structure is evidently decreased with increasing temperature.

Effect of annealing on the optical properties of amorphous Se79Te10Sb4Bi7 thin films

NASA Astrophysics Data System (ADS)

Nyakotyo, H.; Sathiaraj, T. S.; Muchuweni, E.

2017-07-01

Thin films of Se79Te10Sb4Bi7, were prepared by Electron beam deposition technique. The structure of the as-prepared and annealed films has been studied by X-ray diffraction and the surface morphology by the scanning electron microscope (SEM). These studies show that there is a gradual change in structure and the formation of some polycrystalline structures in the amorphous phases is observed when the Se79Te10Sb4Bi7 film is annealed in the temperature range of 333-393 K. The optical transmission of these films has been studied as a function of photon wavelength in the range 300-2500 nm. It has been found that the optical band gap Egopt decreased with increasing annealing temperature in the range 333-393 K. The Urbach energy (Eu), optical conductivity (σopt), imaginary (εi), and real (εr) parts of the complex dielectric constant (ε) and lattice dielectric constant (εL) were also determined. The changes noticed in optical parameters with increasing annealing temperature were explained on the basis of structural relaxation as well as change in defect states and density of localized states due to amorphous-crystalline transformation.

Thermodynamic properties of PbTe, PbSe, and PbS: a first-principles study

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

Zhang, Yi; Ke, Xuezhi; Chen, Changfeng

2009-01-01

The recent discovery of novel lead chalcogenide-based thermoelectric materials has attracted great interest. These materials exhibit low thermal conductivity which is closely related to their lattice dynamics and thermodynamic properties. In this paper, we report a systematic study of electronic structures and lattice dynamics of the lead chalcogenides PbX (X=Te, Se, S) using first-principles density functional theory calculations and a direct force-constant method. We calculate the struc- tural parameters, elastic moduli, electronic band structures, dielectric constants, and Born effective charges. Moreover, we determine phonon dispersions, phonon density of states, and phonon softening modes in these materials. Based on the resultsmore » of these calculations, we further employ quasihar- monic approximation to calculate the heat capacity, internal energy, and vibrational entropy. The obtained results are in good agreement with experimental data. Lattice thermal conductivities are evaluated in terms of the Gruneisen parameters. The mode Gruneisen parameters are calculated to explain the anharmonicity in these materials. The effect of the spin-orbit interaction is found to be negligible in determining the thermodynamic properties of PbTe, PbSe, and PbS.« less

Optical properties of InN thin films

NASA Astrophysics Data System (ADS)

Malakhov, Vladislav Y.

2000-04-01

The basic optical properties of low temperature plasma enhanced chemical reactionary sputtered (PECRS) InN thin films are presented. Optical absorption and reflectance spectra of InN polycrystalline films at room temperature in visible and near infrared (NIR) regions were taken to determine direct band gap energy (2.03 eV), electron plasma resonances energy (0.6 eV), damping constant (0.18 eV), and optical effective mass of electrons (0.11). In addition the UV and visible reflectance spectra have been used to reproduce accurately dielectric function of wurtzite InN for assignments of the peak structures to interband transitions (1.5 - 12.0 eV) as well as to determine dielectric constant (9.3) and refractive index (>3.0). The revealed reflectance peaks at 485 and 590 cm-1 respectively in IR spectra are connected with TO and LO optical vibration modes of InN films. Some TO (485 cm-1) and LO (585 cm-1) phonon features of indium nitride polycrystalline films on ceramics were observed in Raman spectra and also discussed. The excellent possibilities of InN polycrystalline layers for potential application in optoelectronic devices such as LEDs based InGaAlN and high efficiency solar cells are confirmed.

Self-Assembly Strategies for Integrating Light Harvesting and Charge Separation in Artificial Photosynthetic Systems

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

Wasielewski, Michael R.

In natural photosynthesis, organisms optimize solar energy conversion through organized assemblies of photofunctional chromophores and catalysts within proteins that provide specifically tailored environments for chemical reactions. As with their natural counterparts, artificial photosynthetic systems for practical solar fuels production must collect light energy, separate charge, and transport charge to catalytic sites where multielectron redox processes will occur. While encouraging progress has been made on each aspect of this complex problem, researchers have not yet developed self-ordering and self-assembling components and the tailored environments necessary to realize a fully-functional artificial system. Previously researchers have used complex, covalent molecular systems comprised ofmore » chromophores, electron donors, and electron acceptors to mimic both the light-harvesting and the charge separation functions of photosynthetic proteins. These systems allow for study of the dependencies of electron transfer rate constants on donor?acceptor distance and orientation, electronic interaction, and the free energy of the reaction. The most useful and informative systems are those in which structural constraints control both the distance and the orientation between the electron donors and acceptors. Self-assembly provides a facile means for organizing large numbers of molecules into supramolecular structures that can bridge length scales from nanometers to macroscopic dimensions. The resulting structures must provide pathways for migration of light excitation energy among antenna chromophores, and from antennas to reaction centers. They also must incorporate charge conduits, that is, molecular 'wires' that can efficiently move electrons and holes between reaction centers and catalytic sites. The central scientific challenge is to develop small, functional building blocks with a minimum number of covalent linkages, which also have the appropriate molecular recognition properties to facilitate self-assembly of complete, functional artificial photosynthetic systems. In this Account, we explore how self-assembly strategies involving ?-stacking can be used to integrate light harvesting with charge separation and transport.« less

High accuracy electronic material level sensor

DOEpatents

McEwan, T.E.

1997-03-11

The High Accuracy Electronic Material Level Sensor (electronic dipstick) is a sensor based on time domain reflectometry (TDR) of very short electrical pulses. Pulses are propagated along a transmission line or guide wire that is partially immersed in the material being measured; a launcher plate is positioned at the beginning of the guide wire. Reflected pulses are produced at the material interface due to the change in dielectric constant. The time difference of the reflections at the launcher plate and at the material interface are used to determine the material level. Improved performance is obtained by the incorporation of: (1) a high accuracy time base that is referenced to a quartz crystal, (2) an ultrawideband directional sampler to allow operation without an interconnect cable between the electronics module and the guide wire, (3) constant fraction discriminators (CFDs) that allow accurate measurements regardless of material dielectric constants, and reduce or eliminate errors induced by triple-transit or ``ghost`` reflections on the interconnect cable. These improvements make the dipstick accurate to better than 0.1%. 4 figs.

High accuracy electronic material level sensor

DOEpatents

McEwan, Thomas E.

1997-01-01

The High Accuracy Electronic Material Level Sensor (electronic dipstick) is a sensor based on time domain reflectometry (TDR) of very short electrical pulses. Pulses are propagated along a transmission line or guide wire that is partially immersed in the material being measured; a launcher plate is positioned at the beginning of the guide wire. Reflected pulses are produced at the material interface due to the change in dielectric constant. The time difference of the reflections at the launcher plate and at the material interface are used to determine the material level. Improved performance is obtained by the incorporation of: 1) a high accuracy time base that is referenced to a quartz crystal, 2) an ultrawideband directional sampler to allow operation without an interconnect cable between the electronics module and the guide wire, 3) constant fraction discriminators (CFDs) that allow accurate measurements regardless of material dielectric constants, and reduce or eliminate errors induced by triple-transit or "ghost" reflections on the interconnect cable. These improvements make the dipstick accurate to better than 0.1%.

Influence of functional group on the electrical transport properties of polyvinyl alcohol grafted multiwall carbon nanotube composite thick film

NASA Astrophysics Data System (ADS)

Kumar Das, Amit; Dharmana, Reuben; Mukherjee, Ayan; Baba, Koumei; Hatada, Ruriko; Kumar Meikap, Ajit

2018-04-01

We present a novel technique to obtain a higher or lower value of dielectric constant due to the variation of a functional group on the surface of multiwall carbon nanotube (MWCNTs) for a polyvinyl alcohol (PVA) grafted MWCNT system. We have prepared PVA grafted pristine and different types of functionalized (-COOH, -OH, and -NH2) MWCNT nanocomposite films. The strong interfacial interaction between the host PVA matrix and nanofiller is characterized by different experimental techniques. The frequency variation of the electrical transport properties of the composite films is investigated in a wide temperature range (303 ≤ T ≤ 413 K) and frequency range (20 Hz ≤ f ≤ 1 MHz). The dielectric constant of the amine (-NH2) functionalized MWCNT incorporated PVA film is about 2 times higher than that of the pristine MWCNT embedded PVA film. The temperature variation of the dielectric constant shows an anomalous behaviour. The modified Cole-Cole equation simulated the experimentally observed dielectric spectroscopy at high temperature. The ac conductivity of the composite films obeys the correlated barrier hopping model. The imaginary part of the electric modulus study shows the ideal Debye-type behaviour at low frequency and deviation of that at high frequency. To illustrate the impedance spectroscopy of the nanocomposite films, we have proposed an impedance based battery equivalent circuit model. The current-voltage characteristic shows hysteresis behaviour of the nanocomposite films. The trap state height for all composite films is evaluated by simulating the current density-electric field data with the Poole-Frenkel emission model. This investigation opens a new avenue for designing electronic devices with a suitable combination of cost effective soft materials.

Electron-Hole Condensation in Semiconductors: Electrons and holes condense into freely moving liquid metallic droplets, a plasma phase with novel properties.

PubMed

Jeffries, C D

1975-09-19

In Ge and Si, and also in Ge-Si alloys (74), there is extensive evidence for the stable binding of electrons and holes into a cold plasma of constant density, which undergoes a phase separation. Liquid metallic drops 1 to 300 microm in size are formed, with lifetimes ranging from 0.1 to 600 microsec. For Ge a surprising amount is known: the phase diagram, the surface energy, the work function, the decay kinetics. Much less is known for Si. There is good agreement between theoretical and experimental values of the liquid density, the critical density, the critical temperature, and the binding energy. The stability of the liquid phase is strikingly dependent on band structure. The multivalley structure and mass anisotropy of Si, Ge, and Ge-Si, together with their indirect band gap, are no doubt responsible for the observed stability in these crystals. In the similar semiconductor gallium phosphide, drops have not yet been observed, most likely because the high impurity content traps the excitons. In gallium arsenide the existence of drops is controversial (75). Undoubtedly drops will be found to exist in other semiconductors, perhaps at even higher temperatures. This is an exciting field for the experimentalist; new phenomena are being rapidly discovered, usually before they are predicted. For the theorist, the electron-hole drop is of high intrinsic interest. It represents the first example of a quantum liquid of constant density in a periodic crystal lattice. A number of challenging experimental and theoretical problems remain.

Study on plasma pre-functionalized PVC film grafted with TiO2/PVP to improve blood compatible and antibacterial properties

NASA Astrophysics Data System (ADS)

Suganya, Arjunan; Shanmugavelayutham, Gurusamy; Serra Rodríguez, Carmen

2017-04-01

Research into the design of new biopolymers/polymer functionalized with nanoparticles is of tremendous interest to the medical sector, particularly with regard to blood-contacting devices. In this present study, a steady blood compatible and active antibacterial coating was fabricated by the grafting of titanium dioxide (TiO2)/polyvinylpyyrolidone (PVP) onto a polyvinyl chloride (PVC) film surface via the direct-current glow discharge plasma method. To enhance the chemical interaction between TiO2/PVP and PVC, the surfaces of the PVC films were functionalized by different plasmas (air, argon, and oxygen) before coating. In this study, the plasma parameters were varied, such as treatment time of about 5-20 min for a constant power of 100 W, potential 300 V, and a constant gas pressure of 2 Pa for air, argon, and oxygen gas environment. Then, the different plasma treatments on the PVC films, TiO2/PVP were grafted using a simple dip-coating method. In addition, the TiO2/PVP-grafted PVC films were characterized by contact angle, attenuated total reflectance Fourier transform infrared spectroscopy, field-emission scanning electron microscope, and x-ray photo electron spectroscopy. Importantly, TiO2/PVP is grafted onto the PVC surface due to the plasma-based retained functionality and demonstrates adhesive efficiency, which was observed by XPS. The bio-stability of the TiO2/PVP-modified PVC film was evaluated by in vitro platelet activation analysis and protein adsorption analysis. Then, the antibacterial properties were evaluated by the agar diffusion method against Escherichia coli. The result reveals that the grafting of TiO2/PVP was slightly higher for the 15 min oxygen plasma-functionalized PVC, which significantly decreases the platelet adhesion and protein adsorption. Moreover, the antibacterial properties of the 15 min oxygen plasma-functionalized PVC with TiO2/PVP-grafted film is also greatly improved compared with an air- and argon-functionalized surface. Our present study demonstrates that the plasma treatment is a beneficial and eco-friendly method to achieve higher hydrophilicity. Furthermore, our results indicated that the plasma-modified PVC exhibits appropriate anti-fouling performance.

Spectroscopic studies of Np(V) complexation

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

Stout, B.E.

The complexation of Np(V) with aliphatic (oxalic, malonic, succinic, glutaric, and maleic) and aromatic (phthalic, pyromellitic, hemimellitic, trimellitic, and mellitic) polycarboxylic acids was studied by spectrophotometry at 1 M ionic strength (NaClO{sub 4}) and 23 C. For the aliphatic systems, the stability of the neptunyl complexes was found to decrease as the carbon chain length of the ligand increased which was attributed to an entropy effect. In polycarboxylate systems, the stability constant decreased in the order hemimellitate > mellitate > pyromellitate > trimellitate, phthalate. With the exception of hemimellitate, this trend follows the order of decreasing basicity of the ligand.more » After correction of the stability constant for statistical effects, the stability of the mellitate, pyromellitate, trimellitate, and phthalate complexes were approximately the same. The unexpected strength the hemimellitate complexation was attributed to an increase in electron density at the binding site from the non-chelating carboxylate group through induction. The complexation of phthalate, trimellitate and hemimellitate and mellitate were studied as a function of pH. Trimellitate and mellitate were found to form ML as well as ML complexes while for phthalate and hemimellitate only ML species were observed. The stability constants of the cation-cation complexes Np(V)-U(VI) and Np(V)-Np(V), measured at 6 M ionic strength (HClO{sub 4}) and 25 C, were found to be 2.45 {+-} 0.05 and 1.41 {+-} 0.14, respectively. The change in enthalpy for the Np(V)-U(VI) system as determined by the measurement of the stability constant as function of temperature was -14.3 {+-} 1.6 kJ/mol.« less

Vibrational properties and bonding nature of Sb2Se3 and their implications for chalcogenide materials† †Electronic supplementary information (ESI) available: Additional computational data and discussion. See DOI: 10.1039/c5sc00825e Click here for additional data file.

PubMed Central

Deringer, Volker L.; Stoffel, Ralf P.; Wuttig, Matthias

2015-01-01

Antimony selenide (antimonselite, Sb2Se3) is a versatile functional material with emerging applications in solar cells. It also provides an intriguing prototype to study different modes of bonding in solid chalcogenides, all within one crystal structure. In this study, we unravel the complex bonding nature of crystalline Sb2Se3 by using an orbital-based descriptor (the crystal orbital Hamilton population, COHP) and by analysing phonon properties and interatomic force constants. We find particularly interesting behaviour for the medium-range Sb···Se contacts, which still contribute significant stabilisation but are much softer than the “traditional” covalent bonds. These results have implications for the assembly of Sb2Se3 nanostructures, and bond-projected force constants appear as a useful microscopic descriptor for investigating a larger number of chalcogenide functional materials in the future. PMID:29449929

Transporte electronico en nanoestructuras de carbono

NASA Astrophysics Data System (ADS)

Jodar Ferrandez, Esther

The aim of this work is the study of the electronic transport properties in several structures made of carbon nanotubes. This dissertation is divided in four chapters: (1) Chapter 1: Carbon Nanotubes. This chapter is a brief review of the foundations of carbon nanotubes (CNT). Main properties of CNT are explained. The subject developed here is important for the understanding of the results obtained in the bulk of this thesis. We carry out, in the first part of this chapter, an historical review of the discovering of CNT, that includes the history of the discovering of fullerenes, the predecessors for carbon nanotubes. Afterwards, a revision of the different methods for synthesizing nanotubes is done. The main part of this chapter treats of the description of the geometry, properties and electronic structure of CNT. Many equations deduced here will be used later. Finally, we discuss some research lines related to carbon nanotubes. (2) Chapter 2: Theoretical and numerical method. In this chapter we describe the numerical method we have developed to obtain the results presented in this work. For this purpose it is necessary to describe previously the theoretical method on which our calculations are based. We extensively explain the Green's function and its properties. A large part of our calculations are based in the obtention the GF of the system under study. This chapter finishes with the application of the equations described in order to obtain electronic properties associated with pure carbon nanotubes as an example of use. Anyway, these previous results will be used later. (3) Chapter 3: Cavities made of nanotubes. We denote as a cavity to the structure formed with a carbon nanotube sandwiched between other two carbon nanotubes (contacts), provided that the central region is wider than these contacts. In this chapter we perform some calculations of the properties associated to the electronic transport in cavities, as the local density of states and the transmission function. We analyze the influence of the width of the cavity and the distance between them (in the case of multiple cavities). Some interesting results are obtained in these calculations which have been published in international journals (Jodar et al. 2006, Jodar y Perez-Garrido 2007). We emphasize the presence of quasi-localized states in the cavities, which affects to the transmission function, the behaviour of some cavities formed with semi-conductor as quantum dots, or the study of the evolution of the system with multiple cavities to the limit of infinite cavities. (4) Chapter 4: Bloch Oscillations. In this chapter we investigate the properties of carbon nanotubes under a constant electric field. This configuration show Bloch oscillations, according to the work of Bloch and Zener. We study here the dynamics of these oscillations for different geometries as a function of the electric field applied. Specially, the behaviour of the occupation probability and the averaged quadratic displacement as a function of time. We have not found bibliography that deals with this phenomenon in Carbon Nanotubes, which is the aim of this chapter. We first study the behaviour of electrons in pure carbon nanotubes in a constant electric field, for different lengths of the CNT and different values of the electric field applied. We show how wavefunctions oscillate with a period that coincides with that given by theoretical expressions of Bloch oscillations for linear chains of atoms. Besides, we show the different kind of behaviour of localized and extended waves. In the final part of this chapter we apply a constant electric field to the structure studied in the chapter 3, i.e., the cavity. We show in this case that, besides Bloch oscillations, electrons can be confined in certain regions only by inserting the nanotube in an electric field.

Spectroscopy of selected metal-containing diatomic molecules

NASA Astrophysics Data System (ADS)

Gordon, Iouli E.

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7Sigma+ electronic state. The vibration-rotation bands from v = 1 → 0 to v = 3 → 2 for MnH, and from v = 1 → 0 to v = 4 → 3 for MnD were recorded at an instrumental resolution of 0.0085 cm-1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant oe for MnH was found to be 1546.84518(65) cm-1, the equilibrium rotational constant Be was found to be 5.6856789(103) cm-1 and the equilibrium bond distance re was determined to be 1.7308601(47) A. New high resolution emission spectra of CoH and CoD molecules have been recorded in the 640 nm to 3.5 mum region using a Fourier transform spectrometer. Many bands were observed for the A'3phi- X3phi electronic transition of CoH and CoD. In addition, a new [13.3]4 electronic state was found by observing the [13.3]4-X3phi3 and [13.3]4- X3phi4 transitions in the spectrum of CoD. Analysis of the transitions with DeltaO = 0, +/-1 provided more accurate values of spin-orbit splittings between O = 4 and O = 3 components. The ground state for both molecules was fitted both to band and Dunham-type constants. The estimated band constants of the perturbed upper states were also obtained. The emission spectrum of gas-phase YbO has been investigated using a Fourier transform spectrometer. A total of 8 red-degraded bands in the range 9 800--11 300 cm-1 were recorded at a resolution of 0.04 cm-1. Because of the multiple isotopomers present in the spectra, only 3 bands were rotationally analyzed. Perturbations were identified in two of these bands and all 3 transitions were found to terminate at the X1Sigma+ ground electronic state. The electronic configurations that give rise to the observed states are discussed and molecular parameters for all of the analyzed bands are reported. Electronic spectra of the previously unobserved EuH and EuD molecules were studied by means of Fourier transform spectroscopy and laser-induced fluorescence. The extreme complexity of these transitions made rotational assignments of EuH bands impossible. However, the spin-spin interaction constant, lambda, and Fermi contact parameter, bF, in the ground X9Sigma- electronic state were estimated for the 151EuH and 153EuH isotopologues. Electronic spectra of SmH, SmCl, TmH and ErF molecules were recorded for the first time using Fourier transform spectrometer. The poor signal to noise ratio of the observed bands coupled with their complexity prevented a rotational analysis. The electronic states that may be involved in the observed transitions are discussed.

Spectroscopy of selected metal-containing diatomic molecules

NASA Astrophysics Data System (ADS)

Gordon, Iouli

Fourier transform infrared emission spectra of MnH and MnD were observed in the ground X7[sigma]+ electronic state. The vibration-rotation bands from v = 1 to 0 to v = 3 to 2 for MnH, and from v = 1 to 0 to v = 4 to 3 for MnD were recorded at an instrumental resolution of 0. 0085 cm-1. Spectroscopic constants were determined for each vibrational level and equilibrium constants were found from a Dunham-type fit. The equilibrium vibrational constant [omega]e for MnH was found to be 1546. 84518(65) cm-1, the equilibrium rotational constant Be was found to be 5. 6856789(103) cm-1 and the equilibrium bond distance re was determined to be 1. 7308601(47) ?. New high resolution emission spectra of CoH and CoD molecules have been recorded in the 640 nm to 3. 5 _m region using a Fourier transform spectrometer. Many bands were observed for the A'3?-X3? electronic transition of CoH and CoD. In addition, a new [13. 3]4 electronic state was found by observing the [13. 3]4- X3?3 and [13. 3]4-X3?4 transitions in the spectrum of CoD. Analysis of the transitions with [delta][omega] = 0, ?1 provided more accurate values of spin-orbit splittings between [omega] = 4 and [omega] = 3 components. The ground state for both molecules was fitted both to band and Dunham-type constants. The estimated band constants of the perturbed upper states were also obtained. The emission spectrum of gas-phase YbO has been investigated using a Fourier transform spectrometer. A total of 8 red-degraded bands in the range 9 800 ? 11 300 cm-1 were recorded at a resolution of 0. 04 cm-1. Because of the multiple isotopomers present in the spectra, only 3 bands were rotationally analyzed. Perturbations were identified in two of these bands and all 3 transitions were found to terminate at the X1[sigma]+ ground electronic state. The electronic configurations that give rise to the observed states are discussed and molecular parameters for all of the analyzed bands are reported. Electronic spectra of the previously unobserved EuH and EuD molecules were studied by means of Fourier transform spectroscopy and laser-induced fluorescence. The extreme complexity of these transitions made rotational assignments of EuH bands impossible. However, the spin-spin interaction constant, [lambda], and Fermi contact parameter, bF, in the ground X9[sigma]- electronic state were estimated for the 151EuH and 153EuH isotopologues. Electronic spectra of SmH, SmCl, TmH and ErF molecules were recorded for the first time using Fourier transform spectrometer. The poor signal to noise ratio of the observed bands coupled with their complexity prevented a rotational analysis. The electronic states that may be involved in the observed transitions are discussed.

Imaginary parts of coupled electron and phonon propagators

NASA Astrophysics Data System (ADS)

Schwartzman, K.; Lawrence, W. E.

1988-01-01

Quasiparticle and phonon damping rates due to the electron-phonon and Coulomb interactions are obtained directly from the self-energy formalism of strong-coupling theory. This accounts for all processes involving phonon or quasiparticle decay into a single particle-hole pair, or quasiparticle decay by emission or absorption of a single real phonon. The two quasiparticle decay modes are treated on a common footing, without ad hoc separation, by accounting fully for the dynamics of the phonon propagator and the Coulomb vertex-the latter by expansion of the four-point Coulomb vertex function. The results are shown to be expressible in terms of only the physical (i.e., fully renormalized) energies and coupling constants, and are written in terms of spectral functions such as α2F(ω) and its generalizations. Expansion of these in powers of a phonon linewidth parameter distinguishes (in lowest orders) between quasiparticle decay modes involving real and virtual phonons. However, the simplest prescription for calculating decay rates involves an effective scattering amplitude in which this distinction is not made.

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.

A generalized Poisson solver for first-principles device simulations

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

Bani-Hashemian, Mohammad Hossein; VandeVondele, Joost, E-mail: joost.vandevondele@mat.ethz.ch; Brück, Sascha

2016-01-28

Electronic structure calculations of atomistic systems based on density functional theory involve solving the Poisson equation. In this paper, we present a plane-wave based algorithm for solving the generalized Poisson equation subject to periodic or homogeneous Neumann conditions on the boundaries of the simulation cell and Dirichlet type conditions imposed at arbitrary subdomains. In this way, source, drain, and gate voltages can be imposed across atomistic models of electronic devices. Dirichlet conditions are enforced as constraints in a variational framework giving rise to a saddle point problem. The resulting system of equations is then solved using a stationary iterative methodmore » in which the generalized Poisson operator is preconditioned with the standard Laplace operator. The solver can make use of any sufficiently smooth function modelling the dielectric constant, including density dependent dielectric continuum models. For all the boundary conditions, consistent derivatives are available and molecular dynamics simulations can be performed. The convergence behaviour of the scheme is investigated and its capabilities are demonstrated.« less

Time-domain separation of optical properties from structural transitions in resonantly bonded materials.

PubMed

Waldecker, Lutz; Miller, Timothy A; Rudé, Miquel; Bertoni, Roman; Osmond, Johann; Pruneri, Valerio; Simpson, Robert E; Ernstorfer, Ralph; Wall, Simon

2015-10-01

The extreme electro-optical contrast between crystalline and amorphous states in phase-change materials is routinely exploited in optical data storage and future applications include universal memories, flexible displays, reconfigurable optical circuits, and logic devices. Optical contrast is believed to arise owing to a change in crystallinity. Here we show that the connection between optical properties and structure can be broken. Using a combination of single-shot femtosecond electron diffraction and optical spectroscopy, we simultaneously follow the lattice dynamics and dielectric function in the phase-change material Ge2Sb2Te5 during an irreversible state transformation. The dielectric function changes by 30% within 100 fs owing to a rapid depletion of electrons from resonantly bonded states. This occurs without perturbing the crystallinity of the lattice, which heats with a 2-ps time constant. The optical changes are an order of magnitude larger than those achievable with silicon and present new routes to manipulate light on an ultrafast timescale without structural changes.

Strain relaxation in single crystal SrTiO3 grown on Si (001) by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Choi, Miri; Posadas, Agham; Dargis, Rytis; Shih, Chih-Kang; Demkov, Alexander A.; Triyoso, Dina H.; David Theodore, N.; Dubourdieu, Catherine; Bruley, John; Jordan-Sweet, Jean

2012-03-01

An epitaxial layer of SrTiO3 grown directly on Si may be used as a pseudo-substrate for the integration of perovskite oxides onto silicon. When SrTiO3 is initially grown on Si (001), it is nominally compressively strained. However, by subsequent annealing in oxygen at elevated temperature, an SiOx interlayer can be formed which alters the strain state of SrTiO3. We report a study of strain relaxation in SrTiO3 films grown on Si by molecular beam epitaxy as a function of annealing time and oxygen partial pressure. Using a combination of x-ray diffraction, reflection high energy electron diffraction, and transmission electron microscopy, we describe the process of interfacial oxidation and strain relaxation of SrTiO3 on Si (001). Understanding the process of strain relaxation of SrTiO3 on silicon will be useful for controlling the SrTiO3 lattice constant for lattice matching with functional oxide overlayers.

Synthesis and electronic factors in thermal cyclodimerization of functionalized aromatic trifluorovinyl ethers.

PubMed

Spraul, Bryan K; Suresh, S; Jin, Jianyong; Smith, Dennis W

2006-05-31

A series of 19 p-substituted aromatic trifluorovinyl ether compounds were prepared from versatile intermediate p-Br-C(6)H(4)-O-CF=CF(2) and underwent thermal radical mediated cyclodimerization to new difunctional compounds containing the 1,2-disubstituted perfluorocyclobutyl (PFCB) linkage. The synthetic scope demonstrates the functional group transformation tolerance of the fluorovinyl ether, and the dimers are useful as monomers for traditional step-growth polymerization methods. (19)F NMR spectra confirmed that p-substitution affects the trifluorovinyl ether group chemical shifts. The first kinetic studies and substituent effects on thermal cyclodimerization were performed, and the results indicated that electron-withdrawing groups slow the rate of cyclodimerization. The data were further analyzed using the Hammett equation, and reaction constants (rho) of -0.46 at 120 degrees C and -0.59 at 130 degrees C were calculated. This study presents the first liner free energy relationship reported for the cyclodimerization of aromatic trifluorovinyl ethers to PFCB compounds.

Nonadiabatic rate constants for proton transfer and proton-coupled electron transfer reactions in solution: Effects of quadratic term in the vibronic coupling expansion

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

Soudackov, Alexander; Hammes-Schiffer, Sharon

2015-11-17

Rate constant expressions for vibronically nonadiabatic proton transfer and proton-coupled electron transfer reactions are presented and analyzed. The regimes covered include electronically adiabatic and nonadiabatic reactions, as well as high-frequency and low-frequency regimes for the proton donor-acceptor vibrational mode. These rate constants differ from previous rate constants derived with the cumulant expansion approach in that the logarithmic expansion of the vibronic coupling in terms of the proton donor-acceptor distance includes a quadratic as well as a linear term. The analysis illustrates that inclusion of this quadratic term does not significantly impact the rate constants derived using the cumulant expansion approachmore » in any of the regimes studied. The effects of the quadratic term may become significant when using the vibronic coupling expansion in conjunction with a thermal averaging procedure for calculating the rate constant, however, particularly at high temperatures and for proton transfer interfaces with extremely soft proton donor-acceptor modes that are associated with extraordinarily weak hydrogen bonds. Even with the thermal averaging procedure, the effects of the quadratic term for weak hydrogen-bonding systems are less significant for more physically realistic models that prevent the sampling of unphysical short proton donor-acceptor distances, and the expansion of the coupling can be avoided entirely by calculating the couplings explicitly for the range of proton donor-acceptor distances. This analysis identifies the regimes in which each rate constant expression is valid and thus will be important for future applications to proton transfer and proton-coupled electron transfer in chemical and biological processes. We are grateful for support from National Institutes of Health Grant GM056207 (applications to enzymes) and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences (applications to molecular electrocatalysts).« less

New measurement of the electron magnetic moment and the fine structure constant.

PubMed

Hanneke, D; Fogwell, S; Gabrielse, G

2008-03-28

A measurement using a one-electron quantum cyclotron gives the electron magnetic moment in Bohr magnetons, g/2=1.001 159 652 180 73 (28) [0.28 ppt], with an uncertainty 2.7 and 15 times smaller than for previous measurements in 2006 and 1987. The electron is used as a magnetometer to allow line shape statistics to accumulate, and its spontaneous emission rate determines the correction for its interaction with a cylindrical trap cavity. The new measurement and QED theory determine the fine structure constant, with alpha{-1}=137.035 999 084 (51) [0.37 ppb], and an uncertainty 20 times smaller than for any independent determination of alpha.

Cascade Model of Ionization Multiplication of Electrons in Glow Discharge Plasma

NASA Astrophysics Data System (ADS)

Romanenko, V. A.; Solodky, S. A.; Kudryavtsev, A. A.; Suleymanov, I. A.

1996-10-01

For determination of EDF in non-uniform fields a Monte-Carlo simulation(Tran Ngoc An et al., J.Phys.D: Appl. Phys. 10, 2317 (1977))^,(J.P. Boeuf et al., Phys.D: Appl.Phys. 15, 2169 (1982)) is applied. As alternative multi-beam cascade model(H.B. Valentini, Contrib.Plasma Phys. 27, 331 (1987)) is offered. Our model eliminates defects of that model and enables to determine EDF of low pressure plasma in non-uniform fields. A cascade model (with EDF dividing in monoenergetic electron groups) for arbitrary electric potential profile was used. Modeling was carried out for electron forward scattering only, constant electron mean free path; ionization was considered only. The equation system was solved for the region with kinetic energies more than ionization energy. The boundary conditions (on ionization energy curve) take into account electron transitions from higher-lying level in the less than ionization energy region and secondary electron production. The problem solution in analytical functions was obtained. The insertion of additional processes does not make significant difficulties. EDF and electrokinetical parameters in helium from numerical calculations are well agreed with above-mentioned authors. Work was carried out under RFFI (project N 96-02-18417) support.

Microscopic Theory and Simulation of Quantum-Well Intersubband Absorption

NASA Technical Reports Server (NTRS)

Li, Jianzhong; Ning, C. Z.

2004-01-01

We study the linear intersubband absorption spectra of a 15 nm InAs quantum well using the intersubband semiconductor Bloch equations with a three-subband model and a constant dephasing rate. We demonstrate the evolution of intersubband absorption spectral line shape as a function of temperature and electron density. Through a detailed examination of various contributions, such as the phase space filling effects, the Coulomb many-body effects and the non-parabolicity effect, we illuminate the underlying physics that shapes the spectra. Keywords: Intersubband transition, linear absorption, semiconductor heterostructure, InAs quantum well

Functionalization of ( n, 0) CNTs ( n = 3-16) by uracil: DFT studies

NASA Astrophysics Data System (ADS)

Mirzaei, Mahmoud; Harismah, Kun; Jafari, Elham; Gülseren, Oğuz; Rad, Ali Shokuhi

2018-01-01

Density functional theory (DFT) calculations were performed to investigate stabilities and properties for uracil (U)-functionalized carbon nanotubes (CNTs). To this aim, the optimized molecular properties were evaluated for ( n, 0) models of CNTs ( n = 3-16) in the original and U-functionalized forms. The results indicated that the dipole moments and energy gaps were independent of tubular diameters whereas the binding energies showed that the U-functionalization could be better achieved for n = 8-11 curvatures of ( n, 0) CNTs. Further studies based on the evaluated atomic-scale properties, including quadrupole coupling constants ( C Q ), indicated that the electronic properties of atoms could detect the effects of diameters variations of ( n, 0) CNTs, in which the effects were very much significant for the atoms around the U-functionalization regions. Finally, the achieved results of singular U, original CNTs, and CNT-U hybrids were compared to each other to demonstrate the stabilities and properties for the U-functionalized ( n, 0) CNTs.

Many-Body Spectral Functions from Steady State Density Functional Theory.

PubMed

Jacob, David; Kurth, Stefan

2018-03-14

We propose a scheme to extract the many-body spectral function of an interacting many-electron system from an equilibrium density functional theory (DFT) calculation. To this end we devise an ideal scanning tunneling microscope (STM) setup and employ the recently proposed steady-state DFT formalism (i-DFT) which allows one to calculate the steady current through a nanoscopic region coupled to two biased electrodes. In our setup, one of the electrodes serves as a probe ("STM tip"), which is weakly coupled to the system we want to measure. In the ideal STM limit of vanishing coupling to the tip, the system is restored to quasi-equilibrium and the normalized differential conductance yields the exact equilibrium many-body spectral function. Calculating this quantity from i-DFT, we derive an exact relation expressing the interacting spectral function in terms of the Kohn-Sham one. As illustrative examples, we apply our scheme to calculate the spectral functions of two nontrivial model systems, namely the single Anderson impurity model and the Constant Interaction Model.

Multi-wavelength spectrophotometric determination of acidity constant of some newly synthesized Schiff bases and their QSPR study

NASA Astrophysics Data System (ADS)

Hemmateenejad, Bahram; Emami, Leila; Sharghi, Hashem

2010-01-01

The acidity constants of some newly synthesized Schiff base derivatives were determined by hard-model based multivariate data analysis of the spectrophotometric data in the course of pH-metric titration in 50% (v/v) methanol-water binary solvent. The employed data analysis method was also able to extract the pure spectra and pH-dependent concentration profiles of the acid-base species. The molecules that possess different substituents (both electron donating and withdrawing) on the ortho-, meta- and para-positions of one of the phenyl ring showed variable acidity constants ranging from 8.77 to 11.07 whereas the parent molecule had an acidity constant of 10.25. To investigate the quantitative effects of changing of substitution pattern on the acidity constant, a quantitative structure-property relation analysis was conducted using substituent constants and molecular descriptor. Some models with high statistical quality (measured by cross-validation Q2) were obtained. It was found that the acidity constant of the studied molecules in the methanol-water mixed solvent not only is affected by electronic features of the solutes but also by the lipophilic interaction between methanol part of solvent and the deprotonated solutes.

Ab initio investigation of the structural and electronic properties of the MgFBrxCl1-x quaternary alloy

NASA Astrophysics Data System (ADS)

Mokhtari, Ali; Alidoosti, Mohammad

2014-11-01

In the present work, we have performed first principles calculations to study the structural and electronic properties of the MgFBrxCl1-x quaternary alloys using the pseudo-potential plane wave approach within the framework of density functional theory. By using the optimized initial parameters, we have obtained the physical quantities such as equilibrium lattice constants a and c, cohesive energy and band gap and then fitted the results by a quadratic expression for all x compositions. The results of bulk modulus exhibit nearly linear concentration dependence (LCD) but other quantities show nonlinear dependence. Finally, we have calculated the total and angular momentum decomposed (partial) density of states and determined the contributions of different orbitals of each atoms.

Solvent controlled intramolecular electron transfer in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate and acetonitrile

NASA Astrophysics Data System (ADS)

Rumble, Christopher A.; Maroncelli, Mark

2018-05-01

Time-resolved emission techniques were used to study the excited-state intramolecular electron transfer of 9-(4-biphenyl)-10-methylacridinium (BPAc+) in mixtures of 1-butyl-3-methylimidizolium tetrafluoroborate ([Im41][BF4])+ acetonitrile (ACN), a mixture previously shown to be of nearly constant polarity and nearly ideal mixing behavior. Reaction times (τrxn) track solvation times (τsolv) as a function of mixture composition over a range of more than 3 orders of magnitude in τsolv. This same correlation extends to a variety of neat dipolar solvents and ionic liquids. Reaction times are ˜2-fold larger than τsolv over most of the range studied but appear to reach a limiting value of ˜3 ps in the fastest solvents.

Impact of the wetting layer thickness on the emission wavelength of direct band gap GeSn/Ge quantum dots

NASA Astrophysics Data System (ADS)

Ilahi, Bouraoui; Al-Saigh, Reem; Salem, Bassem

2017-07-01

The effects of the wetting layer thickness (t WL) on the electronic properties of direct band gap type-I strained dome shaped Ge(1-x)Sn x quantum dot (QD) embedded in Ge matrix is numerically studied. The emission wavelength and the energy difference between S and P electron levels have been evaluated as a function of t WL for different QD size and composition with constant height to diameter ratio. The emission wavelength is found to be red shifted by increasing the wetting layer thickness, with smaller size QD being more sensitive to the variation of t WL. Furthermore, the minimum Sn composition required to fit the directness criteria is found to reduce by increasing the wetting layer thickness.

Hammett analyses of halocarbene-halocarbanion equilibria.

PubMed

Wang, Lei; Moss, Robert A; Krogh-Jespersen, Karsten

2013-04-19

Substituted arylchlorocarbenes (X = H, p-Cl, p-CF3, p-F, m-Cl) reacted reversibly with Cl(-) in dichloroethane to form the corresponding aryldichloromethide carbanions. Equilibrium constants and rate constants for the forward and reverse reactions were correlated by the Hammett equation. DFT methods were used to compute equilibrium constants and electronic absorption spectra.

Non-Maxwellian electron energy probability functions in the plume of a SPT-100 Hall thruster

NASA Astrophysics Data System (ADS)

Giono, G.; Gudmundsson, J. T.; Ivchenko, N.; Mazouffre, S.; Dannenmayer, K.; Loubère, D.; Popelier, L.; Merino, M.; Olentšenko, G.

2018-01-01

We present measurements of the electron density, the effective electron temperature, the plasma potential, and the electron energy probability function (EEPF) in the plume of a 1.5 kW-class SPT-100 Hall thruster, derived from cylindrical Langmuir probe measurements. The measurements were taken on the plume axis at distances between 550 and 1550 mm from the thruster exit plane, and at different angles from the plume axis at 550 mm for three operating points of the thruster, characterized by different discharge voltages and mass flow rates. The bulk of the electron population can be approximated as a Maxwellian distribution, but the measured distributions were seen to decline faster at higher energy. The measured EEPFs were best modelled with a general EEPF with an exponent α between 1.2 and 1.5, and their axial and angular characteristics were studied for the different operating points of the thruster. As a result, the exponent α from the fitted distribution was seen to be almost constant as a function of the axial distance along the plume, as well as across the angles. However, the exponent α was seen to be affected by the mass flow rate, suggesting a possible relationship with the collision rate, especially close to the thruster exit. The ratio of the specific heats, the γ factor, between the measured plasma parameters was found to be lower than the adiabatic value of 5/3 for each of the thruster settings, indicating the existence of non-trivial kinetic heat fluxes in the near collisionless plume. These results are intended to be used as input and/or testing properties for plume expansion models in further work.

Substituent effects on the redox states of locally functionalized single-walled carbon nanotubes revealed by in situ photoluminescence spectroelectrochemistry.

PubMed

Shiraishi, Tomonari; Shiraki, Tomohiro; Nakashima, Naotoshi

2017-11-09

Single-walled carbon nanotubes (SWNTs) with local chemical modification have been recognized as a novel near infrared (NIR) photoluminescent nanomaterial due to the emergence of a new red-shifted photoluminescence (PL) with enhanced quantum yields. As a characteristic feature of the locally functionalized SWNTs (lf-SWNTs), PL wavelength changes occur with the structural dependence of the substituent structures in the modified aryl groups, showing up to a 60 nm peak shift according to an electronic property difference of the aryl groups. Up to now, however, the structural effect on the electronic states of the lf-SWNTs has been discussed only on the basis of theoretical calculations due to the very limited amount of modifications. Herein, we describe the successfully-determined electronic states of the aryl-modified lf-SWNTs with different substituents (Ar-X SWNTs) using an in situ PL spectroelectrochemical method based on electrochemical quenching of the PL intensities analyzed by the Nernst equation. In particular, we reveal that the local functionalization of (6,5)SWNTs induced potential changes in the energy levels of the HOMO and the LUMO by -23 to -38 meV and +20 to +22 meV, respectively, compared to those of the pristine SWNTs, which generates exciton trapping sites with narrower band gaps. Moreover, the HOMO levels of the Ar-X SWNTs specifically shift in a negative potential direction by 15 meV according to an enhancement of the electron-accepting property of the substituents in the aryl groups that corresponds to an increase in the Hammet substituent constants, suggesting the importance of the dipole effect from the aryl groups on the lf-SWNTs to the level shift of the frontier orbitals. Our method is a promising way to characterize the electronic features of the lf-SWNTs.

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.

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).

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.

8 MeV electron beam induced modifications in the thermal, structural and electrical properties of nanophase CeO2 for potential electronics applications

NASA Astrophysics Data System (ADS)

Babitha, K. K.; Sreedevi, A.; Priyanka, K. P.; Ganesh, S.; Varghese, Thomas

2018-06-01

The effect of 8 MeV electron beam irradiation on the thermal, structural and electrical properties of CeO2 nanoparticles synthesized by chemical precipitation route was investigated. The dose dependent effect of electron irradiation was studied using various characterization techniques such as, thermogravimetric and differential thermal analyses, X-ray diffraction, Fourier transformed infrared spectroscopy and impedance spectroscopy. Systematic investigation based on the results of structural studies confirm that electron beam irradiation induces defects and particle size variation on CeO2 nanoparticles, which in turn results improvements in AC conductivity, dielectric constant and loss tangent. Structural modifications and high value of dielectric constant for CeO2 nanoparticles due to electron beam irradiation make it as a promising material for the fabrication of gate dielectric in metal oxide semiconductor devices.

Ultrafast dynamics of non-equilibrium electrons and strain generation under femtosecond laser irradiation of Nickel

NASA Astrophysics Data System (ADS)

Tsibidis, George D.

2018-04-01

We present a theoretical study of the ultrafast electron dynamics in transition metals of large electron-phonon coupling constant using ultrashort pulsed laser beams. The significant influence of the dynamics of produced nonthermal electrons to electron thermalisation and electron-phonon interaction is thoroughly investigated for various values of the pulse duration (i.e., from 10 fs to 2.3 ps). The model correlates the role of nonthermal electrons, relaxation processes and induced stress-strain fields. Simulations are presented by choosing Nickel (Ni) as a test material to compute electron-phonon relaxation time due to its large electron-phonon coupling constant. We demonstrate that the consideration of the aforementioned factors leads to significant changes compared to the results the traditional two-temperature model provides. The proposed model predicts a substantially ( 33%) smaller damage threshold and a large increase of the stress ( 20%, at early times) which first underlines the role of the nonthermal electron interactions and second enhances its importance with respect to the precise determination of laser specifications in material micromachining techniques.

High-throughput screening of inorganic compounds for the discovery of novel dielectric and optical materials

DOE PAGES

Petousis, Ioannis; Mrdjenovich, David; Ballouz, Eric; ...

2017-01-31

Dielectrics are an important class of materials that are ubiquitous in modern electronic applications. Even though their properties are important for the performance of devices, the number of compounds with known dielectric constant is on the order of a few hundred. Here, we use Density Functional Perturbation Theory as a way to screen for the dielectric constant and refractive index of materials in a fast and computationally efficient way. Our results constitute the largest dielectric tensors database to date, containing 1,056 compounds. Details regarding the computational methodology and technical validation are presented along with the format of our publicly availablemore » data. In addition, we integrate our dataset with the Materials Project allowing users easy access to material properties. Finally, we explain how our dataset and calculation methodology can be used in the search for novel dielectric compounds.« less

Magnetoimpedance and magnetodielectric properties of single phase 45PMN-20PFW-35PT ceramics

NASA Astrophysics Data System (ADS)

Ramachandran, B.; Sudarshan, N.; Rao, M. S. Ramachandra

2010-05-01

Phase pure and dense polycrystalline 45PMN-20PFW-35PT sample has been synthesized using a columbite precursor method. Structure and surface morphology of the samples were studied using x-ray diffraction and scanning electron microscope. The sample showed the expected reduction in dielectric constant and polarization (Pmax=17 μC/cm2) compared with that of the parent compound, 65PMN-35PT (Pmax=22 μC/cm2). The sample is also found to be paramagnetic, which is confirmed by magnetization measurements as a function of temperature and an applied magnetic field. The sample was also tested for magnetoelectric coupling by measuring its dielectric constant and impedance at different applied magnetic fields. The observed colossal negative magnetodielectrics (177%) and colossal positive magnetoimpedance (130%) effect at 7 MHz, which is due to piezoelectric radial vibration. This is an indirect confirmation of the coupling between the electric and magnetic order parameters.

High-throughput screening of inorganic compounds for the discovery of novel dielectric and optical materials

PubMed Central

Petousis, Ioannis; Mrdjenovich, David; Ballouz, Eric; Liu, Miao; Winston, Donald; Chen, Wei; Graf, Tanja; Schladt, Thomas D.; Persson, Kristin A.; Prinz, Fritz B.

2017-01-01

Dielectrics are an important class of materials that are ubiquitous in modern electronic applications. Even though their properties are important for the performance of devices, the number of compounds with known dielectric constant is on the order of a few hundred. Here, we use Density Functional Perturbation Theory as a way to screen for the dielectric constant and refractive index of materials in a fast and computationally efficient way. Our results constitute the largest dielectric tensors database to date, containing 1,056 compounds. Details regarding the computational methodology and technical validation are presented along with the format of our publicly available data. In addition, we integrate our dataset with the Materials Project allowing users easy access to material properties. Finally, we explain how our dataset and calculation methodology can be used in the search for novel dielectric compounds. PMID:28140408

Proposal for the determination of nuclear masses by high-precision spectroscopy of Rydberg states

NASA Astrophysics Data System (ADS)

Wundt, B. J.; Jentschura, U. D.

2010-06-01

The theoretical treatment of Rydberg states in one-electron ions is facilitated by the virtual absence of the nuclear-size correction, and fundamental constants like the Rydberg constant may be in the reach of planned high-precision spectroscopic experiments. The dominant nuclear effect that shifts transition energies among Rydberg states therefore is due to the nuclear mass. As a consequence, spectroscopic measurements of Rydberg transitions can be used in order to precisely deduce nuclear masses. A possible application of this approach to hydrogen and deuterium, and hydrogen-like lithium and carbon is explored in detail. In order to complete the analysis, numerical and analytic calculations of the quantum electrodynamic self-energy remainder function for states with principal quantum number n = 5, ..., 8 and with angular momentum ell = n - 1 and ell = n - 2 are described \\big(j = \\ell \\pm {\\textstyle {\\frac{1}{2}}}\\big).

High-throughput screening of inorganic compounds for the discovery of novel dielectric and optical materials.

PubMed

Petousis, Ioannis; Mrdjenovich, David; Ballouz, Eric; Liu, Miao; Winston, Donald; Chen, Wei; Graf, Tanja; Schladt, Thomas D; Persson, Kristin A; Prinz, Fritz B

2017-01-31

Dielectrics are an important class of materials that are ubiquitous in modern electronic applications. Even though their properties are important for the performance of devices, the number of compounds with known dielectric constant is on the order of a few hundred. Here, we use Density Functional Perturbation Theory as a way to screen for the dielectric constant and refractive index of materials in a fast and computationally efficient way. Our results constitute the largest dielectric tensors database to date, containing 1,056 compounds. Details regarding the computational methodology and technical validation are presented along with the format of our publicly available data. In addition, we integrate our dataset with the Materials Project allowing users easy access to material properties. Finally, we explain how our dataset and calculation methodology can be used in the search for novel dielectric compounds.

Exploring phase stability, electronic and mechanical properties of Ce–Pb intermetallic compounds using first-principles calculations

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

Tao, Xiaoma; Computational Alloy Design Group, IMDEA Materials Institute, Getafe, Madrid 28906; Wang, Ziru

2016-05-15

The phase stability, electronic and mechanical properties of Ce–Pb intermetallics have been investigated by using first-principles calculations. Five stable and four metastable phases of Ce–Pb intermetallics were verified. Among them, CePb{sub 2} has been confirmed as HfGa{sub 2}-type structure. For Ce{sub 5}Pb{sub 3}, the high pressure phase transformation from D8{sub m} to D8{sub 8} with trivalent Ce has been predicted to occur at P=1.2 GPa and a high temperature phase transformation has been predicted from D8{sub m} to D8{sub 8} with tetravalent Ce at 531.5 K. The calculated lattice constants of the five stable phases are in good agreement withmore » experimental values. The electronic density of states, charge density and electron localization function of Ce{sub 3}Pb have been calculated, which indicated that the Ce and Pb show ionic behavior. The polycrystalline bulk modulus, shear modulus, Young's modulus, and Poisson's ratio are also estimated from the calculated single crystalline elastic constants. All of the calculated elastic constants satisfy mechanical stability criteria. The microhardness and mechanical anisotropy are predicted. The anisotropic nature of the Ce–Pb intermetallic compounds are demonstrated by the three-dimensional orientation dependent surfaces of Young's moduli and linear compressibility are also demonstrated. The longitudinal, transverse and average sound velocities and the Debye temperatures are also obtained in this work. The Ce{sub 3}Pb has the largest Debye temperature of 192.6 K, which means the Ce{sub 3}Pb has a highest melting point and high thermal conductivity than other compounds. - Graphical abstract: The convex hull plots of the enthalpies of formation for Ce–Pb binary systems calculated at 0 K. - Highlights: • The five stable and four metastable phases in the Ce–Pb binary system were predicted. • The crystal structure of CePb{sub 2} has been confirmed as HfGa{sub 2}-type.« less

Auger-generated hot carrier current in photo-excited forward biased single quantum well blue light emitting diodes

NASA Astrophysics Data System (ADS)

Espenlaub, Andrew C.; Alhassan, Abdullah I.; Nakamura, Shuji; Weisbuch, Claude; Speck, James S.

2018-04-01

We report on measurements of the photo-modulated current-voltage and electroluminescence characteristics of forward biased single quantum well, blue InGaN/GaN light emitting diodes with and without electron blocking layers. Low intensity resonant optical excitation of the quantum well was observed to induce an additional forward current at constant forward diode bias, in contrast to the usual sense of the photocurrent in photodiodes and solar cells, as well as an increased electroluminescence intensity. The presence of an electron blocking layer only slightly decreased the magnitude of the photo-induced current at constant forward bias. Photo-modulation at constant forward diode current resulted in a reduced diode bias under optical excitation. We argue that this decrease in diode bias at constant current and the increase in forward diode current at constant applied bias can only be due to additional hot carriers being ejected from the quantum well as a result of an increased Auger recombination rate within the quantum well.

Dielectric constant extraction of graphene nanostructured on SiC substrates from spectroscopy ellipsometry measurement using Gauss–Newton inversion method

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

Maulina, Hervin; Santoso, Iman, E-mail: iman.santoso@ugm.ac.id; Subama, Emmistasega

2016-04-19

The extraction of the dielectric constant of nanostructured graphene on SiC substrates from spectroscopy ellipsometry measurement using the Gauss-Newton inversion (GNI) method has been done. This study aims to calculate the dielectric constant and refractive index of graphene by extracting the value of ψ and Δ from the spectroscopy ellipsometry measurement using GNI method and comparing them with previous result which was extracted using Drude-Lorentz (DL) model. The results show that GNI method can be used to calculate the dielectric constant and refractive index of nanostructured graphene on SiC substratesmore faster as compared to DL model. Moreover, the imaginary partmore » of the dielectric constant values and coefficient of extinction drastically increases at 4.5 eV similar to that of extracted using known DL fitting. The increase is known due to the process of interband transition and the interaction between the electrons and electron-hole at M-points in the Brillouin zone of graphene.« less

Seeking maximum linearity of transfer functions

NASA Astrophysics Data System (ADS)

Silva, Filipi N.; Comin, Cesar H.; Costa, Luciano da F.

2016-12-01

Linearity is an important and frequently sought property in electronics and instrumentation. Here, we report a method capable of, given a transfer function (theoretical or derived from some real system), identifying the respective most linear region of operation with a fixed width. This methodology, which is based on least squares regression and systematic consideration of all possible regions, has been illustrated with respect to both an analytical (sigmoid transfer function) and a simple situation involving experimental data of a low-power, one-stage class A transistor current amplifier. Such an approach, which has been addressed in terms of transfer functions derived from experimentally obtained characteristic surface, also yielded contributions such as the estimation of local constants of the device, as opposed to typically considered average values. The reported method and results pave the way to several further applications in other types of devices and systems, intelligent control operation, and other areas such as identifying regions of power law behavior.

Ab-initio investigation of Rb substitution in KTP single crystal

NASA Astrophysics Data System (ADS)

Ghoohestani, Marzieh; Arab, Ali; Hashemifar, S. Javad; Sadeghi, Hossein

2018-01-01

The effects of rubidium doping on the structural, electronic, and optical properties of KTiOPO4 (KTP) are investigated in the framework of density functional theory. The equilibrium structural parameters of KTP and RbTiOPO4 (RTP) are calculated within the local density and Perdew-Burke-Ernzerhof (PBE), Wu-Cohen, and PBEsol formulation of generalized gradient approximations. We discuss that PBEsol predicts better equilibrium parameters for the KTP alloy. In addition, the variation of lattice constants and Ti-O-Ti bond angles are evaluated as a function of rubidium concentration. The modern modified Becke-Johnson functional is applied for more accurate band gap determination in the pure and alloyed KTP/RTP compounds. The phenomenological pseudoinversion parameter is calculated for a qualitative understanding of the effect of impurity on a non-linear optical response of KTP. We also analyze the behavior of the dielectric function, dispersive refractive indices, and birefringence of KTP/RTP alloys.

Ab initio study of the structural, electronic, elastic and thermal conductivity properties of SrClF with pressure effects

NASA Astrophysics Data System (ADS)

Lv, Zhen-Long; Cui, Hong-Ling; Wang, Hui; Li, Xiao-Hong; Ji, Guang-Fu

2017-04-01

SrClF is an important optical crystal and can be used as pressure gauge in diamond anvil cell at high pressure. In this work, we performed a systematic study on the structural, electronic and elastic properties of SrClF under pressure, as well as its thermal conductivity, by first-principles calculation. Different exchange-correlation functionals were tested and PBESOL was finally chosen to study these properties of SrClF. Studies reveal that SrClF has a bulk modulus of about 56.2 GPa (by fitting equation of states) or 54.3 GPa (derived from elastic constants), which agree well with the experimental result. SrClF is mechanically and dynamically stable up to 50 GPa. Its elastic constants increase with the applied pressure, but its mechanical anisotropy deteriorates as the pressure increases. Investigation of its electronic properties reveals that SrClF is a direct band-gap insulator with a gap value of 5.73 eV at 0 GPa, which decreases with the increasing pressure and the reason is found by analysing the partial density of states. Based on the calculated phonon dispersion curves, thermal conductivity of SrClF is predicated. At ambient conditions, the predicted thermal conductivity is about 3.74 Wm-1 K-1, while that obtained using the simplified Slack model give a slightly larger value of 4.62 Wm-1 K-1.

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

DOE PAGES

Wilker, Molly B.; Utterback, James K.; Greene, Sophie; ...

2017-12-08

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

Role of Surface-Capping Ligands in Photoexcited Electron Transfer between CdS Nanorods and [FeFe] Hydrogenase and the Subsequent H 2 Generation

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

Wilker, Molly B.; Utterback, James K.; Greene, Sophie

Complexes of CdS nanorods and [FeFe] hydrogenase from Clostridium acetobutylicum have been shown to photochemically produce H 2. This study examines the role of the ligands that passivate the nanocrystal surfaces in the electron transfer from photoexcited CdS to hydrogenase and the H 2 generation that follows. We functionalized CdS nanorods with a series of mercaptocarboxylate surface-capping ligands of varying lengths and measured their photoexcited electron relaxation by transient absorption (TA) spectroscopy before and after hydrogenase adsorption. Rate constants for electron transfer from the nanocrystals to the enzyme, extracted by modeling of TA kinetics, decrease exponentially with ligand length, suggestingmore » that the ligand layer acts as a barrier to charge transfer and controls the degree of electronic coupling. Relative light-driven H 2 production efficiencies follow the relative quantum efficiencies of electron transfer, revealing the critical role of surface-capping ligands in determining the photochemical activity of these nanocrystal-enzyme complexes. Our results suggest that the H 2 production in this system could be maximized with a choice of a surface-capping ligand that decreases the distance between the nanocrystal surface and the electron injection site of the enzyme.« less

Evaluation of Radiation Belt Space Weather Forecasts for Internal Charging Analyses

NASA Technical Reports Server (NTRS)

Minow, Joseph I.; Coffey, Victoria N.; Jun, Insoo; Garrett, Henry B.

2007-01-01

A variety of static electron radiation belt models, space weather prediction tools, and energetic electron datasets are used by spacecraft designers and operations support personnel as internal charging code inputs to evaluate electrostatic discharge risks in space systems due to exposure to relativistic electron environments. Evaluating the environment inputs is often accomplished by comparing whether the data set or forecast tool reliability predicts measured electron flux (or fluence over a given period) for some chosen period. While this technique is useful as a model metric, it does not provide the information necessary to evaluate whether short term deviances of the predicted flux is important in the charging evaluations. In this paper, we use a 1-D internal charging model to compute electric fields generated in insulating materials as a function of time when exposed to relativistic electrons in the Earth's magnetosphere. The resulting fields are assumed to represent the "true" electric fields and are compared with electric field values computed from relativistic electron environments derived from a variety of space environment and forecast tools. Deviances in predicted fields compared to the "true" fields which depend on insulator charging time constants will be evaluated as a potential metric for determining the importance of predicted and measured relativistic electron flux deviations over a range of time scales.

Correlational and thermodynamic properties of finite-temperature electron liquids in the hypernetted-chain approximation.

PubMed

Tanaka, Shigenori

2016-12-07

Correlational and thermodynamic properties of homogeneous electron liquids at finite temperatures are theoretically analyzed in terms of dielectric response formalism with the hypernetted-chain (HNC) approximation and its modified version. The static structure factor and the local-field correction to describe the strong Coulomb-coupling effects beyond the random-phase approximation are self-consistently calculated through solution to integral equations in the paramagnetic (spin unpolarized) and ferromagnetic (spin polarized) states. In the ground state with the normalized temperature θ=0, the present HNC scheme well reproduces the exchange-correlation energies obtained by quantum Monte Carlo (QMC) simulations over the whole fluid phase (the coupling constant r s ≤100), i.e., within 1% and 2% deviations from putative best QMC values in the paramagnetic and ferromagnetic states, respectively. As compared with earlier studies based on the Singwi-Tosi-Land-Sjölander and modified convolution approximations, some improvements on the correlation energies and the correlation functions including the compressibility sum rule are found in the intermediate to strong coupling regimes. When applied to the electron fluids at intermediate Fermi degeneracies (θ≈1), the static structure factors calculated in the HNC scheme show good agreements with the results obtained by the path integral Monte Carlo (PIMC) simulation, while a small negative region in the radial distribution function is observed near the origin, which may be associated with a slight overestimation for the exchange-correlation hole in the HNC approximation. The interaction energies are calculated for various combinations of density and temperature parameters ranging from strong to weak degeneracy and from weak to strong coupling, and the HNC values are then parametrized as functions of r s and θ. The HNC exchange-correlation free energies obtained through the coupling-constant integration show reasonable agreements with earlier results including the PIMC-based fitting over the whole fluid region at finite degeneracies in the paramagnetic state. In contrast, a systematic difference between the HNC and PIMC results is observed in the ferromagnetic state, which suggests a necessity of further studies on the exchange-correlation free energies from both aspects of analytical theory and simulation.

Transition from the adiabatic to the sudden limit in core-electron photoemission

NASA Astrophysics Data System (ADS)

Hedin, Lars; Michiels, John; Inglesfield, John

1998-12-01

Experimental results for core-electron photoemission Jk(ω) are often compared with the one-electron spectral function Ac(ɛk-ω), where ω is the photon energy, ɛk is the photoelectron energy, and the optical transition matrix elements are taken as constant. Since Jk(ω) is nonzero only for ɛk>0, we must actually compare it with Ac(ɛk-ω)θ(ɛk). For metals Ac(ω) is known to have a quasiparticle (QP) peak with an asymmetric power-law [theories of Mahan, Nozières, de Dominicis, Langreth, and others (MND)] singularity due to low-energy particle-hole excitations. The QP peak starts at the core-electron energy ɛc, and is followed by an extended satellite (shakeup) structure at smaller ω. For photon energies ω just above threshold, ωth=-ɛc, Ac(ɛk-ω)θ(ɛk) as a function of ɛk (ω constant) is cut just behind the quasiparticle peak, and neither the tail of the MND line nor the plasmon satellites are present. The sudden (high-energy) limit is given by a convolution of Ac(ω) and a loss function, i.e., by the Berglund-Spicer two-step expression. Thus Ac(ω) alone does not give the correct photoelectron spectrum, neither at low nor at high energies. We present an extension of the quantum-mechanical (QM) models developed earlier by Inglesfield, and by Bardyszewski and Hedin to calculate Jk(ω). It includes recoil and damping, as well as shakeup effects and extrinsic losses, is exact in the high-energy limit, and allows calculations of Jk(ω) including the MND line and multiple plasmon losses. The model, which involves electrons coupled to quasibosons, is motivated by detailed arguments. As an illustration we have made quantitative calculations for a semi-infinite jellium with the density of aluminum metal and an embedded atom. The coupling functions (fluctuation potentials) between the electron and the quasibosons are related to the random-phase-approximation dielectric function, and different levels of approximations are evaluated numerically. The differences in the predictions for the photoemission spectra are found small. We confirm the finding by Langreth that the BS limit is reached only in the keV range. At no photon energy are the plasmon satellites close to being either purely intrinsic or extrinsic. For photoelectron energies larger than a few times the plasmon energy, a semiclassical approximation gives results very close to our QM model. At lower energies the QM model gives a large peak in the ratio between the total intensity in the first plasmon satellite and the main peak, which is not reproduced by the SC expression. This maximum has a simple physical explanation in terms of different dampings of the electrons in the QP peak and in the satellite. For the MND peak Jk(ω) and Ac(ɛk-ω) agree well for a range of a few eV, and experimental data can thus be used to extract the MND singularity index. For an embedded atom at a small distance from the surface there are, however, substantial deviations from the large-distance limit. Our model is simple enough to perform quantitative calculations allowing for band-structure and surface details.

The factors influencing nonlinear characteristics of the short-circuit current in dye-sensitized solar cells investigated by a numerical model.

PubMed

Shi, Yushuai; Dong, Xiandui

2013-06-24

A numerical model for interpretation of the light-intensity-dependent nonlinear characteristics of the short-circuit current in dye-sensitized solar cells is suggested. The model is based on the continuity equation and includes the influences of the nongeminate recombination between electrons and electron acceptors in the electrolyte and the geminate recombination between electrons and oxidized dye molecules. The influences of the order and rate constant of the nongeminate recombination reaction, the light-absorption coefficient of the dye, the film thickness, the rate constant of geminate recombination, and the regeneration rate constant on the nonlinear characteristics of the short-circuit current are simulated and analyzed. It is proposed that superlinear and sublinear characteristics of the short-circuit current should be attributed to low electron-collection efficiency and low dye-regeneration efficiency, respectively. These results allow a deep understanding of the origin of the nonlinear characteristics of the short-circuit current in solar cells. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

QED Based Calculation of the Fine Structure Constant

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

Lestone, John Paul

2016-10-13

Quantum electrodynamics is complex and its associated mathematics can appear overwhelming for those not trained in this field. Here, semi-classical approaches are used to obtain a more intuitive feel for what causes electrostatics, and the anomalous magnetic moment of the electron. These intuitive arguments lead to a possible answer to the question of the nature of charge. Virtual photons, with a reduced wavelength of λ, are assumed to interact with isolated electrons with a cross section of πλ 2. This interaction is assumed to generate time-reversed virtual photons that are capable of seeking out and interacting with other electrons. Thismore » exchange of virtual photons between particles is assumed to generate and define the strength of electromagnetism. With the inclusion of near-field effects the model presented here gives a fine structure constant of ~1/137 and an anomalous magnetic moment of the electron of ~0.00116. These calculations support the possibility that near-field corrections are the key to understanding the numerical value of the dimensionless fine structure constant.« less

Experimental studies of fundamental issues in electron transfer through nanometer scale devices

NASA Astrophysics Data System (ADS)

Yamamoto, Hiromichi

Electron transfer reactions constitute many of the primary events in materials science, chemistry, physics, and biochemistry, e.g. the electron transport properties and photoexcited processes in solids and molecules, chemical reactions, corrosion, photosynthesis, respiration, and so forth. A self-assembled monolayer (SAM) film provides us with a unique environment not only to understand and manipulate the surface electronic properties of a solid, but also to control electron transfer processes at the interface. The first topic in this thesis describes the structure and electron tunneling characterization of alkanethiol SAMs on InP(100). Angle-resolved X-ray photoelectron spectroscopy was used to characterize the bonding of alkanethiols to n-InP surfaces and to measure the monolayer thickness. The results showed that the sulfur binds to In atoms on the surface, and provided film thicknesses of 6.4 A for C8H17SH, 11.1 A for C12H25SH, and 14.9 A for C16H 33SH, resulting in an average tilt angle of 55°. The analysis indicated that super-exchange coupling between the alkane chains plays an important role in defining electron tunneling barriers, especially for highly tilted chains. The second topic describes studies of cytochrome c bound to pure and mixed SAMs of o-terminated alkanethiol (terminated with pyridine, imidazole or nitrile groups) and alkanethiol on gold. Electrochemical methods are used to determine electron transfer rate constants of cytochrome c, and scanning tunneling microscopy to observe the cytochrome c on the SAM. Detailed analysis revealed direct association of the heme of cytochrome c with the terminal groups of the SAMs and a 'turning-over' of the electron transfer of cytochrome c from adiabatic to non-adiabatic regime. The third topic describes studies of oxidation and reduction of cytochrome c in solution through eleven different self-assembled monolayers (SAMs) on gold electrodes by cyclic voltammetry. Electron transfer rate constants of cytochrome c through the eleven SAMs ranged from ≤10-4 to ˜10-1 cm/sec. A strong correlation between the electron transfer rate constants and the hydrogen bonding ability of the SAM is identified. This correlation is discussed in terms of the dependence of the rate constant on the outer-sphere reorganization energy and the electronic coupling between the cytochrome and the differently terminated monolayer films.

Combined valence bond-molecular mechanics potential-energy surface and direct dynamics study of rate constants and kinetic isotope effects for the H + C2H6 reaction.

PubMed

Chakraborty, Arindam; Zhao, Yan; Lin, Hai; Truhlar, Donald G

2006-01-28

This article presents a multifaceted study of the reaction H+C(2)H(6)-->H(2)+C(2)H(5) and three of its deuterium-substituted isotopologs. First we present high-level electronic structure calculations by the W1, G3SX, MCG3-MPWB, CBS-APNO, and MC-QCISD/3 methods that lead to a best estimate of the barrier height of 11.8+/-0.5 kcal/mol. Then we obtain a specific reaction parameter for the MPW density functional in order that it reproduces the best estimate of the barrier height; this yields the MPW54 functional. The MPW54 functional, as well as the MPW60 functional that was previously parametrized for the H+CH(4) reaction, is used with canonical variational theory with small-curvature tunneling to calculate the rate constants for all four ethane reactions from 200 to 2000 K. The final MPW54 calculations are based on curvilinear-coordinate generalized-normal-mode analysis along the reaction path, and they include scaled frequencies and an anharmonic C-C bond torsion. They agree with experiment within 31% for 467-826 K except for a 38% deviation at 748 K; the results for the isotopologs are predictions since these rate constants have never been measured. The kinetic isotope effects (KIEs) are analyzed to reveal the contributions from subsets of vibrational partition functions and from tunneling, which conspire to yield a nonmonotonic temperature dependence for one of the KIEs. The stationary points and reaction-path potential of the MPW54 potential-energy surface are then used to parametrize a new kind of analytical potential-energy surface that combines a semiempirical valence bond formalism for the reactive part of the molecule with a standard molecular mechanics force field for the rest; this may be considered to be either an extension of molecular mechanics to treat a reactive potential-energy surface or a new kind of combined quantum-mechanical/molecular mechanical (QM/MM) method in which the QM part is semiempirical valence bond theory; that is, the new potential-energy surface is a combined valence bond molecular mechanics (CVBMM) surface. Rate constants calculated with the CVBMM surface agree with the MPW54 rate constants within 12% for 534-2000 K and within 23% for 200-491 K. The full CVBMM potential-energy surface is now available for use in variety of dynamics calculations, and it provides a prototype for developing CVBMM potential-energy surfaces for other reactions.

Effect of molecular conformations on the electronic transport in oxygen-substituted alkanethiol molecular junctions

NASA Astrophysics Data System (ADS)

Wang, Minglang; Wang, Hao; Zhang, Guangping; Wang, Yongfeng; Sanvito, Stefano; Hou, Shimin

2018-05-01

The relationship between the molecular structure and the electronic transport properties of molecular junctions based on thiol-terminated oligoethers, which are obtained by replacing every third methylene unit in the corresponding alkanethiols with an oxygen atom, is investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Our calculations show that the low-bias conductance depends strongly on the conformation of the oligoethers in the junction. Specifically, in the cases of trans-extended conformation, the oxygen-dominated transmission peaks are very sharp and well below the Fermi energy, EF, thus hardly affect the transmission around EF; the Au-S interface hybrid states couple with σ-bonds in the molecular backbone forming the conduction channel at EF, resulting in a conductance decay against the molecular length close to that for alkanethiols. By contrast, for junctions with oligoethers in helical conformations, some π-type oxygen orbitals coupling with the Au-S interface hybrid states contribute to the transmission around EF. The molecule-electrode electronic coupling is also enhanced at the non-thiol side due to the specific spatial orientation introduced by the twist of the molecular backbone. This leads to a much smaller conductance decay constant. Our findings highlight the important role of the molecular conformation of oligoethers in their electronic transport properties and are also helpful for the design of molecular wires with heteroatom-substituted alkanethiols.

Dominance of broken bonds and nonbonding electrons at the nanoscale

NASA Astrophysics Data System (ADS)

Sun, Chang Q.

2010-10-01

Although they exist ubiquitously in human bodies and our surroundings, the impact of nonbonding lone electrons and lone electron pairs has long been underestimated. Recent progress demonstrates that: (i) in addition to the shorter and stronger bonds between under-coordinated atoms that initiate the size trends of the otherwise constant bulk properties when a substance turns into the nanoscale, the presence of lone electrons near to broken bonds generates fascinating phenomena that bulk materials do not demonstrate; (ii) the lone electron pairs and the lone pair-induced dipoles associated with C, N, O, and F tetrahedral coordination bonding form functional groups in biological, organic, and inorganic specimens. By taking examples of surface vacancy, atomic chain end and terrace edge states, catalytic enhancement, conducting-insulating transitions of metal clusters, defect magnetism, Coulomb repulsion at nanoscale contacts, Cu3C2H2 and Cu3O2 surface dipole formation, lone pair neutralized interface stress, etc, this article will focus on the development and applications of theory regarding the energetics and dynamics of nonbonding electrons, aiming to raise the awareness of their revolutionary impact to the society. Discussion will also extend to the prospective impacts of nonbonding electrons on mysteries such as catalytic enhancement and catalysts design, the density anomalies of ice and negative thermal expansion, high critical temperature superconductivity induced by B, C, N, O, and F, the molecular structures and functionalities of CF4 in anti-coagulation of synthetic blood, NO signaling, and enzyme telomeres, etc. Meanwhile, an emphasis is placed on the necessity and effectiveness of understanding the properties of substances from the perspective of bond and nonbond formation, dissociation, relaxation and vibration, and the associated energetics and dynamics of charge repopulation, polarization, densification, and localization. Finding and grasping the factors controlling the nonbonding states and making them of use in functional materials design and identifying their limitations will form, in the near future, a subject area of ``nonbonding electronics and energetics'', which could be even more challenging, fascinating, promising, and rewarding than dealing with core or valence electrons alone.

A highly efficient nano-cluster artificial peroxidase and its direct electrochemistry on a nano complex modified glassy carbon electrode.

PubMed

Hong, Jun; Wang, Wei; Huang, Kun; Yang, Wei-Yun; Zhao, Ying-Xue; Xiao, Bao-Lin; Gao, Yun-Fei; Moosavi-Movahedi, Zainab; Ghourchian, Hedayatollah; Moosavi-Movahedi, Ali Akbar

2012-01-01

A nano-cluster with highly efficient peroxide activity was constructed based on nafion (NF) and cytochrome c (Cyt c). UV-Vis spectrometry and transmission electron microscopy (TEM) methods were utilized for characterization of the nano-structured enzyme or artificial peroxidase (AP). The nano-cluster was composed of a Chain-Ball structure, with an average ball size of about 40 nm. The Michaelis-Menten (K(m)) and catalytic rate (k(cat)) constants of the AP were determined to be 2.5 ± 0.4 µM and 0.069 ± 0.001 s(-1), respectively, in 50 mM PBS at pH 7.0. The catalytic efficiency of the AP was evaluated to be 0.028 ± 0.005 µM(-1) s(-1), which was 39 ± 5% as efficient as the native horseradish peroxidase (HRP). The AP was also immobilized on a functional multi-wall carbon nanotube (MWNCTs)-gold colloid nanoparticles (AuNPs) nano-complex modified glassy carbon (GC) electrode. The cyclic voltammetry of AP on the nano complex modified GC electrode showed a pair of well-defined redox peaks with a formal potential (E°') of -45 ± 2 mV (vs. Ag/AgCl) at a scan rate of 0.05 V/s. The heterogeneous electron transfer rate constant (k(s)) was evaluated to be 0.65 s(-1). The surface concentration of electroactive AP on GC electrode (Γ) was 7 × 10(-10) mol cm(-2). The apparent Michaelis-Menten constant (K(m)(app)) was 0.23 nM.

Thermodynamic and electron paramagnetic resonance characterization of flavin in succinate dehydrogenase.

PubMed

Ohnishi, T; King, T E; Salerno, J C; Blum, H; Bowyer, J R; Maida, T

1981-06-10

Thermodynamic parameters of succinate dehydrogenase flavin were determined potentiometrically from the analysis of free radical signal levels as a function of the oxidation-reduction potential. Midpoint redox potentials of consecutive 1-electron transfer steps are -127 and -31 mV at pH 7.0. This corresponds to a stability constant of intermediate stability, 2.5 x 10(-2), which suggests flavin itself may be a converter from n = 2 to n = 1 electron transfer steps. The pK values of the free radical (FlH . in equilibrium Fl . -) and the fully reduced form (FlH2 in equilibrium FlH-) were estimated as 8.0 +/- 0.2 and 7.7 +/- 0.2, respectively. Succinate dehydrogenase flavosemiquinone elicits an EPR spectrum at g = 2.00 with a peak to peak width of 1.2 mT even in the protonated form, suggesting the delocalization in the unpaired electron density. A close proximity of succinate dehydrogenase flavin and iron-sulfur cluster S-1 was demonstrated based on the enhancement of flavin spin relaxation by Center S-1.

Fluoro-polymer functionalized graphene for flexible ferroelectric polymer-based high-k nanocomposites with suppressed dielectric loss and low percolation threshold.

PubMed

Yang, Ke; Huang, Xingyi; Fang, Lijun; He, Jinliang; Jiang, Pingkai

2014-12-21

Flexible nanodielectric materials with high dielectric constant and low dielectric loss have huge potential applications in the modern electronic and electric industry. Graphene sheets (GS) and reduced-graphene oxide (RGO) are promising fillers for preparing flexible polymer-based nanodielectric materials because of their unique two-dimensional structure and excellent electrical and mechanical properties. However, the easy aggregation of GS/RGO significantly limits the potential of graphene in enhancing the dielectric constant of polymer composites. In addition, the poor filler/matrix nanoscale interfacial adhesion also causes difficulties in suppressing the dielectric loss of the composites. In this work, using a facile and environmentally friendly approach, polydopamine coated RGO (PDA-RGO) and fluoro-polymer functionalized RGO (PF-PDA-RGO) were prepared. Compared with the RGO prepared by the conventional methods [i.e. hydrazine reduced-graphene oxide (H-RGO)] and PDA-RGO, the resulting PF-PDA-RGO nanosheets exhibit excellent dispersion in the ferroelectric polymer matrix [i.e. poly(vinylidene fluoride-co-hexafluoro propylene), P(VDF-HFP)] and strong interfacial adhesion with the matrix, leading to a low percolation threshold (fc = 1.06 vol%) and excellent flexibility for the corresponding nanocomposites. Among the three nanocomposites, the P(VDF-HFP)/PF-PDA-RGO nanocomposites exhibited the optimum performance (i.e. simultaneously having high dielectric constant and low dielectric loss). For instance, at 1000 Hz, the P(VDF-HFP) nanocomposite sample with 1.0 vol% PF-PDA-RGO has a dielectric constant of 107.9 and a dielectric loss of 0.070, showing good potential for dielectric applications. Our strategy provides a new pathway to prepare high performance flexible nanodielectric materials.

A surprisingly complex aqueous chemistry of the simplest amino acid. A pulse radiolysis and theoretical study on H/D kinetic isotope effects in the reaction of glycine anions with hydroxyl radicals.

PubMed

Stefanić, I; Ljubić, I; Bonifacić, M; Sabljić, A; Asmus, K-D; Armstrong, D A

2009-04-07

A pulse radiolysis study was carried out of the reaction rate constants and kinetic isotope effects of hydroxyl-radical-induced H/D abstraction from the most-simple alpha-amino acid glycine in its anionic form in water. The rate constants and yields of three predominantly formed radical products, glycyl (NH2-*CH-CO2-), aminomethyl (NH2-*CH2), and aminyl (*NH-CH2-CO2-) radicals, as well as of their partially or fully deuterated analogs, were found to be of comparable magnitude. The primary, secondary, and primary/secondary H/D kinetic isotope effects on the rate constants were determined with respect to each of the three radicals. The unusual variety of products for such an elementary reaction between two small and simple species indicates a complex mechanism with several reactions taking place simultaneously. Thus, a theoretical modeling of the reaction mechanism and kinetics in the gas- and aqueous phase was performed by using the unrestricted density functional theory with the BB1K functional (employing the polarizable continuum model for the aqueous phase), unrestricted coupled cluster UCCSD(T) method, and improved canonical variational theory. Several hydrogen-bonded prereaction complexes and transition states were detected. In particular, the calculations pointed to a significant mechanistic role of the three-electron two-orbital (sigma/sigma* N therefore O) hemibonded prereaction complexes in the aqueous phase. A good agreement with the experimental rate constants and kinetic isotope effects was achieved by downshifting the calculated reaction barriers by 3 kcal mol(-1) and damping the NH(D) stretching frequency by a factor of 0.86.

Defects and Transport in Lithium Niobium Trioxide

NASA Astrophysics Data System (ADS)

Mehta, Apurva

1990-01-01

This dissertation presents work done on characterizing the defects and transport properties of congruent LiNbO _3. The focus of the study is the high temperature (800^circC to 1000^circC) equilibrium defect structure. The majority defects are described in terms of the 'LiNbO_3-ilmenite' defect model previously presented (26). Here the emphasis is placed on quantifying the defect concentrations. Congruent LiNbO_3 is highly nonstoichiometric. The large concentration of ionic defects present are mobile and contribute to electrical conduction. The ionic conduction was separated from the total conduction using defect chemistry and the transference number thus obtained was checked against the transference number obtained in a galvanic cell measurement. LiNbO_3 is an insulator (band gap = 4 eV). Hence one assumes that almost all of the conduction electrons are created by reduction. The degree of oxygen nonstoichiometry, a measure of the extent of chemical reduction, and the electron concentrations, were quantified as a function of oxygen partial pressure and the temperature by coulometric titration. The nonstoichiometry thus obtained was compared with nonstoichiometry obtained by TGA measurements. By fixing the phase composition of the sample in a buffered system, a set of constant composition measurements could be undertaken. These constant composition measurements were used to obtain the enthalpy of formation of conduction electrons, 1.95 eV, and the hopping energy for their motion at elevated temperatures, 0.55 eV, independently. The sum of the two energies was obtained by measuring the temperature dependence of the electronic conduction. The sum of the energies was found to be in excellent agreement with the energy obtained from equilibrium conduction. In conclusion, a quantitative and self-consistent picture of defects and their migration in LiNbO _3 was obtained.

Modeling and calculation of RKKY exchange coupling to explain Ti-vacancy-induced ferromagnetism in Ta-doped TiO2

NASA Astrophysics Data System (ADS)

Majidi, Muhammad Aziz; Bupu, Annamaria; Fauzi, Angga Dito

2017-12-01

We present a theoretical study on Ti-vacancy-induced ferromagnetism in anatase TiO2. A recent experimental study has revealed room temperature ferromagnetism in Ta-doped anatase TiO2thin films (Rusydi et al., 2012) [7]. Ta doping assists the formation of Ti vacancies which then induce the formation of localized magnetic moments around the Ti vacancies. As neighboring Ti vacancies are a few unit cells apart, the ferromagnetic order is suspected to be mediated by itinerant electrons. We propose that such an electron-mediated ferromagnetism is driven by Ruderman-Kittel-Kasuya-Yosida (RKKY) exchange interaction. To examine our hypothesis, we construct a tight-binding based model Hamiltonian for the anatase TiO2 system. We calculate the RKKY exchange coupling constant of TiO2 as a function of distance between local magnetic moments at various temperatures. We model the system by taking only the layer containing a unit of TiO2, at which the Ti vacancy is believed to form, as our effective two-dimensional unit cell. Our model incorporates the Hubbard repulsive interactions between electrons occupying Ti d orbitals treated within mean-field approximation. The density of states profile resulting from the model captures the relevant electronic properties of TiO2, such as the energy gap of 3.4 eV and the n-type character, which may be a measure of the adequacy of the model. The calculated RKKY coupling constant shows that the ferromagnetic coupling extends up to 3-4 unit cells and enhances slightly as temperature is increased from 0 to 400 K. These results support our hypothesis that the ferromagnetism of this system is driven by RKKY mechanism.

Cubic and orthorhombic structures of aluminum hydride Al H3 predicted by a first-principles study

NASA Astrophysics Data System (ADS)

Ke, Xuezhi; Kuwabara, Akihide; Tanaka, Isao

2005-05-01

The most stable structure of aluminum hydride AlH3 is believed to be a hexagonal symmetry. However, using the density functional theory, we have identified two more stable structures for the AlH3 with the cubic and orthorhombic symmetries. Based on the quasiharmonic approximation, the cubic and orthorhombic AlH3 are almost degenerate when the zero-point energies are included. The geometric and electronic structures, the phonon, and the thermodynamic properties for the hexagonal, cubic, and orthorhombic AlH3 have been studied by means of density functional theory and direct ab initio force constant approach. The calculated electronic structures, phonon density of states, and thermodynamic functions [including S(T) and H(T)-H(0) ] for the three hydrides are similar. The results show that these three hydrides have negative enthalpies of formation, but positive free energies of formation. This conclusion is the same as that made by Wolverton for the hexagonal AlH3 [Phys. Rev. B 69, 144109 (2004)]. The thermodynamic properties indicate that the orthorhombic and cubic AlH3 should be more difficult to dissociate than the hexagonal AlH3 .

Effect of SiO2 grafted MWCNTs on the mechanical and dielectric properties of PEN composite films

NASA Astrophysics Data System (ADS)

Jin, Fei; Feng, Mengna; Huang, Xu; Long, Cheng; Jia, Kun; Liu, Xiaobo

2015-12-01

In this study, the functional poly (arylene ether nitrile) (PEN)/multiwall carbon nanotubes (MWCNTs)/SiO2 nanocomposite with high mechanical and good electrical properties were fabricated through a simple and effective method. Specifically, the surface modification using highly ordered and porous SiO2 not only improves the dispersion of the MWCNTs in polymer matrix, but also combines the excellent properties of SiO2 and MWCNTs. Transmission electron microscopy (TEM), Fourier transform infrared spectra (FTIR), and scanning electron microscope (SEM) were employed to confirm the surface functionalization of MWCNTs. As a result, all the composite films exhibited good dielectric properties with high dielectric constant of 7 as well as low dielectric loss of 0.04. Besides, the results of mechanical tests showed that the tensile strength and modulus reached their highest values at the 2 wt% MWCNTs-SiO2 loading content (125 MPa and 2950 MPa, respectively). The rheological results showed that MWCNTs-SiO2/PEN composites have a typical solid-like viscoelastic response as frequencies changes. Therefore, all the results revealed that surface functionalization has strong influence on the dispersion state of MWCNTs in PEN matrix.

General contraction of Gaussian basis sets. II - Atomic natural orbitals and the calculation of atomic and molecular properties

NASA Technical Reports Server (NTRS)

Almlof, Jan; Taylor, Peter R.

1990-01-01

A recently proposed scheme for using natural orbitals from atomic configuration interaction wave functions as a basis set for linear combination of atomic orbitals (LCAO) calculations is extended for the calculation of molecular properties. For one-electron properties like multipole moments, which are determined largely by the outermost regions of the molecular wave function, it is necessary to increase the flexibility of the basis in these regions. This is most easily done by uncontracting the outermost Gaussian primitives, and/or by adding diffuse primitives. A similar approach can be employed for the calculation of polarizabilities. Properties which are not dominated by the long-range part of the wave function, such as spectroscopic constants or electric field gradients at the nucleus, can generally be treated satisfactorily with the original atomic natural orbital sets.

An ab initio density functional study of the optical functions of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystals.

PubMed

Reshak, Ali H; Kityk, I V; Khenata, R; Al-Douri, Y; Auluck, S

2012-09-01

An ab initio investigation of the optical constants of 9-Methyl-3-Thiophen-2-YI-Thieno [3,2e] [1,2,4] Thriazolo [4,3c] Pyrimidine-8-Carboxylic Acid Ethyl Ester crystal is performed within a framework of local density approximation (LDA), and the Engel-Vosko generalized gradient approximation (EV-GGA) exchange correlation potentials. It is established that there are two independent molecules (A and B) exhibiting different intra-molecular interactions: C-H⋯O (A) and C-H⋯N (B). These intra-molecular interactions favor stabilization of the crystal structure for molecules A and B. It should be emphasized that there exist remarkable π-π interactions between the pyrimidine rings of the two neighbors B molecules giving extra strengths and stabilizations to the superamolecular structure. These different intra-molecular interactions C-H⋯O (A) and C-H⋯N (B) and the π-π interaction between the pyrimidine rings of the two neighbors B molecules give principal contribution to dispersion of optical properties. With a view to seek deeper insight into the electronic structure, the optical properties were investigated. Our calculations show that the optical constants are very anisotropic. The EVGGA calculation shows a blue spectral shift of around 0.024 eV with significant changes in the spectra compared to the LDA calculation. The observed spectral shifts are in agreement with the calculated band structure and corresponding electron density of states. Copyright © 2012 Elsevier B.V. All rights reserved.

Ab initio calculations of deep-level carrier nonradiative recombination rates in bulk semiconductors.

PubMed

Shi, Lin; Wang, Lin-Wang

2012-12-14

Nonradiative carrier recombination is of both applied and fundamental interest. Here a novel algorithm is introduced to calculate such a deep level nonradiative recombination rate using the ab initio density functional theory. This algorithm can calculate the electron-phonon coupling constants all at once. An approximation is presented to calculate the phonon modes for one impurity in a large supercell. The neutral Zn impurity site together with a N vacancy is considered as the carrier-capturing deep impurity level in bulk GaN. Its capture coefficient is calculated as 5.57 × 10(-10)cm(3)/s at 300 K. We found that there is no apparent onset of such a nonradiative process as a function of temperature.

Einstein coefficients and oscillator strengths for low lying state of CO molecules

NASA Astrophysics Data System (ADS)

Swer, S.; Syiemiong, A.; Ram, M.; Jha, A. K.; Saxena, A.

2018-04-01

Einstein Coefficients and Oscillator Strengths for different state of CO molecule have been calculated using LEROY'S LEVEL program and MOLCAS ab initio code. Using the wave function derived from Morse potential and transition dipole moment obtained from ab initio calculation, The potential energy functions were computed for these states using the spectroscopic constants. The Morse potential of these states and electronic transition dipole moment of the transition calculated in a recent ab initio study have been used in LEVEL program to produce transition dipole matrix element for a large number of bands. Einstein Coefficients have also been used to compute the radiative lifetimes of several vibrational levels and the calculated values are compared with other theoretical results and experimental values.

Stress evolution and associated microstructure during transient creep of olivine at 1000-1200 °C

NASA Astrophysics Data System (ADS)

Thieme, M.; Demouchy, S.; Mainprice, D.; Barou, F.; Cordier, P.

2018-05-01

We study the mechanical response and correlated microstructure of axial deformed fine-grained olivine aggregates as a function of incremental finite strains. Deformation experiments were conducted in uniaxial compression in an internally heated gas-medium deformation apparatus at temperatures of 1000 and 1200 °C, at strain rates of 10-6 s-1 to 10-5 s-1 and at confining pressure of 300 MPa. Sample volumes are around 1.2 cm3. Finite strains range from 0.1 to 8.6% and corresponding maximal (final) differential stresses range from 80 to 1073 MPa for deformation at 1000 °C and from 71 to 322 MPa for deformation at 1200 °C. At 1200 °C, samples approach steady state deformation after about 8% of strain. At 1000 °C, significant strain hardening leads to stresses exceeding the confining pressure by a factor of 3.5 with brittle deformation after 3% of strain. Deformed samples were characterized by electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). EBSD maps with step sizes as low as 50 nm were acquired without introducing analytical artifacts for the first time. The grain size of deformed samples ranges from 2.1 to 2.6 μm. Despite clear strain hardening, texture or microstructure do not change as a function of stress or finite strain. This observation is supported by a constant texture strength (J-index) and symmetry (BA-index), constant grain shape and aspect ratio, constant density of geometrically necessary dislocations, grain orientation spread, and constant subgrain boundary spacing and misorientation in between samples. TEM shows that all samples exhibit unambiguous dislocation activity but with a highly heterogeneous dislocation distribution. Olivine grains display evidence of [1 0 0] and [0 0 1] slip activity, but there is no evidence of interaction between the dislocations from the different slip systems. Several observations of grain boundaries acting as dislocation sources have been found. We find no confirmation of increasing dislocation densities as the cause for strain hardening during transient creep. This suggests other, yet not fully understood mechanisms affecting the strength of deformed olivine. These mechanisms could possibly involve grain boundaries. Such mechanisms are relevant for the deformation of uppermost mantle rocks, where the Si diffusion rate is too slow and dislocation glide must be accommodated in another way to fulfill the von Mises criterion.

Influence of Humic Acid Complexation with Metal Ions on Extracellular Electron Transfer Activity.

PubMed

Zhou, Shungui; Chen, Shanshan; Yuan, Yong; Lu, Qin

2015-11-23

Humic acids (HAs) can act as electron shuttles and mediate biogeochemical cycles, thereby influencing the transformation of nutrients and environmental pollutants. HAs commonly complex with metals in the environment, but few studies have focused on how these metals affect the roles of HAs in extracellular electron transfer (EET). In this study, HA-metal (HA-M) complexes (HA-Fe, HA-Cu, and HA-Al) were prepared and characterized. The electron shuttle capacities of HA-M complexes were experimentally evaluated through microbial Fe(III) reduction, biocurrent generation, and microbial azoreduction. The results show that the electron shuttle capacities of HAs were enhanced after complexation with Fe but were weakened when using Cu or Al. Density functional theory calculations were performed to explore the structural geometry of the HA-M complexes and revealed the best binding sites of the HAs to metals and the varied charge transfer rate constants (k). The EET activity of the HA-M complexes were in the order HA-Fe > HA-Cu > HA-Al. These findings have important implications for biogeochemical redox processes given the ubiquitous nature of both HAs and various metals in the environment.

Electronic tunneling through a potential barrier on the surface of a topological insulator

NASA Astrophysics Data System (ADS)

Zhou, Benliang; Zhou, Benhu; Zhou, Guanghui

2016-12-01

We investigate the tunneling transport for electrons on the surface of a topological insulator (TI) through an electrostatic potential barrier. By using the Dirac equation with the continuity conditions for all segments of wave functions at the interfaces between regions inside and outside the barrier, we calculate analytically the transmission probability and conductance for the system. It is demonstrated that, the Klein paradox can also been observed in the system same as in graphene system. Interestingly, the conductance reaches the minimum value when the incident electron energy is equal to the barrier strength. Moreover, with increasing barrier width, the conductance turns up some tunneling oscillation peaks, and larger barrier strength can cause lower conductance, shorter period but larger oscillation amplitude. The oscillation amplitude decreases as the barrier width increases, which is similar as that of the system consisting of the compressive uniaxial strain applied on a TI, but somewhat different from that of graphene system where the oscillation amplitude is a constant. The findings here imply that an electrostatic barrier can greatly influence the electron tunneling transport of the system, and may provide a new way to realize directional filtering of electrons.

Interplay of electronic, structural and magnetic properties as the driving feature of high-entropy CoCrFeNiPd alloys

NASA Astrophysics Data System (ADS)

Calvo-Dahlborg, M.; Cornide, J.; Tobola, J.; Nguyen-Manh, D.; Wróbel, J. S.; Juraszek, J.; Jouen, S.; Dahlborg, U.

2017-05-01

The structural and magnetic properties of CoCrFe y Ni and CoCrFeNi-Pd x alloys earlier investigated experimentally by x-ray and neutron diffraction techniques and magnetometry have been theoretically reproduced using two complementary approaches for electronic structure calculations, i.e. the Korringa-Kohn-Rostoker method with the coherent potential approximation (KKR-CPA) and implemented in the ab initio framework of density functional theory and the Vienna ab initio simulation package (VASP) for supercell models of high-entropy alloy (HEA) structures. The comparison between experimental results and calculations of the lattice constants by both calculation methods indicate that the structure of CoCrFe y Ni is well described by ordered fcc configurations. The values of local magnetic moments on Fe, Co, Cr, and Ni atoms depend not only on the Pd concentration but on chemical disordering. In the case of the CoCrFeNi-Pd x alloys, the KKR-CPA and the VASP calculations of disordered configurations reproduce the experimental values at 5 K up to equimolar composition and at 300 K above. The experimental values above the equimolar composition at 5 K are not satisfactorily reproduced by any of the calculations. The divergence between the experimental and calculated values is related to the variation of the ferromagnetic to paramagnetic transition temperature as a function of palladium content and to the existence of several phases, FeCoCr-rich above room temperature and FeCrPd-rich below, observed by diffraction and detected by microscopy and atom probe investigations. VASP calculations of a FeCrPd-rich phase effectively reproduced both the lattice constant and magnetization of the alloy above equimolar composition. An important conclusion of this work is that the combined analysis of the electronic, structural, and magnetic properties plays an important role in understanding the complexity of magnetic HEAs.

Length dependence of electron transport through molecular wires--a first principles perspective.

PubMed

Khoo, Khoong Hong; Chen, Yifeng; Li, Suchun; Quek, Su Ying

2015-01-07

One-dimensional wires constitute a fundamental building block in nanoscale electronics. However, truly one-dimensional metallic wires do not exist due to Peierls distortion. Molecular wires come close to being stable one-dimensional wires, but are typically semiconductors, with charge transport occurring via tunneling or thermally-activated hopping. In this review, we discuss electron transport through molecular wires, from a theoretical, quantum mechanical perspective based on first principles. We focus specifically on the off-resonant tunneling regime, applicable to shorter molecular wires (<∼4-5 nm) where quantum mechanics dictates electron transport. Here, conductance decays exponentially with the wire length, with an exponential decay constant, beta, that is independent of temperature. Different levels of first principles theory are discussed, starting with the computational workhorse - density functional theory (DFT), and moving on to many-electron GW methods as well as GW-inspired DFT + Sigma calculations. These different levels of theory are applied in two major computational frameworks - complex band structure (CBS) calculations to estimate the tunneling decay constant, beta, and Landauer-Buttiker transport calculations that consider explicitly the effects of contact geometry, and compute the transmission spectra directly. In general, for the same level of theory, the Landauer-Buttiker calculations give more quantitative values of beta than the CBS calculations. However, the CBS calculations have a long history and are particularly useful for quick estimates of beta. Comparing different levels of theory, it is clear that GW and DFT + Sigma calculations give significantly improved agreement with experiment compared to DFT, especially for the conductance values. Quantitative agreement can also be obtained for the Seebeck coefficient - another independent probe of electron transport. This excellent agreement provides confirmative evidence of off-resonant tunneling in the systems under investigation. Calculations show that the tunneling decay constant beta is a robust quantity that does not depend on details of the contact geometry, provided that the same contact geometry is used for all molecular lengths considered. However, because conductance is sensitive to contact geometry, values of beta obtained by considering conductance values where the contact geometry is changing with the molecular junction length can be quite different. Experimentally measured values of beta in general compare well with beta obtained using DFT + Sigma and GW transport calculations, while discrepancies can be attributed to changes in the experimental contact geometries with molecular length. This review also summarizes experimental and theoretical efforts towards finding perfect molecular wires with high conductance and small beta values.

Nanoscale Electronic Structure of Cuprate Superconductors Investigated with Scanning Tunneling Spectroscopy

NASA Astrophysics Data System (ADS)

Williams, Tess Lawanna

Despite 25 years of intense research activity, high-temperature superconductors remain poorly understood, with the underlying pairing mechanism still unidentified. Efforts are complicated by the remarkably complex phase diagram, rich in energy-dependent charge and spin orders. In this thesis I describe the use of a Scanning Tunneling Microscope (STM) to study energy-dependent charge orders in Bi2-- yPbySr2CuO6+delta , a cuprate high-temperature superconductor. STM, a surface-sensitive probe used to map electronic structure with sub-meV energy resolution and sub-A spatial resolution, has contributed greatly to our current understanding of the cuprate high-temperature superconductors. However, STM data is acquired with a constant-current normalization condition. The measured differential conductance, g(x, y, V), is often taken to be proportional to the density of states at energy eV (where V is the voltage applied between tip and sample). In fact, due to the normalization condition, the measured g(x, y, V) is actually the quotient of the density of states at energy eV and the integrated density of states from the Fermi energy to eV. This unavoidable quotient may fold electronic structure from its true energy range into other energies. I discuss a new method to correct STM differential conductance spectra to remove the constant-current normalization condition. Using local work function measurements and the constant-current topograph, I create a map which does not suffer from the setpoint effect and contains a mixture of topographic information and properly normalized spectroscopic information. I apply this method to the extraction of the incommensurate charge modulation at q⃗˜34 2pa0 . I also extend the study of electronic nematic order, an atomic-lattice-periodic C4 → C2 symmetry breaking, from highly underdoped Bi2 Sr2CaCu2O 8+delta [28] to overdoped Bi2--yPb ySr2CuO6+/-delta. I find that the electronic nematic order parameter is robust to change of scan angle. I define and contrast three different electronic nematic orders with different phases with respect to the crystal. I discuss the effect of the choice of normalization and possible alternate explanations for the source of the calculated nematic order. Finally, I discuss a drift-correction technique, which removes picometer scale drift that is introduced into a spectral map by experimental imperfections, and characterize the optimal algorithm and potential artifacts that drift-correction may introduce.

Facile synthesis of Ni/NiO@GO nanocomposites and its enhanced dielectric constant

NASA Astrophysics Data System (ADS)

Sarkar, S.; Giri, N.; Mondal, A.; Ray, R.

2018-05-01

Ni/NiO embedded Graphene Oxide (GO): Ni/NiO@GO is synthesized by citric acid assisted Pechini-type method. Structural and morphological characterizations are performed by X-ray powdered diffraction (XRD), field emission scanning electron microscopy (FESEM) and tunneling electron microscopy (TEM). Defects in GO sheets are probed by RAMAN spectroscopy. The temperature variation of dielectric constant (ɛR) and dielectric loss (tan δ) are investigated in the temperature range 300 - 400 K. Decoration of GO with Ni/NiO nanoparticles enhances its ɛR by˜55 times. Moreover, its dielectric constant measured at 5 MHz is found to be˜430 times to that of Ni/NiO along with the reduction of dielectric loss by a factor˜0.5. The enhanced dielectric constant makes the composite Ni/NiO@GO a potential candidate for using in ecologically friendly energy storage devices.

Electron attachment to CF3 and CF3Br at temperatures up to 890 K: experimental test of the kinetic modeling approach.

PubMed

Shuman, Nicholas S; Miller, Thomas M; Viggiano, Albert A; Troe, Jürgen

2013-05-28

Thermal rate constants and product branching fractions for electron attachment to CF3Br and the CF3 radical have been measured over the temperature range 300-890 K, the upper limit being restricted by thermal decomposition of CF3Br. Both measurements were made in Flowing Afterglow Langmuir Probe apparatuses; the CF3Br measurement was made using standard techniques, and the CF3 measurement using the Variable Electron and Neutral Density Attachment Mass Spectrometry technique. Attachment to CF3Br proceeds exclusively by the dissociative channel yielding Br(-), with a rate constant increasing from 1.1 × 10(-8) cm(3) s(-1) at 300 K to 5.3 × 10(-8) cm(3) s(-1) at 890 K, somewhat lower than previous data at temperatures up to 777 K. CF3 attachment proceeds through competition between associative attachment yielding CF3 (-) and dissociative attachment yielding F(-). Prior data up to 600 K showed the rate constant monotonically increasing, with the partial rate constant of the dissociative channel following Arrhenius behavior; however, extrapolation of the data using a recently proposed kinetic modeling approach predicted the rate constant to turn over at higher temperatures, despite being only ~5% of the collision rate. The current data agree well with the previous kinetic modeling extrapolation, providing a demonstration of the predictive capabilities of the approach.

Pulse EPR distance measurements to study multimers and multimerisation

NASA Astrophysics Data System (ADS)

Ackermann, Katrin; Bode, Bela E.

2018-06-01

Pulse dipolar electron paramagnetic resonance (PD-EPR) has become a powerful tool for structural biology determining distances on the nanometre scale. Recent advances in hardware, methodology, and data analysis have widened the scope to complex biological systems. PD-EPR can be applied to systems containing lowly populated conformers or displaying large intrinsic flexibility, making them all but intractable for cryo-electron microscopy and crystallography. Membrane protein applications are of particular interest due to the intrinsic difficulties for obtaining high-resolution structures of all relevant conformations. Many drug targets involved in critical cell functions are multimeric channels or transporters. Here, common approaches for introducing spin labels for PD-EPR cause the presence of more than two electron spins per multimeric complex. This requires careful experimental design to overcome detrimental multi-spin effects and to secure sufficient distance resolution in presence of multiple distances. In addition to obtaining mere distances, PD-EPR can also provide information on multimerisation degrees allowing to study binding equilibria and to determine dissociation constants.

Inhomogeneous nuclear spin polarization induced by helicity-modulated optical excitation of fluorine-bound electron spins in ZnSe

NASA Astrophysics Data System (ADS)

Heisterkamp, F.; Greilich, A.; Zhukov, E. A.; Kirstein, E.; Kazimierczuk, T.; Korenev, V. L.; Yugova, I. A.; Yakovlev, D. R.; Pawlis, A.; Bayer, M.

2015-12-01

Optically induced nuclear spin polarization in a fluorine-doped ZnSe epilayer is studied by time-resolved Kerr rotation using resonant excitation of donor-bound excitons. Excitation with helicity-modulated laser pulses results in a transverse nuclear spin polarization, which is detected as a change of the Larmor precession frequency of the donor-bound electron spins. The frequency shift in dependence on the transverse magnetic field exhibits a pronounced dispersion-like shape with resonances at the fields of nuclear magnetic resonance of the constituent zinc and selenium isotopes. It is studied as a function of external parameters, particularly of constant and radio frequency external magnetic fields. The width of the resonance and its shape indicate a strong spatial inhomogeneity of the nuclear spin polarization in the vicinity of a fluorine donor. A mechanism of optically induced nuclear spin polarization is suggested based on the concept of resonant nuclear spin cooling driven by the inhomogeneous Knight field of the donor-bound electron.

Effective ionization coefficients, limiting electric fields, and electron energy distributions in CF{sub 3}I + CF{sub 4} + Ar ternary gas mixtures

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

Tezcan, S. S.; Dincer, M. S.; Bektas, S.

2016-07-15

This paper reports on the effective ionization coefficients, limiting electric fields, electron energy distribution functions, and mean energies in ternary mixtures of (Trifluoroiodomethane) CF{sub 3}I + CF{sub 4} + Ar in the E/N range of 100–700 Td employing a two-term solution of the Boltzmann equation. In the ternary mixture, CF{sub 3}I component is increased while the CF{sub 4} component is reduced accordingly and the 40% Ar component is kept constant. It is seen that the electronegativity of the mixture increases with increased CF{sub 3}I content and effective ionization coefficients decrease while the limiting electric field values increase. Synergism in themore » mixture is also evaluated in percentage using the limiting electric field values obtained. Furthermore, it is possible to control the mean electron energy in the ternary mixture by changing the content of CF{sub 3}I component.« less

FP-LAPW calculations of the elastic, electronic and thermoelectric properties of the filled skutterudite CeRu{sub 4}Sb{sub 12}

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

Shankar, A., E-mail: amitshan2009@gmail.com; Rai, D.P.; Chettri, Sandeep

2016-08-15

We have investigated the electronic structure, elastic and thermoelectric properties of the filled skutterudite CeRu{sub 4}Sb{sub 12} using the density functional theory (DFT). The full potential linearized augmented plane wave (FP-LAPW) method within a framework of the generalized gradient approximation (GGA) approach is used to perform the calculations presented here. The electronic structure calculation suggests an indirect band gap semiconducting nature of the material with energy band gap of 0.08 eV. The analysis of the elastic constants at relaxed positions reveals the ductile nature of the sample material with covalent contribution in the inter-atomic bonding. The narrow band gap semiconductingmore » nature with high value of Seebeck coefficient suggests the possibility of the thermoelectric application of the material. The analysis of the thermal transport properties confirms the result obtained from the energy band structure of the material with high thermopower and dimensionless figure of merit 0.19 at room temperature.« less

Anisotropic carrier mobility in single- and bi-layer C3N sheets

NASA Astrophysics Data System (ADS)

Wang, Xueyan; Li, Qingfang; Wang, Haifeng; Gao, Yan; Hou, Juan; Shao, Jianxin

2018-05-01

Based on the density functional theory combined with the Boltzmann transport equation with relaxation time approximation, we investigate the electronic structure and predict the carrier mobility of single- and bi-layer newly fabricated 2D carbon nitrides C3N. Although C3N sheets possess graphene-like planar hexagonal structure, the calculated carrier mobility is remarkably anisotropic, which is found mainly induced by the anisotropic effective masses and deformation potential constants. Importantly, we find that both the electron and hole mobilities are considerable high, for example, the hole mobility along the armchair direction of single-layer C3N sheets can arrive as high as 1.08 ×104 cm2 V-1 s-1, greatly larger than that of C2N-h2D and many other typical 2D materials. Owing to the high and anisotropic carrier mobility and appropriate band gap, single- and bi-layer semiconducting C3N sheets may have great potential applications in high performance electronic and optoelectronic devices.

Efficient fluorescence quenching in electrochemically exfoliated graphene decorated with gold nanoparticles

NASA Astrophysics Data System (ADS)

Hurtado-Morales, M.; Ortiz, M.; Acuña, C.; Nerl, H. C.; Nicolosi, V.; Hernández, Y.

2016-07-01

High surface area graphene sheets were obtained by electrochemical exfoliation of graphite in an acid medium under constant potential conditions. Filtration and centrifugation processes played an important role in order to obtain stable dispersions in water. Scanning electron microscopy and transmission electron microscopy imaging revealed highly exfoliated crystalline samples of ∼5 μm. Raman, Fourier transform infrared and x-ray photoelectron spectroscopy further confirmed the high quality of the exfoliated material. The electrochemically exfoliated graphene (EEG) was decorated with gold nanoparticles (AuNPs) using sodium cholate as a buffer layer. This approach allowed for a non-covalent functionalization without altering the desirable electronic properties of the EEG. The AuNP-EEG samples were characterized with various techniques including absorbance and fluorescence spectroscopy. These samples displayed a fluorescence signal using an excitation wavelength of 290 nm. The calculated quantum yield (Φ) for these samples was 40.04%, a high efficiency compared to previous studies using solution processable graphene.

Structural, electronic, mechanical and magnetic properties of rare earth nitrides REN (RE= Pm, Eu and Yb)

NASA Astrophysics Data System (ADS)

Murugan, A.; Rajeswarapalanichamy, R.; Santhosh, M.; Iyakutti, K.

2015-07-01

The structural, electronic and mechanical properties of rare earth nitrides REN (RE=Pm, Eu and Yb) are investigated in NaCl and CsCl, and zinc blende structures using first principles calculations based on density functional theory. The calculated lattice parameters are in good agreement with the available results. Among the considered structures, these nitrides are most stable in NaCl structure. A pressure induced structural phase transition from NaCl to CsCl phase is observed in all these nitrides. The electronic structure reveals that these rare earth nitrides are half metallic at normal pressure. These nitrides are found to be covalent and ionic in the stable phase. The computed elastic constants indicate that these nitrides are mechanically stable and elastically anisotropic. Our results confirm that these nitrides are ferromagnetic in nature. A ferromagnetic to non-magnetic phase transition is observed at the pressures of 21.5 GPa and 46.1 GPa in PmN and YbN respectively.

First-principles study on the electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites

DOE PAGES

Jia, Ting; Zeng, Zhi; Lin, H. Q.; ...

2017-08-08

The electronic, optical and thermodynamic properties of ABO 3 (A = La,Sr, B = Fe,Co) perovskites are investigated using first-principles calculations. The obtained results indicate that SrCoO 3 and SrFeO 3 are metals, while LaCoO 3 and LaFeO 3 are insulators and all of them exhibit strong hybridization of the Fe/Co-3d and O-2p orbitals. By correlating the energy band structures with the peaks of the imaginary part of the dielectric function, we obtained the origin of each electron excitation to provide information about the active bands for the corresponding optical transitions observed in the experiment. Moreover, the Debye temperatures θmore » D obtained from the phonon frequencies are comparable to the available data. In conclusion, the thermodynamic properties of the Helmholtz free energy F, entropy S, and constant-volume heat capacity C v are investigated based on the phonon spectra.« less

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

Electronically Tunable Differential Integrator: Linear Voltage Controlled Quadrature Oscillator.

PubMed

Nandi, Rabindranath; Pattanayak, Sandhya; Venkateswaran, Palaniandavar; Das, Sagarika

2015-01-01

A new electronically tunable differential integrator (ETDI) and its extension to voltage controlled quadrature oscillator (VCQO) design with linear tuning law are proposed; the active building block is a composite current feedback amplifier with recent multiplication mode current conveyor (MMCC) element. Recently utilization of two different kinds of active devices to form a composite building block is being considered since it yields a superior functional element suitable for improved quality circuit design. The integrator time constant (τ) and the oscillation frequency (ω o ) are tunable by the control voltage (V) of the MMCC block. Analysis indicates negligible phase error (θ e ) for the integrator and low active ω o -sensitivity relative to the device parasitic capacitances. Satisfactory experimental verifications on electronic tunability of some wave shaping applications by the integrator and a double-integrator feedback loop (DIFL) based sinusoid oscillator with linear f o variation range of 60 KHz~1.8 MHz at low THD of 2.1% are verified by both simulation and hardware tests.

Effect of a skin-deep surface zone on the formation of a two-dimensional electron gas at a semiconductor surface

NASA Astrophysics Data System (ADS)

Olszowska, Natalia; Lis, Jakub; Ciochon, Piotr; Walczak, Łukasz; Michel, Enrique G.; Kolodziej, Jacek J.

2016-09-01

Two-dimensional electron gases (2DEGs) at surfaces and interfaces of semiconductors are described straightforwardly with a one-dimensional (1D) self-consistent Poisson-Schrödinger scheme. However, their band energies have not been modeled correctly in this way. Using angle-resolved photoelectron spectroscopy we study the band structures of 2DEGs formed at sulfur-passivated surfaces of InAs(001) as a model system. Electronic properties of these surfaces are tuned by changing the S coverage, while keeping a high-quality interface, free of defects and with a constant doping density. In contrast to earlier studies we show that the Poisson-Schrödinger scheme predicts the 2DEG band energies correctly but it is indispensable to take into account the existence of the physical surface. The surface substantially influences the band energies beyond simple electrostatics, by setting nontrivial boundary conditions for 2DEG wave functions.

Ultraflat Au nanoplates as a new building block for molecular electronics.

PubMed

Jeong, Wooseok; Lee, Miyeon; Lee, Hyunsoo; Lee, Hyoban; Kim, Bongsoo; Park, Jeong Young

2016-05-27

We demonstrate the charge transport properties of a self-assembled organic monolayer on Au nanoplates with conductive probe atomic force microscopy (CP-AFM). Atomically flat Au nanoplates, a few hundred micrometers on each side, that have only (111) surfaces, were synthesized using the chemical vapor transport method; these nanoplates were employed as the substrates for hexadecanethiol (HDT) self-assembled monolayers (SAMs). Atomic-scale high-resolution images show (√3 x √3) R30° molecular periodicity, indicating a well-ordered structure of the HDT on the Au nanoplates. We observed reduced friction and adhesion forces on the HDT SAMs on Au nanoplates, compared with Si substrates, which is consistent with the lubricating nature of HDT SAMs. The electrical properties, such as I-V characteristics and current as a function of load, were measured using CP-AFM. We obtained a tunneling decay constant (β) of 0.57 Å(-1), including through-bond (βtb = 0.99 Å(-1)) and through-space (βts = 1.36 Å(-1)) decay constants for the two-pathway model. This indicates that the charge transport properties of HDT SAMs on Au nanoplates are consistent with those on a Au (111) film, suggesting that SAMs on nanoplates can provide a new building block for molecular electronics.

Flexible Dielectric Nanocomposites with Ultrawide Zero-Temperature Coefficient Windows for Electrical Energy Storage and Conversion under Extreme Conditions.

PubMed

Shehzad, Khurram; Xu, Yang; Gao, Chao; Li, Hanying; Dang, Zhi-Min; Hasan, Tawfique; Luo, Jack; Duan, Xiangfeng

2017-03-01

Polymer dielectrics offer key advantages over their ceramic counterparts such as flexibility, scalability, low cost, and high breakdown voltages. However, a major drawback that limits more widespread application of polymer dielectrics is their temperature-dependent dielectric properties. Achieving dielectric constants with low/zero-temperature coefficient (L/0TC) over a broad temperature range is essential for applications in diverse technologies. Here, we report a hybrid filler strategy to produce polymer composites with an ultrawide L/0TC window of dielectric constant, as well as a significantly enhanced dielectric value, maximum energy storage density, thermal conductivity, and stability. By creating a series of percolative polymer composites, we demonstrated hybrid carbon filler based composites can exhibit a zero-temperature coefficient window of 200 °C (from -50 to 150 °C), the widest 0TC window for all polymer composite dielectrics reported to date. We further show the electric and dielectric temperature coefficient of the composites is highly stable against stretching and bending, even under AC electric field with frequency up to 1 MHz. We envision that our method will push the functional limits of polymer dielectrics for flexible electronics in extreme conditions such as in hybrid vehicles, aerospace, power electronics, and oil/gas exploration.

Magnetic and dielectric properties of Co doped nano crystalline Li ferrites by auto combustion method

NASA Astrophysics Data System (ADS)

Aravind, G.; Raghasudha, M.; Ravinder, D.; Kumar, R. Vijaya

2016-05-01

The ultra fine particles of the cobalt substituted lithium ferrites with the formula [Li0.5Fe0.5]1-xCoxFe2O4 (0.0≤x≤1.0) were synthesized by low temperature citrate-gel auto combustion method. Structural characterization of the samples was carried out using XRD studies and FESEM (Field Emission Scanning Electron Microscopy) analysis. XRD studies confirms the formation of single phased spinel structure with crystallite size in the range of 36-43 nm. The M-H loops have been traced using Vibrating Sample Magnetometer (VSM) for all the compositions at room temperature and hysteresis parameters were evaluated. The hysteresis loops of the prepared samples show clear saturation at an applied field of ±20 k Oe and the loops were highly symmetric in nature. The dielectric parameters such as dielectric constant (ε'), dielectric loss tangent (tan δ) of the samples were studied as a function of frequency in the range of 20 Hz to 2 MHz at room temperature using LCR Meter. The dielectric constant and loss tangent of the samples show a normal dielectric behavior with frequency which reveals that the dispersion is due to the Maxwell-Wagner type interfacial polarization and hopping of electrons between the Fe2+ and Fe3+ ions.

Investigations on the Influence of Parameters During Electron Beam Surface Hardening Using the Flash Technique

NASA Astrophysics Data System (ADS)

Grafe, S.; Hengst, P.; Buchwalder, A.; Zenker, R.

2018-06-01

The electron beam hardening (EBH) process is one of today’s most innovative industrial technologies. Due to the almost inertia-free deflection of the EB (up to 100 kHz), the energy transfer function can be adapted locally to the component geometry and/or loading conditions. The current state-of-the-art technology is that of EBH with continuous workpiece feed. Due to the large range of parameters, the potentials and limitations of EBH using the flash technique (without workpiece feed) have not been investigated sufficiently to date. The aim of this research was to generate surface isothermal energy transfer within the flash field. This paper examines the effects of selected process parameters on the EBH surface layer microstructure and the properties achieved when treating hardened and tempered C45E steel. When using constant point distribution within the flash field and a constant beam current, surface isothermal energy input was not generated. However, by increasing the deflection frequency, point density and beam current, a more homogeneous EBH surface layer microstructure could be achieved, along with higher surface hardness and greater surface hardening depths. Furthermore, using temperature-controlled power regulation, surface isothermal energy transfer could be realised over a larger area in the centre of the sample.

Theoretical investigation of the structural stabilities, optoelectronic properties and thermodynamic characteristics of GaPxSb1-x ternary alloys

NASA Astrophysics Data System (ADS)

Oumelaz, F.; Nemiri, O.; Boumaza, A.; Ghemid, S.; Meradji, H.; Bin Omran, S.; El Haj Hassan, F.; Rai, D. P.; Khenata, R.

2018-06-01

In this theoretical study, we have investigated the structural, phase transition, electronic, thermodynamic and optical properties of GaPxSb1-x ternary alloys. Our calculations are performed with the WIEN2k code based on density functional theory using the full-potential linearized augmented plane wave method. For the electron exchange-correlation potential, a generalized gradient approximation within Wu-Cohen scheme is considered. The recently developed Tran-Blaha modified Becke-Johnson potential has also been used to improve the underestimated band gap. The structural properties, including the lattice constants, the bulk moduli and their pressure derivatives are in very good agreement with the available experimental data and theoretical results. Several structural phase transitions were studied here to establish the stable structure and to predict the phase transition under hydrostatic pressure. The computed transition pressure (Pt) of the material of our interest from the zinc blende (B3) to the rock salt (B1) phase has been determined and found to agree well with the experimental and theoretical data. The calculated band structure shows that GaSb binary compound and the ternary alloys are direct band gap semiconductors. Optical parameters such as the dielectric constants and the refractive indices are calculated and analyzed. The thermodynamic results are also interpreted and analyzed.

FP-LAPW based investigation of structural, electronic and mechanical properties of CePb{sub 3} intermetallic compound

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; Abraham, Jisha Annie, E-mail: disisjisha@yahoo.com

A theoretical study of structural, electronic, elastic and mechanical properties of CePb{sub 3} intermetallic compound has been investigated systematically using first principles density functional theory. The calculations are carried out within the three different forms of generalized gradient approximation (GGA) and LSDA for the exchange correlation potential. The ground state properties such as lattice parameter (a{sub 0}), bulk modulus (B) and its pressure derivative (B′) are calculated and obtained lattice parameter of this compound shows well agreement with the experimental results. We have calculated three independent second order elastic constants (C{sub 11}, C{sub 12} and C{sub 44}), which has notmore » been calculated and measured yet. From energy dispersion curves, it is found that the studied compound is metallic in nature. Ductility of this compound is analyzed using Pugh’s criteria and Cauchy's pressure (C{sub 11}-C{sub 12}). The mechanical properties such as Young's modulus, shear modulus, anisotropic ratio, Poison's ratio have been calculated for the first time using the Voigt–Reuss–Hill (VRH) averaging scheme. The average sound velocities (v{sub m}), density (ρ) and Debye temperature (θ{sub D}) of this compound are also estimated from the elastic constants.« less

Repair Activity of trans-Resveratrol toward 2'-Deoxyguanosine Radicals.

PubMed

Cheng, Xing; An, Ping; Li, Shujin; Zhou, Liping

2018-04-26

In the present study, the repair activity of trans-resveratrol toward 2'-deoxyguanosine (dGuo) radicals in polar and nonpolar solvents was studied using density functional theory. The hydrogen transfer/proton coupled electron transfer and single electron transfer (SET) mechanisms between trans-resveratrol and dGuo-radicals were considered. Taking into consideration the molar fraction of neutral trans-resveratrol (ROH) and anionic trans-resveratrol (RO - ), the overall rate constants for repairing dGuo-radicals by trans-resveratrol are 9.94 × 10 8 and 2.01 × 10 9 dm 3 mol -1 s -1 in polar and nonpolar solvents, respectively, and the overall rate constant of repairing cation radical (dGuo •+ ) by trans-resveratrol via an SET mechanism is 7.17 × 10 9 dm 3 mol -1 s -1 . The repair activity of RO - toward dGuo-radicals is better than that of ROH, but the repair activity of ROH toward dGuo •+ is better than that of RO - . Unfortunately, neither ROH nor RO - can repair the 2'-deoxyribose radicals of dGuo. It can therefore be concluded that trans-resveratrol is an effective antioxidant for repairing base radicals of dGuo and dGuo •+ . The study can help us understand the repair activity of trans-resveratrol toward dGuo radicals.

Electron cyclotron emission from nonthermal tokamak plasmas

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

Harvey, R.W.; O'Brien, M.R.; Rozhdestvensky, V.V.

1993-02-01

Electron cyclotron emission can be a sensitive indicator of nonthermal electron distributions. A new, comprehensive ray-tracing and cyclotron emission code that is aimed at predicting and interpreting the cyclotron emission from tokamak plasmas is described. The radiation transfer equation is solved along Wentzel--Kramers--Brillouin (WKB) rays using a fully relativistic calculation of the emission and absorption from electron distributions that are gyrotropic and toroidally symmetric, but may be otherwise arbitrary functions of the constants of motion. Using a radial array of electron distributions obtained from a bounce-averaged Fokker--Planck code modeling dc electron field and electron cyclotron heating effects, the cyclotron emissionmore » spectra are obtained. A pronounced strong nonthermal cyclotron emission feature that occurs at frequencies relativistically downshifted to second harmonic cyclotron frequencies outside the tokamak is calculated, in agreement with experimental results from the DIII-D [J. L. Luxon and L. G. Davies, Fusion Technol. [bold 8], 441 (1985)] and FT-1 [D. G. Bulyginsky [ital et] [ital al]., in [ital Proceedings] [ital of] [ital the] 15[ital th] [ital European] [ital Conference] [ital on] [ital Controlled] [ital Fusion] [ital and] [ital Plasma] [ital Heating], Dubrovnik, 1988 (European Physical Society, Petit-Lancy, 1988), Vol. 12B, Part II, p. 823] tokamaks. The calculations indicate the presence of a strong loss mechanism that operates on electrons in the 100--150 keV energy range.« less

Effects of Applied Potential and Water Intercalation on the Surface Chemistry of Ti 2C and Mo 2C MXenes

DOE PAGES

Fredrickson, Kurt D.; Anasori, Babak; Seh, Zhi Wei; ...

2016-12-09

Here, two-dimensional transition metal carbides and nitrides, also known as MXenes, represent an attractive class of materials for a multitude of electrochemical and other applications. While single sheets of MXenes have been widely studied theoretically, there have been much fewer studies on layered bulk MXenes, which are more representative of multi- or few-layer MXenes used in actual applications. Herein, we investigate the structural and electronic effects of water intercalation, multiple functional groups and applied potential on layered bulk Ti 2C and Mo 2C MXenes using density functional theory. The out-of plane lattice parameter, c, was found to vary significantly withmore » the functional group, and is greatly increased upon intercalation of water. Experimental results confirm the change in lattice constant due to addition or removal of intercalated water. Under zero applied potential, both Ti 2C and Mo 2C were found to be functionalized by one monolayer of O; bare MXenes were never found to be stable, regardless of the applied potential. Applying a potential changed the adsorbate coverage, changing the systems from O covered to H covered at negative potentials and, in some cases, giving rise to a metal–insulator transition. Understanding of the effects of surface functionalization and water intercalation of MXenes provides a better insight of their use for catalytic and electronic applications.« less