Energy control strategy for a hybrid electric vehicle

DOEpatents

Phillips, Anthony Mark; Blankenship, John Richard; Bailey, Kathleen Ellen; Jankovic, Miroslava

2002-08-27

An energy control strategy (10) for a hybrid electric vehicle that controls an electric motor during bleed and charge modes of operation. The control strategy (10) establishes (12) a value of the power level at which the battery is to be charged. The power level is used to calculate (14) the torque to be commanded to the electric motor. The strategy (10) of the present invention identifies a transition region (22) for the electric motor's operation that is bounded by upper and lower speed limits. According to the present invention, the desired torque is calculated by applying equations to the regions before, during and after the transition region (22), the equations being a function of the power level and the predetermined limits and boundaries.

Energy control strategy for a hybrid electric vehicle

DOEpatents

Phillips, Anthony Mark; Blankenship, John Richard; Bailey, Kathleen Ellen; Jankovic, Miroslava

2002-01-01

An energy control strategy (10) for a hybrid electric vehicle that controls an electric motor during bleed and charge modes of operation. The control strategy (10) establishes (12) a value of the power level at which the battery is to be charged. The power level is used to calculate (14) the torque to be commanded to the electric motor. The strategy (10) of the present invention identifies a transition region (22) for the electric motor's operation that is bounded by upper and lower speed limits. According to the present invention, the desired torque is calculated by applying equations to the regions before, during and after the transition region (22), the equations being a function of the power level and the predetermined limits and boundaries.

Optical properties of 3d transition-metal-doped MgAl2O4 spinels

NASA Astrophysics Data System (ADS)

Izumi, K.; Miyazaki, S.; Yoshida, S.; Mizokawa, T.; Hanamura, E.

2007-08-01

Strong emission bands in the visible region are observed in MgAl2O4 crystals doped with transition-metal ions under excitation at the band-to-band transitions. We report optical responses of Cr-, Co-, and Ni-doped MgAl2O4 and present optical models for M -doped MgAl2O4 ( M=Ti , V, Cr, Mn, Co, and Ni) to describe the charge-transfer transitions and the transitions between multiplet levels of 3d electrons, which are observed competitively or coexisting, depending on the number of 3d electrons. While the optical responses of Cr- and Ni-doped MgAl2O4 are dominated by the multiplet-multiplet transitions, those of Ti- and V-doped MgAl2O4 are governed by the charge-transfer transitions. The two kinds of transitions coexist in the Mn- and Co-doped MgAl2O4 . These behaviors are well understood based on the numerical results of unrestricted Hartree-Fock approximation.

Nonequivalent lanthanide defects: Energy level modeling

NASA Astrophysics Data System (ADS)

Joos, Jonas J.; Poelman, Dirk; Smet, Philippe F.

2016-11-01

Empirical charge-state transition level schemes are popular tools to model the properties of lanthanide-doped materials and their construction has become standard practice. Typically, it is implicitly assumed that all lanthanide ions form isostructural defects. However, in practice, multiple nonequivalent defects related to the same lanthanide can occur or different lanthanides can even incorporate in different ways. The consequences of these complications on the impurity energy levels are discussed in this article. It seems that small structural differences around the lanthanide dopant can give rise to important spectral differences in its emission. These are not always clearly reproduced by the charge-state transition level schemes. Improvements to the existing procedure are suggested and applied to the lanthanide ions in the well-studied host crystals SrAl2O4, Sr2Si5N8 and SrGa2S4.

Energy conversion modeling of the intrinsic persistent luminescence of solids via energy transfer paths between transition levels.

PubMed

Huang, Bolong; Sun, Mingzi

2017-04-05

An energy conversion model has been established for the intrinsic persistent luminescence in solids related to the native point defect levels, formations, and transitions. In this study, we showed how the recombination of charge carriers between different defect levels along the zero phonon line (ZPL) can lead to energy conversions supporting the intrinsic persistent phosphorescence in solids. This suggests that the key driving force for this optical phenomenon is the pair of electrons hopping between different charged defects with negative-U eff . Such a negative correlation energy will provide a sustainable energy source for electron-holes to further recombine in a new cycle with a specific quantum yield. This will help us to understand the intrinsic persistent luminescence with respect to native point defect levels as well as the correlations of electronics and energetics.

Analysis of magnetic-dipole transitions in tungsten plasmas using detailed and configuration-average descriptions

NASA Astrophysics Data System (ADS)

Na, Xieyu; Poirier, Michel

2017-06-01

This paper is devoted to the analysis of transition arrays of magnetic-dipole (M1) type in highly charged ions. Such transitions play a significant role in highly ionized plasmas, for instance in the tungsten plasma present in tokamak devices. Using formulas recently published and their implementation in the Flexible Atomic Code for M1-transition array shifts and widths, absorption and emission spectra arising from transitions inside the 3*n complex of highly-charged tungsten ions are analyzed. A comparison of magnetic-dipole transitions with electric-dipole (E1) transitions shows that, while the latter are better described by transition array formulas, M1 absorption and emission structures reveal some insufficiency of these formulas. It is demonstrated that the detailed spectra account for significantly richer structures than those predicted by the transition array formalism. This is due to the fact that M1 transitions may occur between levels inside the same relativistic configuration, while such inner configuration transitions are not accounted for by the currently available averaging expression. In addition, because of configuration interaction, transition processes involving more than one electron jump, such as 3p1/23d5/2 → 3p3/23d3/2, are possible but not accounted for in the transition array formulas. These missing transitions are collected in pseudo-arrays using a post-processing method described in this paper. The relative influence of inner- and inter-configuration transitions is carefully analyzed in cases of tungsten ions with net charge around 50. The need for an additional theoretical development is emphasized.

Ab initio studies of isolated hydrogen vacancies in graphane

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Chetty, N.

2016-05-01

We present a density functional study of various hydrogen vacancies located on a single hexagonal ring of graphane (fully hydrogenated graphene) considering the effects of charge states and the position of the Fermi level. We find that uncharged vacancies that lead to a carbon sublattice balance are energetically favorable and are wide band gap systems just like pristine graphane. Vacancies that do create a sublattice imbalance introduce spin polarized states into the band gap, and exhibit a half-metallic behavior with a magnetic moment of 1.00 μB per vacancy. The results show the possibility of using vacancies in graphane for novel spin-based applications. When charging such vacancy configurations, the deep donor (+1/0) and deep acceptor (0/-1) transition levels within the band gap are noted. We also note a half-metallic to metallic transition and a significant reduction of the induced magnetic moment due to both negative and positive charge doping.

Origin of the Counterintuitive Dynamic Charge in the Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Pike, Nicholas; van Troeye, Benoit; Dewandre, Antoine; Gonze, Xavier; Verstraete, Matthieu

Our recent first-principles calculations of the electronic and vibrational properties of the hexagonal transition-metal dichalcogenides reveal that their Born effective charges display a counterintuitive sign when compared to most other materials or transition-metal dichalcogenides with trigonal symmetry. We determine the origin of this counterintuitive sign by calculating the electronic, vibrational, and optical properties of these systems. We show that the sign of the Born effective charge is directly related to the electric field response of the electronic density, and, in turn, to the bonding characteristics of the material.There is a filled anti-bonding molecular orbital at the Fermi level, which is localized on the transition-metal atom and corresponds to a form of solid state π back-bonding in these material. We propose a method of determining if other materials display a similar counterintuitive sign, based on their bonding characteristics, and propose experiments which could measure the sign of the Born effective charge using different spectroscopies. The authors acknowledge the Belgian Fonds National de la Recherche Scientifique FNRS under PDR T.1077.15-1/7, a FRIA Grant, ULg, and from the Communauté Française de Belgique (ARC AIMED 15/19-09).

Zn vacancy-donor impurity complexes in ZnO

NASA Astrophysics Data System (ADS)

Frodason, Y. K.; Johansen, K. M.; Bjørheim, T. S.; Svensson, B. G.; Alkauskas, A.

2018-03-01

Results from hybrid density functional theory calculations on the thermodynamic stability and optical properties of the Zn vacancy (VZn) complexed with common donor impurities in ZnO are reported. Complexing VZn with donors successively removes its charge-state transition levels in the band gap, starting from the most negative one. Interestingly, the presence of a donor leads only to modest shifts in the positions of the VZn charge-state transition levels, the sign and magnitude of which can be interpreted from a polaron energetics model by taking hole-donor repulsion into account. By employing a one-dimensional configuration coordinate model, luminescence lineshapes and positions were calculated. Due to the aforementioned effects, the isolated VZn gradually changes from a mainly nonradiative defect with transitions in the infrared region in n -type material, to a radiative one with broad emission in the visible range when complexed with shallow donors.

Circuits and methods for determination and control of signal transition rates in electrochemical cells

DOEpatents

Jamison, David Kay

2016-04-12

A charge/discharge input is for respectively supplying charge to, or drawing charge from, an electrochemical cell. A transition modifying circuit is coupled between the charge/discharge input and a terminal of the electrochemical cell and includes at least one of an inductive constituent, a capacitive constituent and a resistive constituent selected to generate an adjusted transition rate on the terminal sufficient to reduce degradation of a charge capacity characteristic of the electrochemical cell. A method determines characteristics of the transition modifying circuit. A degradation characteristic of the electrochemical cell is analyzed relative to a transition rate of the charge/discharge input applied to the electrochemical cell. An adjusted transition rate is determined for a signal to be applied to the electrochemical cell that will reduce the degradation characteristic. At least one of an inductance, a capacitance, and a resistance is selected for the transition modifying circuit to achieve the adjusted transition rate.

Transition metal ions in ZnO: Effects of intrashell coulomb repulsion on electronic properties

NASA Astrophysics Data System (ADS)

Ciechan, A.; Bogusławski, P.

2018-05-01

Electronic structure of the transition metal (TM) dopants in ZnO is calculated by first principles approach. Analysis of the results is focused on the properties determined by the intrashell Coulomb coupling. The role of both direct and exchange interaction channel is analyzed. The coupling is manifested in the strong charge state dependence of the TM gap levels, which leads to the metastability of photoexcited Mn, and determines the accessible equilibrium charge states of TM ions. The varying magnitude of the exchange coupling is reflected in the dependence of the spin splitting energy on the chemical identity across the 3d series, as well as the charge state dependence of spin-up spin-down exchange splitting.

Rare earth substitutional impurities in germanium: A hybrid density functional theory study

NASA Astrophysics Data System (ADS)

Igumbor, E.; Omotoso, E.; Tunhuma, S. M.; Danga, H. T.; Meyer, W. E.

2017-10-01

The Heyd, Scuseria, and Ernzerhof (HSE06) hybrid functional by means of density functional theory has been used to model the electronic and structural properties of rare earth (RE) substitutional impurities in germanium (REGe) . The formation and charge state transition energies for the REGe (RE = Ce, Pr, Er and Eu) were calculated. The energy of formation for the neutral charge state of the REGe lies between -0.14 and 3.13 eV. The formation energy result shows that the Pr dopant in Ge (PrGe) has the lowest formation energy of -0.14 eV, and is most energetically favourable under equilibrium conditions. The REGe induced charge state transition levels within the band gap of Ge. Shallow acceptor levels were induced by both the Eu (EuGe) and Pr (PrGe) dopants in Ge. The CeGe and ErGe exhibited properties of negative-U ordering with effective-U values of -0.85 and -1.07 eV, respectively.

Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

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

Glaser, Mathias; Peisert, Heiko, E-mail: heiko.peisert@uni-tuebingen.de; Adler, Hilmar

2015-03-14

The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the chargemore » transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.« less

Influence of dense plasma on the energy levels and transition properties in highly charged ions

NASA Astrophysics Data System (ADS)

Chen, Zhan-Bin; Hu, Hong-Wei; Ma, Kun; Liu, Xiao-Bin; Guo, Xue-Ling; Li, Shuang; Zhu, Bo-Hong; Huang, Lian; Wang, Kai

2018-03-01

The studies of the influence of plasma environments on the level structures and transition properties for highly charged ions are presented. For the relativistic treatment, we implemented the multiconfiguration Dirac-Fock method incorporating the ion sphere (IS) model potential, in which the plasma screening is taken into account as a modified interaction potential between the electron and the nucleus. For the nonrelativistic treatment, analytical solutions of the Schrödinger equation with two types of the IS screened potential are proposed. The Ritz variation method is used with hydrogenic wave function as a trial wave function that contains two unknown variational parameters. Bound energies are derived from an energy equation, and the variational parameters are obtained from the minimisation condition of the expectation value of the energy. Numerical results for hydrogen-like ions in dense plasmas are presented as examples. A detailed analysis of the influence of relativistic effects on the energy levels and transition properties is also reported. Our results are compared with available results in the literature showing a good quantitative agreement.

Formal Valence, 3 d Occupation, and Charge Ordering Transitions

NASA Astrophysics Data System (ADS)

Pickett, Warren

2014-03-01

The metal-insulator transition (MIT), discovered by Verwey in the late 1930s, has been thought to be one of the best understood of MITs, the other ones being named after Wigner, Peierls, Mott, and Anderson. Continuing work on these transitions finds in some cases less and less charge to order, raising the fundamental question of just where the entropy is coming from, and just what is ordering. To provide insight into the mechanism of charge-ordering transitions, which conventionally are pictured as a disproportionation, I will (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new theoretical results for the rare earth nickelates (viz. YNiO3), the putative charge ordering compound AgNiO2, and the dual charge state insulator AgO, and (3) analyze cationic occupations of actual (not formal) charge, and work to reconcile the conundrums that arise. Several of the clearest cases of charge ordering transitions involve no disproportion; moreover, the experimental data used to support charge ordering can be accounted for within density functional based calculations that contain no charge transfer The challenge of modeling charge ordering transitions with model Hamiltonians will be discussed. Acknowledgment: Y. Quan, V. Pardo. Supported by NSF award DMR-1207622-0.

Theoretical level energies and transition data for 4p64d4, 4p64d34f and 4p54d5 configurations of W34+ ion

NASA Astrophysics Data System (ADS)

Karpuškienė, R.; Bogdanovich, P.; Kisielius, R.

2017-05-01

The ab initio quasirelativistic approach developed specifically for the calculation of spectral parameters of highly charged ions was used to derive transition data for the tungsten ion W34+. The configuration interaction method was applied to include electron correlation effects. The relativistic effects were taken into account in the Breit-Pauli approximation. The level energies, radiative lifetimes τ, Landé g-factors are determined for the ground configuration 4p64d4 and two excited configurations 4p64d34f and 4p54d5. The radiative transition wavelengths λ and emission transition probabilities A for the electric dipole, electric quadrupole, electric octupole, magnetic dipole, and magnetic quadrupole transitions among the levels of these configurations are produced.

Direct Evidence for Delocalization of Charge Carriers at the Fermi Level in a Doped Conducting Polymer

NASA Astrophysics Data System (ADS)

Zhuo, Jing-Mei; Zhao, Li-Hong; Chia, Perq-Jon; Sim, Wee-Sun; Friend, Richard H.; Ho, Peter K. H.

2008-05-01

The infrared absorption spectrum of the polaron charges at the Fermi level EF in a heavily p-doped conducting poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonic acid) film has been measured using interferogram-modulated Fourier-transform charge-modulation spectroscopy. The spectrum indicates softer phonons and weaker electron-phonon coupling riding on a strongly redshifted Drude-like electronic transition, different from the population-averaged “bulk” spectrum. This provides direct evidence that the EF holes are sufficiently delocalized even in such disordered materials to reside in an energy continuum (band states) while the rest of the hole population resides in self-localized gap states.

Charge states of ions, and mechanisms of charge ordering transitions

NASA Astrophysics Data System (ADS)

Pickett, Warren E.; Quan, Yundi; Pardo, Victor

2014-07-01

To gain insight into the mechanism of charge ordering transitions, which conventionally are pictured as a disproportionation of an ion M as 2Mn+→M(n+1)+ + M(n-1)+, we (1) review and reconsider the charge state (or oxidation number) picture itself, (2) introduce new results for the putative charge ordering compound AgNiO2 and the dual charge state insulator AgO, and (3) analyze the cationic occupations of the actual (not formal) charge, and work to reconcile the conundrums that arise. We establish that several of the clearest cases of charge ordering transitions involve no disproportion (no charge transfer between the cations, and hence no charge ordering), and that the experimental data used to support charge ordering can be accounted for within density functional-based calculations that contain no charge transfer between cations. We propose that the charge state picture retains meaning and importance, at least in many cases, if one focuses on Wannier functions rather than atomic orbitals. The challenge of modeling charge ordering transitions with model Hamiltonians isdiscussed.

Magnetic circular dichroism of UCl 6– in the ligand-to-metal charge-transfer spectral region

DOE PAGES

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.; ...

2017-06-23

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

Electronic doping of transition metal oxide perovskites

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

Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz; Rondinelli, James M.

2016-05-23

CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

Emergence of charge density waves and a pseudogap in single-layer TiTe 2

DOE PAGES

Chen, P.; Pai, Woei Wu; Chan, Y. -H.; ...

2017-09-11

Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here in this paper we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermimore » level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.« less

Radio frequency charge parity meter.

PubMed

Schroer, M D; Jung, M; Petersson, K D; Petta, J R

2012-10-19

We demonstrate a total charge parity measurement by detecting the radio frequency signal that is reflected by a lumped-element resonator coupled to a single InAs nanowire double quantum dot. The high frequency response of the circuit is used to probe the effects of the Pauli exclusion principle at interdot charge transitions. Even parity charge transitions show a striking magnetic field dependence that is due to a singlet-triplet transition, while odd parity transitions are relatively insensitive to a magnetic field. The measured response agrees well with cavity input-output theory, allowing accurate measurements of the interdot tunnel coupling and the resonator-charge coupling rate g(c)/2π~17 MHz.

State-to-State Internal Energy Relaxation Following the Quantum-Kinetic Model in DSMC

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2014-01-01

A new model for chemical reactions, the Quantum-Kinetic (Q-K) model of Bird, has recently been introduced that does not depend on macroscopic rate equations or values of local flow field data. Subsequently, the Q-K model has been extended to include reactions involving charged species and electronic energy level transitions. Although this is a phenomenological model, it has been shown to accurately reproduce both equilibrium and non-equilibrium reaction rates. The usefulness of this model becomes clear as local flow conditions either exceed the conditions used to build previous models or when they depart from an equilibrium distribution. Presently, the applicability of the relaxation technique is investigated for the vibrational internal energy mode. The Forced Harmonic Oscillator (FHO) theory for vibrational energy level transitions is combined with the Q-K energy level transition model to accurately reproduce energy level transitions at a reduced computational cost compared to the older FHO models.

Wavelengths and energy levels for the Zn I isoelectronic sequence Ga[sup 1+] through Xe[sup 24+

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

Seely, J.F.; Bar-Shalom, A.

Calculated and experimentally determined transition energies were compared for the Zn I isoelectronic sequence for the elements with atomic numbers Z = 31-54. Using the Hebrew Univ. Lawrence Livermore Atomic Code, the excitation energies were calculated for the 109 levels belonging to the lowest 16 configurations of the types 4/4/[prime] and 4/5/[prime]. The analysis of the energy-level structure along the isoelectronic sequence accounted for a number of avoided level crossings. The differences between the calculated and experimental transition energies were determined for 24 transitions among the 4s[sup 2], 4s4p, 4p[sup 2], 4s4d, and 4s4f configurations. Wavelengths were predicted for previouslymore » unobserved transitions in the highly charged ions. 15 refs., 4 figs., 3 tabs.« less

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

Chen, P.; Pai, Woei Wu; Chan, Y. -H.

Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here in this paper we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermimore » level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.« less

Mechanism of charge transfer and its impacts on Fermi-level pinning for gas molecules adsorbed on monolayer WS2.

PubMed

Zhou, Changjie; Yang, Weihuang; Zhu, Huili

2015-06-07

Density functional theory calculations were performed to assess changes in the geometric and electronic structures of monolayer WS2 upon adsorption of various gas molecules (H2, O2, H2O, NH3, NO, NO2, and CO). The most stable configuration of the adsorbed molecules, the adsorption energy, and the degree of charge transfer between adsorbate and substrate were determined. All evaluated molecules were physisorbed on monolayer WS2 with a low degree of charge transfer and accept charge from the monolayer, except for NH3, which is a charge donor. Band structure calculations showed that the valence and conduction bands of monolayer WS2 are not significantly altered upon adsorption of H2, H2O, NH3, and CO, whereas the lowest unoccupied molecular orbitals of O2, NO, and NO2 are pinned around the Fermi-level when these molecules are adsorbed on monolayer WS2. The phenomenon of Fermi-level pinning was discussed in light of the traditional and orbital mixing charge transfer theories. The impacts of the charge transfer mechanism on Fermi-level pinning were confirmed for the gas molecules adsorbed on monolayer WS2. The proposed mechanism governing Fermi-level pinning is applicable to the systems of adsorbates on recently developed two-dimensional materials, such as graphene and transition metal dichalcogenides.

Surface Charge Transfer Doping via Transition Metal Oxides for Efficient p-Type Doping of II-VI Nanostructures.

PubMed

Xia, Feifei; Shao, Zhibin; He, Yuanyuan; Wang, Rongbin; Wu, Xiaofeng; Jiang, Tianhao; Duhm, Steffen; Zhao, Jianwei; Lee, Shuit-Tong; Jie, Jiansheng

2016-11-22

Wide band gap II-VI nanostructures are important building blocks for new-generation electronic and optoelectronic devices. However, the difficulty of realizing p-type conductivity in these materials via conventional doping methods has severely handicapped the fabrication of p-n homojunctions and complementary circuits, which are the fundamental components for high-performance devices. Herein, by using first-principles density functional theory calculations, we demonstrated a simple yet efficient way to achieve controlled p-type doping on II-VI nanostructures via surface charge transfer doping (SCTD) using high work function transition metal oxides such as MoO 3 , WO 3 , CrO 3 , and V 2 O 5 as dopants. Our calculations revealed that these oxides were capable of drawing electrons from II-VI nanostructures, leading to accumulation of positive charges (holes injection) in the II-VI nanostructures. As a result, Fermi levels of the II-VI nanostructures were shifted toward the valence band regions after surface modifications, along with the large enhancement of work functions. In situ ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy characterizations verified the significant interfacial charge transfer between II-VI nanostructures and surface dopants. Both theoretical calculations and electrical transfer measurements on the II-VI nanostructure-based field-effect transistors clearly showed the p-type conductivity of the nanostructures after surface modifications. Strikingly, II-VI nanowires could undergo semiconductor-to-metal transition by further increasing the SCTD level. SCTD offers the possibility to create a variety of electronic and optoelectronic devices from the II-VI nanostructures via realization of complementary doping.

Multilevel effects on the balance of dipole-allowed to dipole-forbidden transitions in Rydberg atoms induced by a dipole interaction with slow charged projectiles

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

Syrkin, M.I.

1996-02-01

In collisions of Rydberg atoms with charged projectiles at velocities approximately matching the speed of the Rydberg electron {ital v}{sub {ital n}} (matching velocity), {ital n} being the principal quantum number of the Rydberg level, the dipole-forbidden transitions with large angular-momentum transfer {Delta}{ital l}{gt}1 substantially dominate over dipole-allowed transitions {Delta}{ital l}=1, although both are induced by the dipole interaction. Here it is shown that as the projectile velocity decreases the adiabatic character of the depopulation depends on the energy distribution of states in the vicinity of the initial level. If the spectrum is close to degeneracy (as for high-{ital l}more » levels) the dipole-forbidden depopulation prevails practically over the entire low-velocity region, down to velocities {approximately}{ital n}{sup 3}[{Delta}{ital E}/Ry]{ital v}{sub {ital n}}, where {Delta}{ital E} is the energy spacing adjoining to the level due to either a quantum defect or the relevant level width or splitting, whichever is greater. If the energy gaps are substantial (as for strongly nonhydrogenic {ital s} and {ital p} levels in alkali-metal atoms), then the fraction of dipole transitions in the total depopulation reaches a flat minimum just below the matching velocity and then grows again, making the progressively increasing contribution to the low-velocity depopulation. The analytic models based on the first-order Born amplitudes (rather than the two-level adiabatic approximation) furnish reasonable estimates of the fractional dipole-allowed and dipole-forbidden depopulations. {copyright} {ital 1996 The American Physical Society.}« less

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics

NASA Astrophysics Data System (ADS)

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M.; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-01

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV–vis spectroscopy and AFM measurements show that this functionality stems from the films’ ability to structurally tune their HOMO–LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures’ plausibility for on-chip molecular electronics operative at room temperature.

Size-dependent single electron transfer and semi-metal-to-insulator transitions in molecular metal oxide electronics.

PubMed

Balliou, Angelika; Bouroushian, Mirtat; Douvas, Antonios M; Skoulatakis, George; Kennou, Stella; Glezos, Nikos

2018-07-06

All-inorganic self-arranged molecular transition metal oxide hyperstructures based on polyoxometalate molecules (POMs) are fabricated and tested as electronically tunable components in emerging electronic devices. POM hyperstructures reveal great potential as charging nodes of tunable charging level for molecular memories and as enhancers of interfacial electron/hole injection for photovoltaic stacks. STM, UPS, UV-vis spectroscopy and AFM measurements show that this functionality stems from the films' ability to structurally tune their HOMO-LUMO levels and electron localization length at room temperature. By adapting POM nanocluster size in solution, self-doping and current modulation of four orders of magnitude is monitored on a single nanocluster on SiO 2 at voltages as low as 3 Volt. Structurally driven insulator-to-semi-metal transitions and size-dependent current regulation through single electron tunneling are demonstrated and examined with respect to the stereochemical and electronic structure of the molecular entities. This extends the value of self-assembly as a tool for correlation length and electronic properties tuning and demonstrate POM hyperstructures' plausibility for on-chip molecular electronics operative at room temperature.

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

Watson, R.E.; Bennett, L.H.

This review is concerned with similarities and differences between noble and transition metal alloying. Two classes of experiments are inspected: impurity Moessbauer isomer shifts and photoemission of core and valence electron levels. At first glance they would appear to be in conflict concerning the direction of any charge transfer. In noble metal alloys this is associated with changes in d-electron count which are compensated by the non-d electrons. The sign of the change in d occupation is readily understood in terms of d band hybridization. The normalized isomer shifts show that the balance of d and non-d transfer terms mustmore » vary across a transition metal row and that while the noble metals, when acting as impurities, act much like the transition elements immediately adjacent to them, the charge transfer, when the noble metals are hosts, is quite different. These observations, taken with recent band theory population analyses, indicate that three charge transfer terms, those associated with d, s and p-like charge, have visible effects on alloying properties. The review also considers the long standing discrepancy between the elemental fcc-bcc structural energy differences of Kaufman and Bernstein which are standardly employed in phase diagram constructs versus those appropriate to the Engel-Brewer model of transition and noble metals. Comparison with recent 5d metal estimates, based on electron band theory total energy calculations, show one region of agreement with the Engel-Brewer values and another of agreement with Kaufman and Bernstein.« less

Surface charge sensing by altering the phase transition in VO2

NASA Astrophysics Data System (ADS)

Kumar, S.; Esfandyarpour, R.; Davis, R.; Nishi, Y.

2014-08-01

Detection of surface charges has various applications in medicine, electronics, biotechnology, etc. The source of surface charge induction may range from simple charge-polarized molecules like water to complicated proteins. It was recently discovered that surface charge accumulation can alter the temperature at which VO2 undergoes a Mott transition. Here, we deposited polar molecules onto the surface of two-terminal thin-film VO2 lateral devices and monitored the joule-heating-driven Mott transition, or conductance switching. We observed that the power required to induce the conductance switching reduced upon treatment with polar molecules and, using in-situ blackbody-emission direct measurement of local temperature, we show that this reduction in power was accompanied by reduction in the Mott transition temperature. Further evidence suggested that this effect has specificity to the nature of the species used to induce surface charges. Using x-ray absorption spectroscopy, we also show that there is no detectable change in oxidation state of vanadium or structural phase in the bulk of the 40 nm VO2 thin-film even as the phase transition temperature is reduced by up to 20 K by the polar molecules. The ability to alter the phase transition parameters by depositing polar molecules suggests a potential application in sensing surface charges of different origins and this set of results also highlights interesting aspects of the phase transition in VO2.

Temperature dependent charge transport studies across thermodynamic glass transition in P3HT:PCBM bulk heterojunction: insight from J-V and impedance spectroscopy

NASA Astrophysics Data System (ADS)

Sarkar, Atri; Rahaman, Abdulla Bin; Banerjee, Debamalya

2018-03-01

Temperature dependent charge transport properties of P3HT:PCBM bulk heterojunction are analysed by dc and ac measurements under dark conditions across a wide temperature range of 110-473 K, which includes the thermodynamic glass transition temperature (Tg ˜320 K) of the system. A change from Ohmic conduction to space charge limited current conduction at higher (⩾1.2 V) applied bias voltages above  ⩾200 K is observed from J-V characteristics. From capacitance-voltage (C-V) measurement at room temperature, the occurrence of a peak near the built-in voltage is observed below the dielectric relaxation frequency, originating from the competition between drift and diffusion driven motions of charges. Carrier concentration (N) is calculated from C-V measurements taken at different temperatures. Room temperature mobility values at various applied bias voltages are in accordance with that obtained from transient charge extraction by linearly increasing voltage measurement. Sample impedance is measured over five decades of frequency across temperature range by using lock-in detection. This data is used to extract temperature dependence of carrier mobility (μ), and dc conductivity (σ_dc ) which is low frequency extrapolation of ac conductivity. An activation energy of  ˜126 meV for the carrier hopping process at the metal-semiconductor interface is estimated from temperature dependence of σ_dc . Above T g, μ levels off to a constant value, whereas σ_dc starts to decrease after a transition knee at T g that can be seen as a combined effect of changes in μ and N. All these observed changes across T g can be correlated to enhanced polymer motion above the glass transition.

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species with Application to DSMC Simulations

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2014-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for near-equilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion.

47 CFR 61.48 - Transition rules for price cap formula calculations.

Code of Federal Regulations, 2014 CFR

2014-10-01

... percentage of Base Period Price Cap Revenues at the holding company level greater than the industry wide... filing entity is shifted to the CMT basket within price caps. Pooled local switching revenue will not be... section, to pooled elements after the Average Traffic Sensitive Charge reaches the target level. For the...

47 CFR 61.48 - Transition rules for price cap formula calculations.

Code of Federal Regulations, 2012 CFR

2012-10-01

... percentage of Base Period Price Cap Revenues at the holding company level greater than the industry wide... filing entity is shifted to the CMT basket within price caps. Pooled local switching revenue will not be... section, to pooled elements after the Average Traffic Sensitive Charge reaches the target level. For the...

47 CFR 61.48 - Transition rules for price cap formula calculations.

Code of Federal Regulations, 2013 CFR

2013-10-01

... percentage of Base Period Price Cap Revenues at the holding company level greater than the industry wide... filing entity is shifted to the CMT basket within price caps. Pooled local switching revenue will not be... section, to pooled elements after the Average Traffic Sensitive Charge reaches the target level. For the...

Interface and phase transition between Moore-Read and Halperin 331 fractional quantum Hall states: Realization of chiral Majorana fermion

NASA Astrophysics Data System (ADS)

Yang, Kun

2017-12-01

We consider an interface separating the Moore-Read state and Halperin 331 state in a half-filled Landau level, which can be realized in a double quantum well system with varying interwell tunneling and/or interaction strengths. In the presence of electron tunneling and strong Coulomb interactions across the interface, we find that all charge modes localize and the only propagating mode left is a chiral Majorana fermion mode. Methods to probe this neutral mode are proposed. A quantum phase transition between the Moore-Read and Halperin 331 states is described by a network of such Majorana fermion modes. In addition to a direct transition, they may also be separated by a phase in which the Majorana fermions are delocalized, realizing an incompressible state which exhibits quantum Hall charge transport and bulk heat conduction.

Theory of Spin States of Quantum Dot Molecules

NASA Astrophysics Data System (ADS)

Ponomarev, I. V.; Reinecke, T. L.; Scheibner, M.; Stinaff, E. A.; Bracker, A. S.; Doty, M. F.; Gammon, D.; Korenev, V. L.

2007-04-01

The photoluminescence spectrum of an asymmetric pair of coupled InAs quantum dots in an applied electric field shows a rich pattern of level anticrossings, crossings and fine structure that can be understood as a superposition of charge and spin configurations. We present a theoretical model that provides a description of the energy positions and intensities of the optical transitions in exciton, biexciton and charged exciton states of coupled quantum dots molecules.

Emergence of charge density waves and a pseudogap in single-layer TiTe2.

PubMed

Chen, P; Pai, Woei Wu; Chan, Y-H; Takayama, A; Xu, C-Z; Karn, A; Hasegawa, S; Chou, M Y; Mo, S-K; Fedorov, A-V; Chiang, T-C

2017-09-11

Two-dimensional materials constitute a promising platform for developing nanoscale devices and systems. Their physical properties can be very different from those of the corresponding three-dimensional materials because of extreme quantum confinement and dimensional reduction. Here we report a study of TiTe 2 from the single-layer to the bulk limit. Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy and spectroscopy, we observed the emergence of a (2 × 2) charge density wave order in single-layer TiTe 2 with a transition temperature of 92 ± 3 K. Also observed was a pseudogap of about 28 meV at the Fermi level at 4.2 K. Surprisingly, no charge density wave transitions were observed in two-layer and multi-layer TiTe 2 , despite the quasi-two-dimensional nature of the material in the bulk. The unique charge density wave phenomenon in the single layer raises intriguing questions that challenge the prevailing thinking about the mechanisms of charge density wave formation.Due to reduced dimensionality, the properties of 2D materials are often different from their 3D counterparts. Here, the authors identify the emergence of a unique charge density wave (CDW) order in monolayer TiTe 2 that challenges the current understanding of CDW formation.

48 CFR 47.305-13 - Transit arrangements.

Code of Federal Regulations, 2010 CFR

2010-10-01

..., as specified in carrier tariffs or rate tenders. A single through rate is charged from origin to final destination plus a transit or other related charge, rather than a more expensive combination of... contractors' earned commercial transit credits, which are recorded with the carriers. A transit credit...

Holographic Van der Waals phase transition of the higher-dimensional electrically charged hairy black hole

NASA Astrophysics Data System (ADS)

Li, Hui-Ling; Feng, Zhong-Wen; Zu, Xiao-Tao

2018-01-01

With motivation by holography, employing black hole entropy, two-point connection function and entanglement entropy, we show that, for the higher-dimensional Anti-de Sitter charged hairy black hole in the fixed charged ensemble, a Van der Waals-like phase transition can be observed. Furthermore, based on the Maxwell equal-area construction, we check numerically the equal-area law for a first order phase transition in order to further characterize the Van der Waals-like phase transition.

Correlation between defect transition levels and thermoelectric operational temperature of doped CrSi2

NASA Astrophysics Data System (ADS)

Singh, Abhishek; Pandey, Tribhuwan

2014-03-01

The performance of a thermoelectric material is quantified by figure of merit ZT. The challenge in achieving high ZT value requires simultaneously high thermopower, high electrical conductivity and low thermal conductivity at optimal carrier concentration. So far doping is the most versatile approach used for modifying thermoelectric properties. Previous studies have shown that doping can significantly improve the thermoelectric performance, however the tuning the operating temperature of a thermoelectric device is a main issue. Using first principles density functional theory, we report for CrSi2, a linear relationship between thermodynamic charge state transition levels of defects and temperature at which thermopower peaks. We show for doped CrSi2 that the peak of thermopower occurs at the temperature Tm, which corresponds to the position of defect transition level. Therefore, by modifying the defect transition level, a thermoelectric material with a given operational temperature can be designed. The authors thankfully acknowledge support from ADA under NpMASS.

Photoinduced charge transfer from vacuum-deposited molecules to single-layer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Osada, Kazuki; Tanaka, Masatoshi; Ohno, Shinya; Suzuki, Takanori

2016-06-01

Variations of photoluminescence (PL) and Raman spectra of single-layer MoS2, MoSe2, WS2, and WSe2 due to the vacuum deposition of C60 or copper phthalocyanine (CuPc) molecules have been investigated. PL spectra are decomposed into two competitive components, an exciton and a charged exciton (trion), depending on carrier density. The variation of PL spectra is interpreted in terms of charge transfer across the interfaces between transition metal dichalcogenides (TMDs) and dopant molecules. We find that deposited C60 molecules inject photoexcited electrons into MoS2, MoSe2, and WS2 or holes into WSe2. CuPc molecules also inject electrons into MoS2, MoSe2, and WS2, while holes are depleted from WSe2 to CuPc. We then propose a band alignment between TMDs and dopant molecules. Peak shifts of Raman spectra and doped carrier density estimated using a three-level model also support the band alignment. We thus demonstrate photoinduced charge transfer from dopant molecules to single-layer TMDs.

Free-energy landscape of ion-channel voltage-sensor–domain activation

PubMed Central

Delemotte, Lucie; Kasimova, Marina A.; Klein, Michael L.; Tarek, Mounir; Carnevale, Vincenzo

2015-01-01

Voltage sensor domains (VSDs) are membrane-bound protein modules that confer voltage sensitivity to membrane proteins. VSDs sense changes in the transmembrane voltage and convert the electrical signal into a conformational change called activation. Activation involves a reorganization of the membrane protein charges that is detected experimentally as transient currents. These so-called gating currents have been investigated extensively within the theoretical framework of so-called discrete-state Markov models (DMMs), whereby activation is conceptualized as a series of transitions across a discrete set of states. Historically, the interpretation of DMM transition rates in terms of transition state theory has been instrumental in shaping our view of the activation process, whose free-energy profile is currently envisioned as composed of a few local minima separated by steep barriers. Here we use atomistic level modeling and well-tempered metadynamics to calculate the configurational free energy along a single transition from first principles. We show that this transition is intrinsically multidimensional and described by a rough free-energy landscape. Remarkably, a coarse-grained description of the system, based on the use of the gating charge as reaction coordinate, reveals a smooth profile with a single barrier, consistent with phenomenological models. Our results bridge the gap between microscopic and macroscopic descriptions of activation dynamics and show that choosing the gating charge as reaction coordinate masks the topological complexity of the network of microstates participating in the transition. Importantly, full characterization of the latter is a prerequisite to rationalize modulation of this process by lipids, toxins, drugs, and genetic mutations. PMID:25535341

Free-energy landscape of ion-channel voltage-sensor-domain activation.

PubMed

Delemotte, Lucie; Kasimova, Marina A; Klein, Michael L; Tarek, Mounir; Carnevale, Vincenzo

2015-01-06

Voltage sensor domains (VSDs) are membrane-bound protein modules that confer voltage sensitivity to membrane proteins. VSDs sense changes in the transmembrane voltage and convert the electrical signal into a conformational change called activation. Activation involves a reorganization of the membrane protein charges that is detected experimentally as transient currents. These so-called gating currents have been investigated extensively within the theoretical framework of so-called discrete-state Markov models (DMMs), whereby activation is conceptualized as a series of transitions across a discrete set of states. Historically, the interpretation of DMM transition rates in terms of transition state theory has been instrumental in shaping our view of the activation process, whose free-energy profile is currently envisioned as composed of a few local minima separated by steep barriers. Here we use atomistic level modeling and well-tempered metadynamics to calculate the configurational free energy along a single transition from first principles. We show that this transition is intrinsically multidimensional and described by a rough free-energy landscape. Remarkably, a coarse-grained description of the system, based on the use of the gating charge as reaction coordinate, reveals a smooth profile with a single barrier, consistent with phenomenological models. Our results bridge the gap between microscopic and macroscopic descriptions of activation dynamics and show that choosing the gating charge as reaction coordinate masks the topological complexity of the network of microstates participating in the transition. Importantly, full characterization of the latter is a prerequisite to rationalize modulation of this process by lipids, toxins, drugs, and genetic mutations.

Transition-Metal-Doped p-Type ZnO Nanoparticle-Based Sensory Array for Instant Discrimination of Explosive Vapors.

PubMed

Qu, Jiang; Ge, Yuru; Zu, Baiyi; Li, Yuxiang; Dou, Xincun

2016-03-09

The development of portable, real-time, and cheap platforms to monitor ultratrace levels of explosives is of great urgence and importance due to the threat of terrorism attacks and the need for homeland security. However, most of the previous chemiresistor sensors for explosive detection are suffering from limited responses and long response time. Here, a transition-metal-doping method is presented to remarkably promote the quantity of the surface defect states and to significantly reduce the charge transfer distance by creating a local charge reservoir layer. Thus, the sensor response is greatly enhanced and the response time is remarkably shortened. The resulting sensory array can not only detect military explosives, such as, TNT, DNT, PNT, PA, and RDX with high response, but also can fully distinguish some of the improvised explosive vapors, such as AN and urea, due to the huge response reaching to 100%. Furthermore, this sensory array can discriminate ppb-level TNT and ppt-level RDX from structurally similar and high-concentration interfering aromatic gases in less than 12 s. Through comparison with the previously reported chemiresistor or Schottky sensors for explosive detection, the present transition-metal-doping method resulting ZnO sensor stands out and undoubtedly challenges the best. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion Mobility Spectrometry-Hydrogen Deuterium Exchange Mass Spectrometry of Anions: Part 1. Peptides to Proteins

NASA Astrophysics Data System (ADS)

Donohoe, Gregory C.; Khakinejad, Mahdiar; Valentine, Stephen J.

2015-04-01

Ion mobility spectrometry (IMS) coupled with hydrogen deuterium exchange (HDX)-mass spectrometry (MS) has been used to study the conformations of negatively-charged peptide and protein ions. Results are presented for ion conformers of angiotensin 1, a synthetic peptide (SP), bovine insulin, ubiquitin, and equine cytochrome c. In general, the SP ion conformers demonstrate a greater level of HDX efficiency as a greater proportion of the sites undergo HDX. Additionally, these ions exhibit the fastest rates of exchange. Comparatively, the angiotensin 1 ions exhibit a lower rate of exchange and HDX level presumably because of decreased accessibility of exchange sites by charge sites. The latter are likely confined to the peptide termini. Insulin ions show dramatically reduced HDX levels and exchange rates, which can be attributed to decreased conformational flexibility resulting from the disulfide bonds. For the larger ubiquitin and protein ions, increased HDX is observed for larger ions of higher charge state. For ubiquitin, a conformational transition from compact to more elongated species (from lower to higher charge states) is reflected by an increase in HDX levels. These results can be explained by a combination of interior site protection by compact conformers as well as decreased access by charge sites. The elongated cytochrome c ions provide the largest HDX levels where higher values correlate with charge state. These results are consistent with increased exchange site accessibility by additional charge sites. The data from these enhanced IMS-HDX experiments are described in terms of charge site location, conformer rigidity, and interior site protection.

Relativistic all-order many-body calculation of energies, wavelengths, and M 1 and E 2 transition rates for the 3 dn configurations in tungsten ions

NASA Astrophysics Data System (ADS)

Safronova, M. S.; Safronova, U. I.; Porsev, S. G.; Kozlov, M. G.; Ralchenko, Yu.

2018-01-01

Energy levels, wavelengths, magnetic-dipole and electric-quadrupole transition rates between the low-lying states are evaluated for W51 + to W54 + ions with 3 dn (n =2 to 5) electronic configurations by using an approach combining configuration interaction with the linearized coupled-cluster single-double method. The QED corrections are directly incorporated into the calculations and their effect is studied in detail. Uncertainties of the calculations are discussed. This study of such highly charged ions with the present method opens the way for future applications allowing an accurate prediction of properties for a very wide range of highly charged ions aimed at providing precision benchmarks for various applications.

Switching Hole and Electron Transports of Molecules on Metal Oxides by Energy Level Alignment Tuning.

PubMed

Bao, Zhong-Min; Xu, Rui-Peng; Li, Chi; Xie, Zhong-Zhi; Zhao, Xin-Dong; Zhang, Yi-Bo; Li, Yan-Qing; Tang, Jian-Xin

2016-08-31

Charge transport at organic/inorganic hybrid contacts significantly affects the performance of organic optoelectronic devices because the unfavorable energy level offsets at these interfaces can hinder charge injection or extraction due to large barrier heights. Herein, we report a technologically relevant method to functionalize a traditional hole-transport layer of solution-processed nickel oxide (NiOx) with various interlayers. The photoemission spectroscopy measurements reveal the continuous tuning of the NiOx substrate work function ranging from 2.5 to 6.6 eV, enabling the alignment transition of energy levels between the Schottky-Mott limit and Fermi level pinning at the organic/composite NiOx interface. As a result, switching hole and electron transport for the active organic material on the composite NiOx layer is achieved due to the controlled carrier injection/extraction barriers. The experimental findings indicate that tuning the work function of metal oxides with optimum energy level offsets can facilitate the charge transport at organic/electrode contacts.

Negatively Charged Lipid Membranes Promote a Disorder-Order Transition in the Yersinia YscU Protein

PubMed Central

Weise, Christoph F.; Login, Frédéric H.; Ho, Oanh; Gröbner, Gerhard; Wolf-Watz, Hans; Wolf-Watz, Magnus

2014-01-01

The inner membrane of Gram-negative bacteria is negatively charged, rendering positively charged cytoplasmic proteins in close proximity likely candidates for protein-membrane interactions. YscU is a Yersinia pseudotuberculosis type III secretion system protein crucial for bacterial pathogenesis. The protein contains a highly conserved positively charged linker sequence that separates membrane-spanning and cytoplasmic (YscUC) domains. Although disordered in solution, inspection of the primary sequence of the linker reveals that positively charged residues are separated with a typical helical periodicity. Here, we demonstrate that the linker sequence of YscU undergoes a largely electrostatically driven coil-to-helix transition upon binding to negatively charged membrane interfaces. Using membrane-mimicking sodium dodecyl sulfate micelles, an NMR derived structural model reveals the induction of three helical segments in the linker. The overall linker placement in sodium dodecyl sulfate micelles was identified by NMR experiments including paramagnetic relaxation enhancements. Partitioning of individual residues agrees with their hydrophobicity and supports an interfacial positioning of the helices. Replacement of positively charged linker residues with alanine resulted in YscUC variants displaying attenuated membrane-binding affinities, suggesting that the membrane interaction depends on positive charges within the linker. In vivo experiments with bacteria expressing these YscU replacements resulted in phenotypes displaying significantly reduced effector protein secretion levels. Taken together, our data identify a previously unknown membrane-interacting surface of YscUC that, when perturbed by mutations, disrupts the function of the pathogenic machinery in Yersinia. PMID:25418176

Negatively charged lipid membranes promote a disorder-order transition in the Yersinia YscU protein.

PubMed

Weise, Christoph F; Login, Frédéric H; Ho, Oanh; Gröbner, Gerhard; Wolf-Watz, Hans; Wolf-Watz, Magnus

2014-10-21

The inner membrane of Gram-negative bacteria is negatively charged, rendering positively charged cytoplasmic proteins in close proximity likely candidates for protein-membrane interactions. YscU is a Yersinia pseudotuberculosis type III secretion system protein crucial for bacterial pathogenesis. The protein contains a highly conserved positively charged linker sequence that separates membrane-spanning and cytoplasmic (YscUC) domains. Although disordered in solution, inspection of the primary sequence of the linker reveals that positively charged residues are separated with a typical helical periodicity. Here, we demonstrate that the linker sequence of YscU undergoes a largely electrostatically driven coil-to-helix transition upon binding to negatively charged membrane interfaces. Using membrane-mimicking sodium dodecyl sulfate micelles, an NMR derived structural model reveals the induction of three helical segments in the linker. The overall linker placement in sodium dodecyl sulfate micelles was identified by NMR experiments including paramagnetic relaxation enhancements. Partitioning of individual residues agrees with their hydrophobicity and supports an interfacial positioning of the helices. Replacement of positively charged linker residues with alanine resulted in YscUC variants displaying attenuated membrane-binding affinities, suggesting that the membrane interaction depends on positive charges within the linker. In vivo experiments with bacteria expressing these YscU replacements resulted in phenotypes displaying significantly reduced effector protein secretion levels. Taken together, our data identify a previously unknown membrane-interacting surface of YscUC that, when perturbed by mutations, disrupts the function of the pathogenic machinery in Yersinia.

Charge state manipulation of qubits in diamond

PubMed Central

Grotz, Bernhard; Hauf, Moritz V.; Dankerl, Markus; Naydenov, Boris; Pezzagna, Sébastien; Meijer, Jan; Jelezko, Fedor; Wrachtrup, Jörg; Stutzmann, Martin; Reinhard, Friedemann; Garrido, Jose A.

2012-01-01

The nitrogen-vacancy (NV) centre in diamond is a promising candidate for a solid-state qubit. However, its charge state is known to be unstable, discharging from the qubit state NV− into the neutral state NV0 under various circumstances. Here we demonstrate that the charge state can be controlled by an electrolytic gate electrode. This way, single centres can be switched from an unknown non-fluorescent state into the neutral charge state NV0, and the population of an ensemble of centres can be shifted from NV0 to NV−. Numerical simulations confirm the manipulation of the charge state to be induced by the gate-controlled shift of the Fermi level at the diamond surface. This result opens the way to a dynamic control of transitions between charge states and to explore hitherto inaccessible states, such as NV+. PMID:22395620

Interface Superconductivity in Cuprates Defies Fermi-Liquid Description

DOE PAGES

Radović, Zoran; Vanević, Mihajlo; Wu, Jie; ...

2016-07-26

La 2-xSr xCuO 4/La 2CuO 4 bilayers show interface superconductivity that originates from accumulation and depletion of mobile charge carriers across the interface. Surprisingly, the doping level can be varied broadly (within the interval 0.15 < x < 0.47) without affecting the transition temperature, which stays essentially constant and equal to that in optimally doped material, T c ≈ 40 K. Here we argue that this finding implies that doping up to the optimum level does not shift the chemical potential, unlike in ordinary Fermi liquids. Lastly, we discuss possible physical scenarios that can give doping-independent chemical potential in themore » pseudogap regime: electronic phase separation, formation of charge-density waves, strong Coulomb interactions, or self-trapping of mobile charge carriers.« less

Optical backbone-sidechain charge transfer transitions in proteins sensitive to secondary structure and modifications.

PubMed

Mandal, I; Paul, S; Venkatramani, R

2018-04-17

The absorption of light by proteins can induce charge transfer (CT) transitions in the UV-visible range of the electromagnetic spectrum. Metal-ligand complexes or active site prosthetic groups which absorb in the visible region exhibit prominent CT transitions. Furthermore, the protein backbone also exhibits CT transitions in the far UV range. In this manuscript, we present a detailed computational study of new near UV-visible CT transitions that involve amino acids with charged side chains. Specifically, using time dependent density functional theory calculations, we examine the absorption spectra of naturally charged amino acids (Lys, Glu, Arg, Asp and His), extracted from solution phase protein structures generated by classical molecular dynamics simulations, and phosphorylated amino acids (Tyr, Thr and Ser) from experimentally determined protein structures. We show that amino acids with charged sidechains present a directed electronic donor-bridge-acceptor paradigm, with the lowest energy optical excitations demonstrating peptide backbone-sidechain charge separations. The UV-visible spectral range of the backbone-sidechain CT transitions is determined by the chemical nature of the donor, bridge and acceptor groups within each amino acid, amino acid conformation and the protein secondary structure where the amino acids are located. Photoinduced CT occurs in opposite directions for the anionic and cationic amino acids along the ground state dipole moment vector for the chromophores. We find that photoinduced charge separation is more facile for the anionic amino acids (Asp, Glu, pSer, pThr and pTyr) relative to that for the cationic amino acids (Lys, Arg and Hsp). Our results provide a foundation for the development of spectroscopic markers based on the recently proposed Protein Charge Transfer Spectra (ProCharTS) which are relevant for the study of DNA-binding or intrinsically disordered proteins that are rich in charged amino acids.

An unusual metallic behavior in a Ag4SSe single crystal

NASA Astrophysics Data System (ADS)

Matteppanavar, Shidaling; Bui, Nguyen Hai An; van Smaalen, Sander; Thamizhavel, A.; Ramakrishnan, S.

2018-04-01

We report the magnetic susceptibility, resistivity and heat capacity measurements on high quality single crystalline tetra silver sulphoselenide (Ag4SSe). The magnetic susceptibility and resistivity measurements show anomalies around 260 K. The large diamagnetic drop with hysteresis at the transition implies a first order transition. Such a diamagnetic drop cannot be ascribed to the formation of charge density wave (CDW) since the temperature dependence of the resistivity shows no upturn at this transition. Infact the resistivity is decreasing with decreasing temperature, indicating a metallic behavior. However, unlike normal metals, the resistivity is almost temperature independent in the temperature range from 4-180 K. Usually, when one observes a diamagnetic transition, it is assumed to be due to a drop in the density of states at the Fermi level which leads to the decrease in the Pauli paramagnetic susceptibility. Such a decrease in the density of states often results in an increase in resistivity unless mobility of the charge carriers changes significantly. Hence, we believe that in Ag4SSe, the structural transition causes an unusual Fermi surface reconstruction which in turn leads to a strange metallic behavior at low temperatures.

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

Gendron, Frederic; Fleischauer, Valerie R.; Duignan, Thomas J.

Here, we present a combined ab initio theoretical and experimental study of the magnetic circular dichroism (MCD) spectrum of the octahedral UCl 6- complex ion in the UV-Vis spectral region. The ground state is an orbitally non-degenerate doublet E 5/2u and the MCD is a $C$-term spectrum caused by spin–orbit coupling. Calculations of the electronic spectrum at various levels of theory indicate that differential dynamic electron correlation has a strong influence on the energies of the dipole-allowed transitions and the envelope of the MCD spectrum. The experimentally observed bands are assigned to dipole-allowed ligand-to-metal charge transfer into the 5f shell,more » and 5f to 6d transitions. Charge transfer excitations into the U 6d shell appear at much higher energies. The MCD-allowed transitions can be assigned via their signs of the $C$-terms: Under O h double group symmetry, E 5/2u → E 5/2g transitions have negative $C$-terms whereas E 5/2u → F 3/2g transitions have positive $C$-terms if the ground state g-factor is negative, as it is the case for UCl 6-.« less

Phase transitions of a water overlayer on charged graphene: from electromelting to electrofreezing.

PubMed

Zhu, Xueyan; Yuan, Quanzi; Zhao, Ya-Pu

2014-05-21

We show by using molecular dynamics simulations that a water overlayer on charged graphene experiences first-order ice-to-liquid (electromelting), and then liquid-to-ice (electrofreezing) phase transitions with the increase of the charge value. Corresponding to the ice-liquid-ice transition, the variations of the order parameters indicate an order-disorder-order transition. The key to this novel phenomenon is the surface charge induced change of the orientations of water dipoles, which leads to the change of the water-water interactions from being attractive to repulsive at a critical charge value qc. To further uncover how the orientations of water dipoles influence the interaction strength between water molecules, a theoretical model considering both the Coulomb and van der Waals interactions is established. The results show that with the increase of the charge value, the interaction strength between water molecules decreases below qc, then increases above qc. These two inverse processes lead to electromelting and electrofreezing, respectively. Combining this model with the Eyring equation, the diffusion coefficient is obtained, the variation of which is in qualitative agreement with the simulation results. Our findings not only expand our knowledge of the graphene-water interface, but related analyses could also help recognize the controversial role of the surface charge or electric field in promoting phase transitions of water.

Cu doped diamond: Effect of charge state and defect aggregation on spin interactions in a 3d transition metal doped wide band-gap semiconductor

NASA Astrophysics Data System (ADS)

Benecha, E. M.; Lombardi, E. B.

2018-05-01

We present a first principles study of Cu in diamond using DFT+U electronic structure methods, by carefully considering the impact of co-doping, charge state, and Fermi level position on its stability, lattice location, spin states, and electronic properties. We show that the energetic stability and spin states of Cu are strongly dependent on the Fermi level position and the type of diamond co-doping, with Cu being energetically more favorable in n-type or p-type co-doped diamond compared to intrinsic diamond. Since Cu has been predicted to order magnetically in a number of other wide band-gap semiconductors, we have also evaluated this possibility for Cu doped diamond. We show that while Cu exhibits strong spin interactions at specific interatomic separations in diamond, a detailed consideration of the impact of Fermi level position and Cu aggregation precludes magnetic ordering, with Cu forming non-magnetic, antiferromagnetic, or paramagnetic clusters. These results have important implications in the understanding of the properties of transition metal dopants in diamond for device applications.

Optical absorption and thermally stimulated depolarization current studies of nickel chloride-doped poly(vinyl alcohol) irradiated with low-level fast neutron doses

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

Abd El-Kader, F.H.; Ibrahim, S.S.; Attia, G.

1993-11-15

The influence of neutron irradiation on ultraviolet/visible absorption and thermally stimulated depolarization current in nickel chloride-poly(vinyl alcohol) (PVA) cast films has been investigated. The spectral measurements indicate the responsibility of the Ni[sup 2][sup +] ion in its octahedral symmetry. Dopant concentrations higher than 10 wt % NiCl[sub 2] are found to make the samples more resistant to a degradation effect caused by neutron irradiation. The thermally stimulated depolarization currents (TSDC) of pure PVA revealed the existence of the glass transition T[sub g] and space charge relaxation peaks, whereas doped-PVA samples show a new sub-T[sub g] relaxation peak. A proposed mechanismmore » is introduced to account for the neutron effects on both glass transition and space charge relaxation peaks. The peak positions, peak currents, and stored charges of the sub-T[sub g] relaxation peak are strongly affected by both the concentration of the dopant and neutron exposure doses.« less

Automatic charge control system for satellites

NASA Technical Reports Server (NTRS)

Shuman, B. M.; Cohen, H. A.

1985-01-01

The SCATHA and the ATS-5 and 6 spacecraft provided insights to the problem of spacecraft charging at geosychronous altitudes. Reduction of the levels of both absolute and differential charging was indicated, by the emission of low energy neutral plasma. It is appropriate to complete the transition from experimental results to the development of a system that will sense the state-of-charge of a spacecraft, and, when a predetermined threshold is reached, will respond automatically to reduce it. A development program was initiated utilizing sensors comparable to the proton electrostatic analyzer, the surface potential monitor, and the transient pulse monitor that flew in SCATHA, and combine these outputs through a microprocessor controller to operate a rapid-start, low energy plasma source.

Double ionization of helium by ion impact: second Born order treatment at the fully differential level

NASA Astrophysics Data System (ADS)

López, S. D.; Otranto, S.; Garibotti, C. R.

2015-01-01

In this work, a theoretical study of the double ionization of He by ion impact at the fully differential level is presented. Emphasis is made in the role played by the projectile in the double emission process depending on its charge and the amount of momentum transferred to the target. A Born-CDW model including a second-order term in the projectile charge is introduced and evaluated within an on-shell treatment. We find that emission geometries for which the second-order term dominates lead to asymmetric structures around the momentum transfer direction, a typical characteristic of higher order transitions.

Intrinsic point defects in β-In2S3 studied by means of hybrid density-functional theory

NASA Astrophysics Data System (ADS)

Ghorbani, Elaheh; Albe, Karsten

2018-03-01

We have employed first principles total energy calculations in the framework of density functional theory, with plane wave basis sets and screened exchange hybrid functionals to study the incorporation of intrinsic defects in bulk β-In2S3. The results are obtained for In-rich and S-rich experimental growth conditions. The charge transition level is discussed for all native defects, including VIn, VS, Ini, Si, SIn, and InS, and a comparison between the theoretically calculated charge transition levels and the available experimental findings is presented. The results imply that β-In2S3 shows n-type conductivity under both In-rich and S-rich growth conditions. The indium antiisite (InS), the indium interstitial (Ini), and the sulfur vacancy ( VS ' ) are found to be the leading sources of sample's n-type conductivity. When going from the In-rich to the S-rich condition, the conductivity of the material decreases; however, the type of conductivity remains unchanged.

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

Mironov, Alexey Yu.; Silevitch, Daniel M.; Proslier, Thomas

Three decades after the prediction of charge-vortex duality in the critical vicinity of the two-dimensional superconductor-insulator transition (SIT), one of the fundamental implications of this duality-the charge Berezinskii-Kosterlitz-Thouless (BKT) transition that should occur on the insulating side of the SIT-has remained unobserved. The dual picture of the process points to the existence of a superinsulating state endowed with zero conductance at finite temperature. Here, we report the observation of the charge BKT transition on the insulating side of the SIT in 10 nm thick NbTiN films, identified by the BKT critical behavior of the temperature and magnetic field dependent resistance,more » and map out the magnetic-field dependence of the critical temperature of the charge BKT transition. Finally, we ascertain the effects of the finite electrostatic screening length and its divergence at the magnetic field-tuned approach to the superconductor-insulator transition.« less

Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

PubMed

Padilha, A C M; Raebiger, H; Rocha, A R; Dalpian, G M

2016-07-01

Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

Anisotropy-driven transition from the Moore-Read state to quantum Hall stripes

NASA Astrophysics Data System (ADS)

Zhu, Zheng; Sodemann, Inti; Sheng, D. N.; Fu, Liang

2017-05-01

We investigate the nature of the quantum Hall liquid in a half-filled second Landau level (n =1 ) as a function of band mass anisotropy using numerical exact diagonalization and density matrix renormalization group methods. We find increasing the mass anisotropy induces a quantum phase transition from the Moore-Read state to a charge density wave state. By analyzing the energy spectrum, guiding center structure factors, and by adding weak pinning potentials, we show that this charge density wave is a unidirectional quantum Hall stripe, which has a periodicity of a few magnetic lengths and survives in the thermodynamic limit. We find smooth profiles for the guiding center occupation function that reveal the strong coupling nature of the array of chiral Luttinger liquids residing at the stripe edges.

Characteristics of the Mott transition and electronic states of high-temperature cuprate superconductors from the perspective of the Hubbard model

NASA Astrophysics Data System (ADS)

Kohno, Masanori

2018-04-01

A fundamental issue of the Mott transition is how electrons behaving as single particles carrying spin and charge in a metal change into those exhibiting separated spin and charge excitations (low-energy spin excitation and high-energy charge excitation) in a Mott insulator. This issue has attracted considerable attention particularly in relation to high-temperature cuprate superconductors, which exhibit electronic states near the Mott transition that are difficult to explain in conventional pictures. Here, from a new viewpoint of the Mott transition based on analyses of the Hubbard model, we review anomalous features observed in high-temperature cuprate superconductors near the Mott transition.

Spectroscopy of Highly Charged Tin Ions for AN Extreme Ultraviolet Light Source for Lithography

NASA Astrophysics Data System (ADS)

Torretti, Francesco; Windberger, Alexander; Ubachs, Wim; Hoekstra, Ronnie; Versolato, Oscar; Ryabtsev, Alexander; Borschevsky, Anastasia; Berengut, Julian; Crespo Lopez-Urrutia, Jose

2017-06-01

Laser-produced tin plasmas are the prime candidates for the generation of extreme ultraviolet (EUV) light around 13.5 nm in nanolithographic applications. This light is generated primarily by atomic transitions in highly charged tin ions: Sn^{8+}-Sn^{14+}. Due to the electronic configurations of these charge states, thousands of atomic lines emit around 13.5 nm, clustered in a so-called unresolved transition array. As a result, accurate line identification becomes difficult in this regime. Nevertheless, this issue can be circumvented if one turns to the optical: with far fewer atomic states, only tens of transitions take place and the spectra can be resolved with far more ease. We have investigated optical emission lines in an electron-beam-ion-trap (EBIT), where we managed to charge-state resolve the spectra. Based on this technique and on a number of different ab initio techniques for calculating the level structure, the optical spectra could be assigned [1,2]. As a conclusion the assignments of EUV transitions in the literature require corrections. The EUV and optical spectra are measured simultaneously in the controlled conditions of the EBIT as well as in a droplet-based laser-produced plasma source providing information on the contribution of Sn^{q+} charge states to the EUV emission. [1] A. Windberger, F. Torretti, A. Borschevsky, A. Ryabtsev, S. Dobrodey, H. Bekker, E. Eliav, U. Kaldor, W. Ubachs, R. Hoekstra, J.R. Crespo Lopez-Urrutia, O.O. Versolato, Analysis of the fine structure of Sn^{11+} - Sn^{14+} ions by optical spectroscopy in an electron beam ion trap, Phys. Rev. A 94, 012506 (2016). [2] F. Torretti, A. Windberger, A. Ryabtsev, S. Dobrodey, H. Bekker, W. Ubachs, R. Hoekstra, E.V. Kahl, J.C. Berengut, J.R. Crespo Lopez-Urrutia, O.O. Versolato, Optical spectroscopy of complex open 4d-shell ions Sn^{7+} - Sn^{10+}, arXiv:1612.00747

Transition energy measurements in hydrogenlike and heliumlike ions strongly supporting bound-state QED calculations

NASA Astrophysics Data System (ADS)

Kubiček, K.; Mokler, P. H.; Mäckel, V.; Ullrich, J.; López-Urrutia, J. R. Crespo

2014-09-01

For the hydrogenlike Ar17+ ion, the 1s Lamb shift was absolutely determined with a 1.4% accuracy based on Lyman-α wavelength measurements that have negligible uncertainties from nuclear size effects. The result agrees with state-of-the-art quantum electrodynamics (QED) calculations, and demonstrates the suitability of Lyman-α transitions in highly charged ions as x-ray energy standards, accurate at the five parts-per-million level. For the heliumlike Ar16+ ion the transition energy for the 1s2p1P1→1s21S0 line was also absolutely determined on an even higher level of accuracy. Additionally, we present relative measurements of transitions in S15+,S14+, and Fe24+ ions. The data for the heliumlike S14+,Ar16+, and Fe24+ ions stringently confirm advanced bound-state QED predictions including screened QED terms that had recently been contested.

47 CFR 51.909 - Transition of rate-of-return carrier access charges.

Code of Federal Regulations, 2012 CFR

2012-10-01

... charges. 51.909 Section 51.909 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.909 Transition of...; and (2) Cap, in accordance with § 51.505(b)(2), the rates for rate all elements in its intrastate...

47 CFR 51.909 - Transition of rate-of-return carrier access charges.

Code of Federal Regulations, 2013 CFR

2013-10-01

... charges. 51.909 Section 51.909 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.909 Transition of...; and (2) Cap, in accordance with § 51.505(b)(2), the rates for rate all elements in its intrastate...

47 CFR 51.909 - Transition of rate-of-return carrier access charges.

Code of Federal Regulations, 2014 CFR

2014-10-01

... charges. 51.909 Section 51.909 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.909 Transition of...; and (2) Cap, in accordance with § 51.505(b)(2), the rates for rate all elements in its intrastate...

Reentrant metal-insulator transition in the Cu-doped manganites La1-x Pbx MnO3 (x˜0.14) single crystals

NASA Astrophysics Data System (ADS)

Zhao, B. C.; Song, W. H.; Ma, Y. Q.; Ang, R.; Zhang, S. B.; Sun, Y. P.

2005-10-01

Single crystals of La1-x Pbx Mn1-y-z Cuy O3 ( x˜0.14 ; y=0 ,0.01,0.02,0.04,0.06; z=0.02 ,0.08,0.11,0.17,0.20) are grown by the flux growth technique. The effect of Cu doping at the Mn-site on magnetic and transport properties is studied. All studied samples undergo a paramagnetic-ferromagnetic transition. The Curie temperature TC decreases and the transition becomes broader with increasing Cu-doping level. The high-temperature insulator-metal (I-M) transition moves to lower temperature with increasing Cu-doping level. A reentrant M-I transition at the low temperature T* is observed for samples with y⩾0.02 . In addition, T* increases with increasing Cu-doping level and is not affected by applied magnetic fields. Accompanying the appearance of T* , there exists a large, almost constant magnetoresistance (MR) below T* except for a large MR peak near TC . This reentrant M-I transition is ascribed to charge carrier localization due to lattice distortion caused by the Cu doping at Mn sites.

Extension of a Kinetic Approach to Chemical Reactions to Electronic Energy Levels and Reactions Involving Charged Species With Application to DSMC Simulations

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2013-01-01

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties are extended in the current work to include electronic energy level transitions and reactions involving charged particles. These extensions are shown to agree favorably with reported transition and reaction rates from the literature for nearequilibrium conditions. Also, the extensions are applied to the second flight of the Project FIRE flight experiment at 1634 seconds with a Knudsen number of 0.001 at an altitude of 76.4 km. In order to accomplish this, NASA's direct simulation Monte Carlo code DAC was rewritten to include the ability to simulate charge-neutral ionized flows, take advantage of the recently introduced chemistry model, and to include the extensions presented in this work. The 1634 second data point was chosen for comparisons to be made in order to include a CFD solution. The Knudsen number at this point in time is such that the DSMC simulations are still tractable and the CFD computations are at the edge of what is considered valid because, although near-transitional, the flow is still considered to be continuum. It is shown that the inclusion of electronic energy levels in the DSMC simulation is necessary for flows of this nature and is required for comparison to the CFD solution. The flow field solutions are also post-processed by the nonequilibrium radiation code HARA to compute the radiative portion of the heating and is then compared to the total heating measured in flight.

Unravelling Doping Effects on PEDOT at the Molecular Level: From Geometry to Thermoelectric Transport Properties.

PubMed

Shi, Wen; Zhao, Tianqi; Xi, Jinyang; Wang, Dong; Shuai, Zhigang

2015-10-14

Tuning carrier concentration via chemical doping is the most successful strategy to optimize the thermoelectric figure of merit. Nevertheless, how the dopants affect charge transport is not completely understood. Here we unravel the doping effects by explicitly including the scattering of charge carriers with dopants on thermoelectric properties of poly(3,4-ethylenedioxythiophene), PEDOT, which is a p-type thermoelectric material with the highest figure of merit reported. We corroborate that the PEDOT exhibits a distinct transition from the aromatic to quinoid-like structure of backbone, and a semiconductor-to-metal transition with an increase in the level of doping. We identify a close-to-unity charge transfer from PEDOT to the dopant, and find that the ionized impurity scattering dominates over the acoustic phonon scattering in the doped PEDOT. By incorporating both scattering mechanisms, the doped PEDOT exhibits mobility, Seebeck coefficient and power factors in very good agreement with the experimental data, and the lightly doped PEDOT exhibits thermoelectric properties superior to the heavily doped one. We reveal that the thermoelectric transport is highly anisotropic in ordered crystals, and suggest to utilize large power factors in the direction of polymer backbone and low lattice thermal conductivity in the stacking and lamellar directions, which is viable in chain-oriented amorphous nanofibers.

Observation of Mollow Triplets with Tunable Interactions in Double Lambda Systems of Individual Hole Spins.

NASA Astrophysics Data System (ADS)

Lagoudakis, K. G.; Fischer, K. A.; Sarmiento, T.; McMahon, P. L.; Radulaski, M.; Zhang, J. L.; Kelaita, Y.; Dory, C.; Mueller, K. M.; Vuckovic, J.

Although individual spins in quantum dots have been extensively used as qubits, their investigation under strong resonant driving in view of accessing Mollow physics is still an open question. We have grown high quality positively charged quantum dots (QD) embedded in a planar microcavity that enable enhanced light matter interactions. Applying a strong magnetic field in the Voigt configuration, individual positively charged quantum dots provide a double lambda level structure. Using a combination of above band and resonant excitation, we observe the formation of Mollow triplets. We investigate the regime where the Mollow sideband splittings are equal to the Zeeman splitting; we observe strong interactions between the Mollow sidebands of the inner transitions and the outer transitions in the form of very clear anticrossings. We investigated these anticrossings and we were able to modify the observed anticrossing splittings on demand by rotating the polarization of the resonant laser. We also developed a quantum-optical model of our system that fully captures the experimentally observed spectra and provides insight on the complicated level structure that results from the strong driving of our positively charged quantum dot. The authors acknowledge financial support from the Army Research Office (Grant No. W911NF1310309) and support from the National Science Foundation, Division of Materials Research (Grant No. 1503759).

Atmospheric Chemiluminescence: COCHISE (COld CHemical Infrared Simulation Experiment) and Related Experiments.

DTIC Science & Technology

1982-10-13

35. 𔄁. Wiese, W.L., Smith, M.W., and Miles , B.M. (1969) Atomic Transition Probabilities, Vol. II, NSRDS-NBS 22. 8. Green, B.D., private communication...sidearms simultane- ously changes the flow velocity (that is, the residence time) and the ratio of charge to number density E/N in the discharge plasma , as...Levels, Vol. I, NSRDS-NBS 35. 7. Wiese, W. L., Smith, M. W., and Miles , B. M. (1969’, Atomic Transition Probabilities, Vol. II, NSRDS-NBS 22. 8. Green, B

Superconducting and charge density wave transition in single crystalline LaPt2Si2

NASA Astrophysics Data System (ADS)

Gupta, Ritu; Dhar, S. K.; Thamizhavel, A.; Rajeev, K. P.; Hossain, Z.

2017-06-01

We present results of our comprehensive studies on single crystalline LaPt2Si2. Pronounced anomaly in electrical resistivity and heat capacity confirms the bulk nature of superconductivity (SC) and charge density wave (CDW) transition in the single crystals. While the charge density wave transition temperature is lower, the superconducting transition temperature is higher in single crystal compared to the polycrystalline sample. This result confirms the competing nature of CDW and SC. Another important finding is the anomalous temperature dependence of upper critical field H C2(T). We also report the anisotropy in the transport and magnetic measurements of the single crystal.

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H–SiC

NASA Astrophysics Data System (ADS)

Igumbor, E.; Olaniyan, O.; Mapasha, R. E.; Danga, H. T.; Omotoso, E.; Meyer, W. E.

2018-05-01

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H–SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H–SiC are presented. We explore complexes where substitutional N/N or B/B sits near a Si (V) or C (V) vacancy to form vacancy-complexes (NV, NV, NV, NV, BV, BV, BV and BV). The energies of formation of the N related vacancy-complexes showed the NV to be energetically stable close to the valence band maximum in its double positive charge state. The NV is more energetically stable in the double negative charge state close to the conduction band minimum. The NV on the other hand, induced double donor level and the NV induced a double acceptor level. For B related complexes, the BV and BV were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the BV become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals - II. Application to Fe2+ --> Ti4+ charge transfer transitions in oxides and silicates

USGS Publications Warehouse

Sherman, David M.

1987-01-01

A molecular orbital description, based on Xα-Scattered wave calculations on a (FeTiO10)14− cluster, is given for Fe2+ → Ti4+ charge transfer transitions in minerals. The calculated energy for the lowest Fe2+ → Ti4+ metal-metal charge transfer transition is 18040 cm−1 in reasonable agreement with energies observed in the optical spectra of Fe-Ti oxides and silicates. As in the case of Fe2+ → Fe3+ charge transfer in mixed-valence iron oxides and silicates, Fe2+ → Ti4+ charge transfer is associated with Fe-Ti bonding across shared polyhedral edges. Such bonding results from the overlap of the Fe(t 2g ) and Ti(t 2g ) 3d orbitals.

First-principles study of Sr2Ir1-xRhxO4: charge transfer, spin-orbit coupling change, and the metal-insulator transition

NASA Astrophysics Data System (ADS)

Sim, Jae-Hoon; Kim, Heung-Sik; Han, Myung Joon

2015-03-01

Using first-principles density functional theory (DFT) calculations, we investigated the electronic structure of Rh-doped iridate, Sr2Ir1-xRhxO4 for which the doping (x) dependent metal-insulator transition (MIT) has been reported experimentally and the controversial discussion developed regarding the origin of this transition. Our DFT+U calculation shows that the value of < L . S > remains largely intact over the entire doping range considered here (x = 0 . 0 , 0 . 125 , 0 . 25 , 0 . 50 , 0 . 75 , and 1 . 0) in good agreement with the branching ratio measured by x-ray absorption spectroscopy. Also contrary to a previous picture to explain MIT based on the charge transfer between the transition-metal sites, our calculation clearly shows that those sites remain basically isoelectronic while the impurity bands of predominantly rhodium character are introduced near the Fermi level. As the doping increases, this impurity band overlaps with lower Hubbard band of iridium, leading to metal-insulator transition. The results will be discussed with comparison to the case of Ru doping. Computational resources were suported by The National Institute of Supercomputing and Networking/Korea Institute of Science and Technology Information with supercomputing resources including technical spport (Grant No. KSC-2013-C2-23).

Radio frequency reflectometry and charge sensing of a precision placed donor in silicon

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

Hile, Samuel J., E-mail: samhile@gmail.com; House, Matthew G.; Peretz, Eldad

2015-08-31

We compare charge transitions on a deterministic single P donor in silicon using radio frequency reflectometry measurements with a tunnel coupled reservoir and DC charge sensing using a capacitively coupled single electron transistor (SET). By measuring the conductance through the SET and comparing this with the phase shift of the reflected radio frequency (RF) excitation from the reservoir, we can discriminate between charge transfer within the SET channel and tunneling between the donor and reservoir. The RF measurement allows observation of donor electron transitions at every charge degeneracy point in contrast to the SET conductance signal where charge transitions aremore » only observed at triple points. The tunnel coupled reservoir has the advantage of a large effective lever arm (∼35%), allowing us to independently extract a neutral donor charging energy ∼62 ± 17 meV. These results demonstrate that we can replace three terminal transistors by a single terminal dispersive reservoir, promising for high bandwidth scalable donor control and readout.« less

Charge Order in (TMTTF)2TaF6 by Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Oka, Yuki; Matsunaga, Noriaki; Nomura, Kazushige; Kawamoto, Atsuhi; Yamamoto, Kaoru; Yakushi, Kyuya

2015-11-01

We have performed infrared spectroscopy in (TMTTF)2TaF6 (TMTTF: tetramethyltetrathiafulvalene) to investigate the relationship between the charge order (CO) state and the antiferromagnetic (AF) insulating ground state. A clear peak splitting corresponding to the charge disproportionation was observed below the CO transition temperature. We estimated the degree of charge disproportionation, Δρ = ρrich - ρpoor, as 0.28e from the peak splitting and found that the CO state coexists with the AF state and there is no charge redistribution below the AF transition.

Nuclear Dynamics at Molecule–Metal Interfaces: A Pseudoparticle Perspective

DOE PAGES

Galperin, Michael; Nitzan, Abraham

2015-11-20

We discuss nuclear dynamics at molecule-metal interfaces including nonequilibrium molecular junctions. Starting from the many-body states (pseudoparticle) formulation of the molecule-metal system in the molecular vibronic basis, we introduce gradient expansion to reduce the adiabatic nuclear dynamics (that is, nuclear dynamics on a single molecular potential surface) into its semiclassical form while maintaining the effect of the nonadiabatic electronic transitions between different molecular charge states. Finally, this yields a set of equations for the nuclear dynamics in the presence of these nonadiabatic transitions, which reproduce the surface-hopping formulation in the limit of small metal-molecule coupling (where broadening of the molecularmore » energy levels can be disregarded) and Ehrenfest dynamics (motion on the potential of mean force) when information on the different charging states is traced out.« less

Optimal Charge-to-Spin Conversion in Graphene on Transition-Metal Dichalcogenides

NASA Astrophysics Data System (ADS)

Offidani, Manuel; Milletarı, Mirco; Raimondi, Roberto; Ferreira, Aires

2017-11-01

When graphene is placed on a monolayer of semiconducting transition metal dichalcogenide (TMD) its band structure develops rich spin textures due to proximity spin-orbital effects with interfacial breaking of inversion symmetry. In this work, we show that the characteristic spin winding of low-energy states in graphene on a TMD monolayer enables current-driven spin polarization, a phenomenon known as the inverse spin galvanic effect (ISGE). By introducing a proper figure of merit, we quantify the efficiency of charge-to-spin conversion and show it is close to unity when the Fermi level approaches the spin minority band. Remarkably, at high electronic density, even though subbands with opposite spin helicities are occupied, the efficiency decays only algebraically. The giant ISGE predicted for graphene on TMD monolayers is robust against disorder and remains large at room temperature.

Optical studies of the charge localization and delocalization in conducting polymers

NASA Astrophysics Data System (ADS)

Kim, Youngmin

A systematic charge transport study on the thermochromism of polyaniline (PAN) doped with a plasticizing dopant, and on a field effect device using conducting poly (3,4-ethylenedioxythiophene) (PEDOT) as its active material, was made at optical (20--45,000 cm-1) frequencies to probe the charge localization and delocalization phenomena and the insulator to metal transition (IMT) in the inhomogeneous conducting polymer system. Temperature dependent reflectance [20--8000 cm -1 (2.5 meV--1eV)] of the PAN sample, together with absorbance and do transport study done by Dr. Pron at the Laboratoire de Physique des Metaux Synthetiques in Grenoble, France, shows spectral weight loss in the infrared region but the reflectance in the very low frequency (below 100 cm-1) remains unaffected. There are two localization transitions. The origin of the 200 K localization transition that affect >˜15% of the electrons is the glass transition emanating from the dopants. The transition principally affects the IR response in the range of 200--8000 cm -1. The low temperature (<75K) localization transition affects the few electrons that provide the high conductivity. It is suggested that these electrons are localized by disorder at the lowest temperature and become delocalized through phonon induced delocalization as the temperature increases to 75K. It is noted that this temperature is typical of a Debye temperature in many organic materials. The thermocromism is attributed to the weak localization to strong localization transition through the glass transition temperature. Below the glass transition temperature (Tg), the lattice is "frozen" in configuration that reduces the charge delocalization and lead to cause increase of strongly localized polarons. Time variation of source-drain current, real-time IR reflectance [20--8000 cm-1 (2.5 meV--1eV)] modulation, and real-time UV/VIS/NIR absorbance [380--2400 nm (0.5--3.3 eV)] modulation were measured to investigate the field induced charge localization of PEDOT field effect device. Layer by layer thin film analysis showed strong localization of free carriers. The temperature dependence of the do conductivity changes with application of the gate voltage demonstrating that the electric field effect has changed bulk charge transport in the active channel despite the expected screening due to mobile charge carriers. Mid IR (500--8000 cm-1) reflectance showed little change in the vibrational modes, which distinguish this phenomenon from the doping-dedoping induced electrochemical MIT. UV/Vis/NIR absorbance modulation clearly showed that the increase of the strong localization of charges with the pi-pi* bandgap transition unchanged. It is proposed that conducting polymer is near the metal to insulator transition and that the applied gate voltage leads to this transition through field induced ion motion.

Pressure-Induced Charge-Order Melting and Reentrant Charge Carrier Localization in the Mixed-Valent Pb 3Rh 7O 15

DOE PAGES

Li, Yan; Sun, Zhao; Cai, Jia -Wei; ...

2017-07-01

Here, the mixed-valent Pbmore » $${}_{3}$$Rh $${}_{7}$$O$${}_{15}$$ undergoes a Verwey-type transition at $${T}_{{\\rm{v}}}\\approx 180$$ K, below which the development of Rh$${}^{3+}$$ /Rh$${}^{4+}$$ charge order induces an abrupt conductor-to-insulator transition in resistivity. Here we investigate the effect of pressure on the Verwey-type transition of Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ by measuring its electrical resistivity under hydrostatic pressures up to 8 GPa with a cubic anvil cell apparatus. We find that the application of high pressure can suppress the Verwey-type transition around 3 GPa, above which a metallic state is realized at temperatures below ~70 K, suggesting the melting of charge order by pressure. Interestingly, the low-temperature metallic region shrinks gradually upon further increasing pressure and disappears completely at P > 7 GPa, which indicates that the charge carriers in Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ undergo a reentrant localization under higher pressures. We have constructed a temperature-pressure phase diagram for Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ and compared to that of Fe$${}_{3}$$O$${}_{4}$$, showing an archetype Verwey transition.« less

Cooling atomic ions with visible and infra-red light

NASA Astrophysics Data System (ADS)

Lindenfelser, F.; Marinelli, M.; Negnevitsky, V.; Ragg, S.; Home, J. P.

2017-06-01

We demonstrate the ability to load, cool and detect singly charged calcium ions in a surface electrode trap using only visible and infrared lasers for the trapped-ion control. As opposed to the standard methods of cooling using dipole-allowed transitions, we combine power broadening of a quadrupole transition at 729 nm with quenching of the upper level using a dipole allowed transition at 854 nm. By observing the resulting 393 nm fluorescence we are able to perform background-free detection of the ion. We show that this system can be used to smoothly transition between the Doppler cooling and sideband cooling regimes, and verify theoretical predictions throughout this range. We achieve scattering rates which reliably allow recooling after collision events and allow ions to be loaded from a thermal atomic beam. This work is compatible with recent advances in optical waveguides, and thus opens a path in current technologies for large-scale quantum information processing. In situations where dielectric materials are placed close to trapped ions, it carries the additional advantage of using wavelengths which do not lead to significant charging, which should facilitate high rate optical interfaces between remotely held ions.

Anomalous metallic state with strong charge fluctuations in BaxTi8O16 +δ revealed by hard x-ray photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Dash, S.; Kajita, T.; Okawa, M.; Saitoh, T.; Ikenaga, E.; Saini, N. L.; Katsufuji, T.; Mizokawa, T.

2018-04-01

We have studied a charge-orbital driven metal-insulator transition (MIT) in hollandite-type BaxTi8O16 +δ by means of hard x-ray photoemission spectroscopy (HAXPES). The Ti 2 p HAXPES indicates strong Ti3 +/Ti4 + charge fluctuation in the metallic phase above the MIT temperature. The metallic phase is characterized by a power-law spectral function near the Fermi level which would be a signature of bad metal with non-Drude polaronic behavior. The power-law spectral shape is associated with the large Seebeck coefficient of the metallic phase in BaxTi8O16 +δ .

Charge modulation in two-dimensional compounds

NASA Astrophysics Data System (ADS)

Monceau, Pierre

2015-03-01

Although the first measurements demonstrating charge modulation were performed forty years ago, many open questions are now the matter of intense research. In the first part of this short review, some recent results obtained on transition metal dichalcogenides (MX2) compounds will be presented such as: mechanism of the Peierls transition, effect of strong electron-phonon coupling, soft mode in the phonon dispersion, chirality effects,....Charge order, ferroelectricity, frustration, glassiness in organic 2D systems will be the subject of the second part. The third part will be devoted to describe the properties of a new family of 2D compounds, namely rare earth tritellurides, in which the size of the rare earth determine the charge density wave transition temperature.

Investigation of ground state charge transfer complex between paracetamol and p-chloranil through DFT and UV-visible studies

NASA Astrophysics Data System (ADS)

Shukla, Madhulata; Srivastava, Nitin; Saha, Satyen

2012-08-01

The present report deals with the theoretical investigation on ground state structure and charge transfer (CT) transitions in paracetamol (PA)/p-chloranil (CA) complex using Density Functional Theory (DFT) and Time Dependent Density Functional Theory (TD-DFT) method. It is found that Cdbnd O bond length of p-chloranil increases on complexation with paracetamol along with considerable amount of charge transfer from PA to CA. TD-DFT calculations have been performed to analyse the observed UV-visible spectrum of PA-CA charge transferred complex. Interestingly, in addition to expected CT transition, a weak symmetry relieved π-π* transition in the chloranil is also observed.

Evidence for a Peierls phase-transition in a three-dimensional multiple charge-density waves solid

PubMed Central

Mansart, Barbara; Cottet, Mathieu J. G.; Penfold, Thomas J.; Dugdale, Stephen B.; Tediosi, Riccardo; Chergui, Majed; Carbone, Fabrizio

2012-01-01

The effect of dimensionality on materials properties has become strikingly evident with the recent discovery of graphene. Charge ordering phenomena can be induced in one dimension by periodic distortions of a material’s crystal structure, termed Peierls ordering transition. Charge-density waves can also be induced in solids by strong coulomb repulsion between carriers, and at the extreme limit, Wigner predicted that crystallization itself can be induced in an electrons gas in free space close to the absolute zero of temperature. Similar phenomena are observed also in higher dimensions, but the microscopic description of the corresponding phase transition is often controversial, and remains an open field of research for fundamental physics. Here, we photoinduce the melting of the charge ordering in a complex three-dimensional solid and monitor the consequent charge redistribution by probing the optical response over a broad spectral range with ultrashort laser pulses. Although the photoinduced electronic temperature far exceeds the critical value, the charge-density wave is preserved until the lattice is sufficiently distorted to induce the phase transition. Combining this result with ab initio electronic structure calculations, we identified the Peierls origin of multiple charge-density waves in a three-dimensional system for the first time. PMID:22451898

Pseudo-direct bandgap transitions in silicon nanocrystals: effects on optoelectronics and thermoelectrics

NASA Astrophysics Data System (ADS)

Singh, Vivek; Yu, Yixuan; Sun, Qi-C.; Korgel, Brian; Nagpal, Prashant

2014-11-01

While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon.While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr04688a

Influence of defects on the charge density wave of ([SnSe] 1+δ) 1(VSe 2) 1 ferecrystals

DOE PAGES

Falmbigl, Matthias; Putzky, Daniel; Ditto, Jeffrey; ...

2015-07-14

A series of ferecrystalline compounds ([SnSe] 1+δ) 1(VSe 2) 1 with varying Sn/V ratios were synthesized using the modulated elemental reactant technique. Temperature-dependent specific heat data reveal a phase transition at 102 K, where the heat capacity changes abruptly. An abrupt increase in electrical resistivity occurs at the same temperature, correlated with an abrupt increase in the Hall coefficient. Combined with the magnitude and nature of the specific heat discontinuity, this suggests that the transition is similar to the charge density wave transitions in transition metal dichalcogenides. An ordered intergrowth was formed over a surprisingly wide compositional range of Sn/Vmore » ratios of 0.89 ≤ 1 + δ ≤ 1.37. X-ray diffraction and transmission electron microscopy reveal the formation of various volume defects in the compounds in response to the nonstoichiometry. The electrical resistivity and Hall coefficient data of samples with different Sn/V ratios show systematic variation in the carrier concentration with the Sn/V ratio. There is no significant change in the onset temperature of the charge density wave transition, only a variation in the carrier densities before and after the transition. Given the sensitivity of the charge density wave transitions of transition metal dichalcogenides to variations in composition, it is very surprising that the charge density wave transition observed at 102 K for ([SnSe] 1.15) 1(VSe 2) 1 is barely influenced by the nonstoichiometry and structural defects. As a result, this might be a consequence of the two-dimensional nature of the structurally independent VSe 2 layers.« less

The role of charge transfer in the energy level alignment at the pentacene/C60 interface.

PubMed

Beltrán, J; Flores, F; Ortega, J

2014-03-07

Understanding the mechanism of energy level alignment at organic-organic interfaces is a crucial line of research to optimize applications in organic electronics. We address this problem for the C60-pentacene interface by performing local-orbital Density Functional Theory (DFT) calculations, including the effect of the charging energies on the energy gap of both organic materials. The results are analyzed within the induced density of interface states (IDIS) model. We find that the induced interface potential is in the range of 0.06-0.10 eV, in good agreement with the experimental evidence, and that such potential is mainly induced by the small, but non-negligible, charge transfer between the two compounds and the multipolar contribution associated with pentacene. We also suggest that an appropriate external intercompound potential could create an insulator-metal transition at the interface.

Visualization of the evolution of charged droplet formation and jet transition in electrostatic atomization

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

Huo, Yuanping, E-mail: huoyuanping@gmail.com; Wang, Junfeng, E-mail: wangjunfeng@ujs.edu.cn; Zuo, Ziwen

2015-11-15

A detailed experimental study on the evolution of charged droplet formation and jet transition from a capillary is reported. By means of high-speed microscopy, special attention has been paid to the dynamics of the liquid thread and satellite droplets in the dripping mode, and a method for calculating the surface charge on the satellite droplet is proposed. Jet transition behavior based on the electric Bond number has been visualized, droplet sizes and velocities are measured to obtain the ejection characteristic of the spray plume, and the charge and hydrodynamic relaxation are linked to give explanations for ejection dynamics with differentmore » properties. The results show that the relative length is very sensitive to the hydrodynamic relaxation time. The magnitude of the electric field strength dominates the behavior of coalescence and noncoalescence, with the charge relationship between the satellite droplet and the main droplet being clear for every noncoalescence movement. Ejection mode transitions mainly depend on the magnitude of the electric Bond number, and the meniscus dynamics is determined by the ratio of the charge relaxation time to the hydrodynamic relaxation time.« less

Valency configuration of transition metal impurities in ZnO

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

Petit, Leon; Schulthess, Thomas C; Svane, Axel

2006-01-01

We use the self-interaction corrected local spin-density approximation to investigate the ground state valency configuration of transition metal (TM=Mn, Co) impurities in n- and p-type ZnO. We find that in pure Zn{sub 1-x}TM{sub x}O, the localized TM{sup 2+} configuration is energetically favored over the itinerant d-electron configuration of the local spin density (LSD) picture. Our calculations indicate furthermore that the (+/0) donor level is situated in the ZnO gap. Consequently, for n-type conditions, with the Fermi energy {epsilon}F close to the conduction band minimum, TM remains in the 2+ charge state, while for p-type conditions, with {epsilon}F close to themore » valence band maximum, the 3+ charge state is energetically preferred. In the latter scenario, modeled here by co-doping with N, the additional delocalized d-electron charge transfers into the entire states at the top of the valence band, and hole carriers will only exist, if the N concentration exceeds the TM impurity concentration.« less

Charge transfer and optical properties of trifluoromethyl substituted benzodithiophene (TFMBDT): A theoretical study

NASA Astrophysics Data System (ADS)

Sahoo, Smruti Ranjan; Sahu, Sridhar; Sharma, Sagar

2018-05-01

We present density functional study of the charge transport and optical properties of trifluoromethyl substituted benzodithiophene (TFMBDT) molecule. We found the hole reorganization energy, reduced by 0.354 eV compared to the electron reorganization energy, thus favoring the hole transport across the molecular barrier. We found the maximum tH and tL at the tilting angle 85°, to be 0.473 eV and 0.472 eV, respectively. Although, both tH and tL are found to equivalent, however, low λh can contribute to the larger hole mobility. In the TD-DFT calculation, the low energy electronic transition (H→L) was found to be accordance with the electronic HOMO-LUMO energy gap of the conjugated organic molecule. The calculated gas phase maximum absorption (λmax) of TFMBDT molecule was observed at 337.31 nm (3.67 eV) for B3LYP/6-311+G(d, p) level and 328.04 nm (3.77 eV) for PBE1PBE/6-311+G(d, p) level, which is mostly associated with HOMO→LUMO transition.

Stress Induced Charge-Ordering Process in LiMn 2O 4

DOE PAGES

Chen, Yan; Yu, Dunji; An, Ke

2016-07-25

In this letter we report the stress-induced Mn charge-ordering process in the LiMn 2O 4 spinel, evidenced by the lattice strain evolutions due to the Jahn–Teller effects. In situ neutron diffraction reveals the initial stage of this process at low stress, indicating the eg electron localization at the preferential Mn sites during the early phase transition as an underlying charge-ordering mechanism in the charge-frustrated LiMn 2O 4. The initial stage of this transition exhibits as a progressive lattice and charge evolution, without showing a first-order behavior.

SFG and SPR Study of Sodium Dodecyl Sulfate Film Assembly on Positively Charged Surfaces

NASA Astrophysics Data System (ADS)

Song, Sanghun; Weidner, Tobias; Wagner, Matthew; Castner, David

2012-02-01

This study uses sum frequency generation (SFG) vibrational spectroscopy and surface plasmon resonance (SPR) sensing to investigate the structure of sodium dodecyl sulfate (SDS) films formed on positively charged and hydrophilic surfaces. The SPR signals show a good surface coverage suggesting that full monolayer coverage is reached at 1 mM. SFG spectra of SDS adsorbed exhibits well resolved CH3 peaks and OH peaks. At both 0.2 mM and 1 mM SDS concentration the intensity of both the CH3 and OH peaks decreased close to background levels. We found that the loss of SFG signal at 0.2 mM occurs at this concentration independent of surface charge density. It is more likely that the loss of signal is related to structural inhomogeneity induced by a striped phase - stand-up phase transition. This is supported by a distinct change of the relative SFG phase between CH3/OH near 0.2 mM. The second intensity minimum might be related to charge compensation effects. We observed a substrate dependence for the high concentration transition. We also observed distinct SFG signal phase changes for water molecules associated with SDS layers at different SDS solution concentrations indicating that the orientation of bound water changed with SDS surface structure.

Models of charge pair generation in organic solar cells.

PubMed

Few, Sheridan; Frost, Jarvist M; Nelson, Jenny

2015-01-28

Efficient charge pair generation is observed in many organic photovoltaic (OPV) heterojunctions, despite nominal electron-hole binding energies which greatly exceed the average thermal energy. Empirically, the efficiency of this process appears to be related to the choice of donor and acceptor materials, the resulting sequence of excited state energy levels and the structure of the interface. In order to establish a suitable physical model for the process, a range of different theoretical studies have addressed the nature and energies of the interfacial states, the energetic profile close to the heterojunction and the dynamics of excited state transitions. In this paper, we review recent developments underpinning the theory of charge pair generation and phenomena, focussing on electronic structure calculations, electrostatic models and approaches to excited state dynamics. We discuss the remaining challenges in achieving a predictive approach to charge generation efficiency.

Nonradiative Transitions in Media of Different Polarities and Their Modeling for 12'-Apo-β-Caroten-12'-Al and 8'-Apo-β-Caroten-8'-Al

NASA Astrophysics Data System (ADS)

Pavlovich, V. S.

2014-09-01

The theory of nonradiative transitions, based on the model of orientational broadening of electronic levels, is used to interpret known data on the effect of the polarity of the medium and temperature on the lifetime of the S 1( A {/g -}) state for 12'-apo-β-caroten-12'-al and 8'-apo-β-caroten-8'-al. The effect of promoting vibrations on the rate constant for nonradiative transitions is considered. The results make it possible to hypothesize that the internal electric field created by the environment strongly perturbs the pigment molecules. Consequently, in the excited S 1( A {/g -}) state, both pigments exist as different conformers I and II. Their structures differ by a 180° rotation of the cyclohexene ring relative to the polyene chain. Conformer II predominates in polar media, and is found in an intramolecular charge-transfer state S 1( A {/g -}/ ICT). In addition, as a result of fluctuations in the internal electric field, it can also be found in a charge-separated state S 1( A {/g -}/ CS).

QED theory of multiphoton transitions in atoms and ions

NASA Astrophysics Data System (ADS)

Zalialiutdinov, Timur A.; Solovyev, Dmitry A.; Labzowsky, Leonti N.; Plunien, Günter

2018-03-01

This review surveys the quantum theory of electromagnetic radiation for atomic systems. In particular, a review of current theoretical studies of multiphoton processes in one and two-electron atoms and highly charged ions is provided. Grounded on the quantum electrodynamics description the multiphoton transitions in presence of cascades, spin-statistic behaviour of equivalent photons and influence of external electric fields on multiphoton in atoms and anti-atoms are discussed. Finally, the nonresonant corrections which define the validity of the concept of the excited state energy levels are introduced.

Band engineering in transition metal dichalcogenides: Stacked versus lateral heterostructures

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

Guo, Yuzheng; Robertson, John

2016-06-06

We calculate a large difference in the band alignments for transition metal dichalcogenide (TMD) heterojunctions when arranged in the stacked layer or lateral (in-plane) geometries, using direct supercell calculations. The stacked case follows the unpinned limit of the electron affinity rule, whereas the lateral geometry follows the strongly pinned limit of alignment of charge neutrality levels. TMDs therefore provide one of the few clear tests of band alignment models, whereas three-dimensional semiconductors give less stringent tests because of accidental chemical trends in their properties.

Electron impact excitation of highly charged sodium-like ions

NASA Technical Reports Server (NTRS)

Blaha, M.; Davis, J.

1978-01-01

Optical transition probabilities and electron collision strengths for Ca X, Fe XVI, Zn XX, Kr XXVI and Mo XXXII are calculated for transitions between n equal to 3 and n equal to 4 levels. The calculations neglect relativistic effects on the radial functions. A semi-empirical approach provides wave functions of the excited states; a distorted wave function without exchange is employed to obtain the excitation cross sections. The density dependence of the relative intensities of certain emission lines in the sodium isoelectronic sequence is also discussed.

Theoretical (in B3LYP/6-3111++G** level), spectroscopic (FT-IR, FT-Raman) and thermogravimetric studies of gentisic acid and sodium, copper(II) and cadmium(II) gentisates.

PubMed

Regulska, E; Kalinowska, M; Wojtulewski, S; Korczak, A; Sienkiewicz-Gromiuk, J; Rzączyńska, Z; Swisłocka, R; Lewandowski, W

2014-11-11

The DFT calculations (B3LYP method with 6-311++G(d,p) mixed with LanL2DZ for transition metals basis sets) for different conformers of 2,5-dihydroxybenzoic acid (gentisic acid), sodium 2,5-dihydroxybenzoate (gentisate) and copper(II) and cadmium(II) gentisates were done. The proposed hydrated structures of transition metal complexes were based on the results of experimental findings. The theoretical geometrical parameters and atomic charge distribution were discussed. Moreover Na, Cu(II) and Cd(II) gentisates were synthesized and the composition of obtained compounds was revealed by means of elemental and thermogravimetric analyses. The FT-IR and FT-Raman spectra of gentisic acid and gentisates were registered and the effect of metals on the electronic charge distribution of ligand was discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel Electronic Behavior Driving NdNiO 3 Metal-Insulator Transition

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

Upton, M. H.; Choi, Yongseong; Park, Hyowon

2015-07-01

We present evidence that the metal-insulator transition (MIT) in a tensile-strained NdNiO3 (NNO) film is facilitated by a redistribution of electronic density and that it neither requires Ni charge disproportionation nor a symmetry change [U. Staub et al., Phys. Rev. Lett. 88, 126402 (2002); R. Jaramillo et al., Nat. Phys. 10, 304 (2014)]. Given that epitaxial tensile strain in thin NNO films induces preferential occupancy of the e(g) d(x2-y2) orbital we propose that the larger transfer integral of this orbital state with the O 2p orbital state mediates a redistribution of electronic density from the Ni atom. A decrease inmore » the Ni d(x2-y2) orbital occupation is directly observed by resonant inelastic x-ray scattering below the MIT temperature. Furthermore, an increase in the Nd charge occupancy is measured by x-ray absorption at the Nd L-3 edge. Both spin-orbit coupling and crystal field effects combine to break the degeneracy of the Nd 5d states, shifting the energy of the Nd e(g) d(x2-y2) orbit towards the Fermi level, allowing the A site to become an active acceptor during the MIT. This work identifies the relocation of electrons from the Ni 3d to the Nd 5d orbitals across the MIT. We propose that the insulating gap opens between the Ni 3d and O 2p states, resulting from Ni 3d electron localization. The transition seems to be neither a purely Mott-Hubbard transition nor a simple charge transfer.« less

Plug-In Electric Vehicle Fast Charge Station Operational Analysis with Integrated Renewables: Preprint

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

Simpson, M.; Markel, T.

2012-08-01

The growing, though still nascent, plug-in electric vehicle (PEV) market currently operates primarily via level 1 and level 2 charging in the United States. Fast chargers are still a rarity, but offer a confidence boost to oppose 'range anxiety' in consumers making the transition from conventional vehicles to PEVs. Because relatively no real-world usage of fast chargers at scale exists yet, the National Renewable Energy Laboratory developed a simulation to help assess fast charging needs based on real-world travel data. This study documents the data, methods, and results of the simulation run for multiple scenarios, varying fleet sizes, and themore » number of charger ports. The grid impact of this usage is further quantified to assess the opportunity for integration of renewables; specifically, a high frequency of fast charging is found to be in demand during the late afternoons and evenings coinciding with grid peak periods. Proper integration of a solar array and stationary battery thus helps ease the load and reduces the need for new generator construction to meet the demand of a future PEV market.« less

Controlling the electric charge of gold nanoplatelets on an insulator by field emission nc-AFM

NASA Astrophysics Data System (ADS)

Baris, Bulent; Alchaar, Mohanad; Prasad, Janak; Gauthier, Sébastien; Dujardin, Erik; Martrou, David

2018-03-01

Charging of 2D Au nanoplatelets deposited on an insulating SiO2 substrate to or from the tip of a non-contact atomic force microscope (nc-AFM) is demonstrated. Charge transfer is controlled by monitoring the resonance frequency shift Δf(V) during the bias voltage ramp V applied to the tip-back electrode junction. The onset of charge transfer is revealed by a transition from a capacitive parabolic behavior to a constant Δf(V) region for both polarities. An analytical model, based on charging by electron field emission, shows that the field-emitted current saturates shortly after the onset of the charging, due to the limiting effect of the charge-induced rise of the Au platelet potential. The value of this current plateau depends only on the rate of the bias voltage ramp and on the value of the platelet/SiO2/back electrode capacitance. This analysis is confirmed by numerical simulations based on a virtual nc-AFM model that faithfully matches the experimental data. Our charging protocol could be used to tune the potential of the platelets at the single charge level.

Project Startup: Evaluating the Performance of Electric Buses

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

2016-04-01

The National Renewable Energy Laboratory (NREL) is evaluating the in-service performance of fast-charge battery electric buses compared to compressed natural gas (CNG) buses operated by Foothill Transit in West Covina, California. Launched in 2015 in collaboration with the California Air Resources Board, this study aims to improve understanding of the overall use and effectiveness of fast-charge electric buses and associated charging infrastructure in transit operation.

Reversible structure manipulation by tuning carrier concentration in metastable Cu2S

PubMed Central

Tao, Jing; Chen, Jingyi; Li, Jun; Mathurin, Leanne; Zheng, Jin-Cheng; Li, Yan; Lu, Deyu; Cao, Yue; Wu, Lijun; Cava, Robert Joseph; Zhu, Yimei

2017-01-01

The optimal functionalities of materials often appear at phase transitions involving simultaneous changes in the electronic structure and the symmetry of the underlying lattice. It is experimentally challenging to disentangle which of the two effects––electronic or structural––is the driving force for the phase transition and to use the mechanism to control material properties. Here we report the concurrent pumping and probing of Cu2S nanoplates using an electron beam to directly manipulate the transition between two phases with distinctly different crystal symmetries and charge-carrier concentrations, and show that the transition is the result of charge generation for one phase and charge depletion for the other. We demonstrate that this manipulation is fully reversible and nonthermal in nature. Our observations reveal a phase-transition pathway in materials, where electron-induced changes in the electronic structure can lead to a macroscopic reconstruction of the crystal structure. PMID:28855335

In-Use Fleet Evaluation of Fast-Charge Battery Electric Transit Buses

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

Prohaska, Robert; Kelly, Kenneth; Eudy

2016-06-27

With support from the U.S. Department of Energy's Vehicle Technologies Office, the National Renewable Energy Laboratory (NREL) conducts real-world performance evaluations of advanced medium- and heavy-duty fleet vehicles. Evaluation results can help vehicle manufacturers fine-tune their designs and assist fleet managers in selecting fuel-efficient, low-emission vehicles that meet their economic and operational goals. In 2015, NREL launched an in-service evaluation of 12 battery electric buses (BEBs) compared to conventional compressed natural gas (CNG) buses operated by Foothill Transit in West Covina, California. The study aims to improve understanding of the overall usage and effectiveness of fast-charge BEBs and associated chargingmore » infrastructure in transit operation. To date, NREL researchers have analyzed more than 148,000 km of in-use operational data, including driving and charging events. Foothill Transit purchased the BEBs with grant funding from the Federal Transit Administration's Transit Investments for Greenhouse Gas and Energy Reduction Program.« less

Gamow-Teller transitions in the 64Ni(3He, t)64Cu reaction

NASA Astrophysics Data System (ADS)

Popescu, L.; Adachi, T.; Berg, G. P. A.; von Brentano, P.; De Frenne, D.; Fujita, K.; Fujita, Y.; Hatanaka, K.; Jacobs, E.; Negret, A.; Nakanishi, K.; Sakemi, Y.; Shimbara, Y.; Shimizu, Y.; Tameshige, Y.; Tamii, A.; Uchida, M.; Yosoi, M.

2005-10-01

In order to study the Gamow-Teller (GT) transitions in the fp-shell nucleus 64Cu, the 64Ni(3He, t)64Cu charge-exchange reaction was investigated at E3He= 140 MeV/nucleon [1]. The outgoing tritons were momentum analysed by the Grand Raiden spectrometer at 0°. The very high energy resolution of 35 keV (FWHM) allowed the separation of individual levels in the excitation energy region from 0 to 3.5 MeV. An angular distribution analysis was performed for the observed transitions to these states. In addition to the ground state (g.s.), known to be a Jπ = 1+ GT state, several excited states showed L = 0 nature, making them candidates of GT states. At higher excitation energies, the level density becomes very high and a bump-like structure, the so-called GT Giant Resonance, dominates the spectrum.

Large impact of reorganization energy on photovoltaic conversion due to interfacial charge-transfer transitions.

PubMed

Fujisawa, Jun-ichi

2015-05-14

Interfacial charge-transfer (ICT) transitions are expected to be a novel charge-separation mechanism for efficient photovoltaic conversion featuring one-step charge separation without energy loss. Photovoltaic conversion due to ICT transitions has been investigated using several TiO2-organic hybrid materials that show organic-to-inorganic ICT transitions in the visible region. In applications of ICT transitions to photovoltaic conversion, there is a significant problem that rapid carrier recombination is caused by organic-inorganic electronic coupling that is necessary for the ICT transitions. In order to solve this problem, in this work, I have theoretically studied light-to-current conversions due to the ICT transitions on the basis of the Marcus theory with density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations. An apparent correlation between the reported incident photon-to-current conversion efficiencies (IPCE) and calculated reorganization energies was clearly found, in which the IPCE increases with decreasing the reorganization energy consistent with the Marcus theory in the inverted region. This activation-energy dependence was systematically explained by the equation formulated by the Marcus theory based on a simple excited-state kinetic scheme. This result indicates that the reduction of the reorganization energy can suppress the carrier recombination and enhance the IPCE. The reorganization energy is predominantly governed by the structural change in the chemical-adsorption moiety between the ground and ICT excited states. This work provides crucial knowledge for efficient photovoltaic conversion due to ICT transitions.

High resolution photoemission investigation: The oxidation of W

NASA Astrophysics Data System (ADS)

Morar, J. F.; Himpsel, F. J.; Hughes, G. J.; Jordan, J. L.; McFeely, F. R.; Hollinge, G.

High resolution photoemission measurements of surface oxide layers on tungsten has revealed a set of well resolved core level shifts characteristic of individual metal oxidation states. Measurement and analysis of this type of data can provide specific and quantitative chemical information about surface oxides. The formation of bonds between transition metals and strongly electronegative elements such as oxygen and fluorine results in charge transfer with the effect of shifting the metal core electron binding energies. The magnitude of such shifts depends primarily on two factors; the amount of charge transfer and the screening ability of the metals electrons. The size of core-level shifts tend to increase with additional charge transfer and be decreased by screening. In the case of tungsten the amount of screening should be a function of oxygen content since the oxygen ties up free electrons which are effective at screening. A continuous change in the tungsten core level shifts is observed with increasing oxygen content, i.e., as the screening changes from that characteristic of a metal screened to that characteristic of an insulator unscreened.

23 CFR 810.212 - Use to be without charge.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 23 Highways 1 2010-04-01 2010-04-01 false Use to be without charge. 810.212 Section 810.212 Highways FEDERAL HIGHWAY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION PUBLIC TRANSPORTATION MASS TRANSIT AND SPECIAL USE HIGHWAY PROJECTS Making Highway Rights-of-Way Available for Mass Transit Projects...

Triangulated IEP Transition Goals: Developing Relevant and Genuine Annual Goals

ERIC Educational Resources Information Center

Peterson, Lori Y.; Burden, Jon Paul; Sedaghat, Jennifer M.; Gothberg, June E.; Kohler, Paula D.; Coyle, Jennifer L.

2013-01-01

Special education professionals are charged to develop relevant, compliant, and legally defensible IEPs for transition-age students with disabilities. This charge is intensified as educators strive to provide plans that will genuinely prepare students for postsecondary education, employment, and independent living. This manuscript demonstrates how…

Secondary ion emission from Ti, V, Cu, Ag and Au surfaces under KeV Cs + irradiation

NASA Astrophysics Data System (ADS)

van der Heide, P. A. W.

2005-02-01

Low energy mono-atomic singly charged secondary ion emissions from Ti, V, Cu, Ag and Au substrates during the initial stages of sputtering with Cs + primary ions have been studied. With the exception of the Ag - secondary ions, all exhibited exponential like correlations with the Cs induced work function changes. This, along with the lack of variations in the valence band structure around the Fermi edge, is consistent with resonance charge transfer to/from states located at the Fermi edge. The insensitivity of Ag - to work function appears to stem from the dominance of a separate ion formation process, namely charge transfer into vacant 4d states in the sputtered population, which themselves appear to be produced through collective oscillations. A similar excitation-mediated process involving different levels also appears to be active in the formation of other negatively charged transition metal ions, albeit to a much lesser degree.

The behavior of exciplex decay processes and interplay of radiationless transition and preliminary reorganization mechanisms of electron transfer in loose and tight pairs of reactants.

PubMed

Kuzmin, Michael G; Soboleva, Irina V; Dolotova, Elena V

2007-01-18

Exciplex emission spectra and rate constants of their decay via internal conversion and intersystem crossing are studied and discussed in terms of conventional radiationless transition approach. Exciplexes of 9-cyanophenanthrene with 1,2,3-trimethoxybenzene and 1,3,5-trimethoxybenzene were studied in heptane, toluene, butyl acetate, dichloromethane, butyronitrile, and acetonitrile. A better description of spectra and rate constants is obtained using 0-0 transition energy and Gauss broadening of vibrational bands rather than the free energy of electron transfer and reorganization energy. The coincidence of parameters describing exciplex emission spectra and dependence of exciplex decay rate constants on energy gap gives the evidence of radiationless quantum transition mechanism rather than thermally activated medium reorganization mechanism of charge recombination in exciplexes and excited charge transfer complexes (contact radical ion pairs) as well as in solvent separated radical ion pairs. Radiationless quantum transition mechanism is shown to provide an appropriate description also for the main features of exergonic excited-state charge separation reactions if fast mutual transformations of loose and tight pairs of reactants are considered. In particular, very fast electron transfer (ET) in tight pairs of reactants with strong electronic coupling of locally excited and charge transfer states can prevent the observation of an inverted region in bimolecular excited-state charge separation even for highly exergonic reactions.

Hidden Criticality of Counterion Condensation Near a Charged Cylinder.

PubMed

Cha, Minryeong; Yi, Juyeon; Kim, Yong Woon

2017-09-05

Counterion condensation onto a charged cylinder, known as the Manning transition, has received a great deal of attention since it is essential to understand the properties of polyelectrolytes in ionic solutions. However, the current understanding is still far from complete and poses a puzzling question: While the strong-coupling theory valid at large ionic correlations suggests a discontinuous nature of the counterion condensation, the mean-field theory always predicts a continuous transition at the same critical point. This naturally leads to a question how one can reconcile the mean-field theory with the strong-coupling prediction. Here, we study the counterion condensation transition on a charged cylinder via Monte Carlo simulations. Varying the cylinder radius systematically in relation to the system size, we find that in addition to the Manning transition, there exists a novel transition where all counterions are bound to the cylinder and the heat capacity shows a drop at a finite Manning parameter. A finite-size scaling analysis is carried out to confirm the criticality of the complete condensation transition, yielding the same critical exponents with the Manning transition. We show that the existence of the complete condensation is essential to explain how the condensation nature alters from continuous to discontinuous transition.

Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

NASA Astrophysics Data System (ADS)

Rogge, Paul C.; Chandrasena, Ravini U.; Cammarata, Antonio; Green, Robert J.; Shafer, Padraic; Lefler, Benjamin M.; Huon, Amanda; Arab, Arian; Arenholz, Elke; Lee, Ho Nyung; Lee, Tien-Lin; Nemšák, Slavomír; Rondinelli, James M.; Gray, Alexander X.; May, Steven J.

2018-01-01

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ˜5 -10 % in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.

Magnetic field enhancement of organic photovoltaic cells performance.

PubMed

Oviedo-Casado, S; Urbina, A; Prior, J

2017-06-27

Charge separation is a critical process for achieving high efficiencies in organic photovoltaic cells. The initial tightly bound excitonic electron-hole pair has to dissociate fast enough in order to avoid photocurrent generation and thus power conversion efficiency loss via geminate recombination. Such process takes place assisted by transitional states that lie between the initial exciton and the free charge state. Due to spin conservation rules these intermediate charge transfer states typically have singlet character. Here we propose a donor-acceptor model for a generic organic photovoltaic cell in which the process of charge separation is modulated by a magnetic field which tunes the energy levels. The impact of a magnetic field is to intensify the generation of charge transfer states with triplet character via inter-system crossing. As the ground state of the system has singlet character, triplet states are recombination-protected, thus leading to a higher probability of successful charge separation. Using the open quantum systems formalism we demonstrate that the population of triplet charge transfer states grows in the presence of a magnetic field, and discuss the impact on carrier population and hence photocurrent, highlighting its potential as a tool for research on charge transfer kinetics in this complex systems.

In-beam γ-ray spectroscopy of the N=Z+1 nucleus 63Ga

NASA Astrophysics Data System (ADS)

Balamuth, D. P.; Hüttmeier, U. J.; Chapuran, T.; Popescu, D. G.; Arrison, J. W.

1991-05-01

A total of ten previously observed γ rays have been assigned to the N=Z+1 nucleus 63Ga; these provide the first information on excited states reported in this neutron-deficient system. 63Ga has been populated using the 40Ca(28Si, αp), 40Ca(32S, 2αp), and 40Ca(29Si, αpn) reactions at beam energies of 80-100 MeV. Particle-γ coincidence techniques provide a definitive identification of γ transitions in 63Ga. An yrast-level scheme is proposed on the basis of charged-particle-γ, charged-particle-γ-γ, and neutron-γ-γ coincidences. Spin and parity assignments are based on neutron-gated γ-ray angular distributions, directional correlation with oriented nuclei ratios and systematics. Nine new energy levels are identified in addition to the previously known ground state, with the highest level at an excitation energy of 7.7 MeV. The results are interpreted in terms of the relevant single-particle orbitals and the systematics of the neighboring nuclei. In addition, a new determination has been made of the E2/M1 mixing ratio for the (5/2-)1-->(3/2-)1 transition in 65Ga, resolving a disagreement between two previous measurements.

Melting of Pb Charge Glass and Simultaneous Pb-Cr Charge Transfer in PbCrO 3 as the Origin of Volume Collapse

DOE PAGES

Yu, Runze; Hojo, Hajime; Watanuki, Tetsu; ...

2015-09-15

A metal to insulator transition in integer or half integer charge systems can be regarded as crystallization of charges. The insulating state tends to have a glassy nature when randomness or geometrical frustration exists. In this paper, we report that the charge glass state is realized in a perovskite compound PbCrO 3, which has been known for almost 50 years, without any obvious inhomogeneity or triangular arrangement in the charge system. PbCrO 3 has a valence state of Pb 2+ 0.5Pb 4+ 0.5Cr 3+O 3 with Pb 2+–Pb 4+ correlation length of three lattice-spacings at ambient condition. A pressure inducedmore » melting of charge glass and simultaneous Pb–Cr charge transfer causes an insulator to metal transition and ~10% volume collapse.« less

Unusual Thermoelectric Behavior Indicating a Hopping to Bandlike Transport Transition in Pentacene

NASA Astrophysics Data System (ADS)

Germs, W. Chr.; Guo, K.; Janssen, R. A. J.; Kemerink, M.

2012-07-01

An unusual increase in the Seebeck coefficient with increasing charge carrier density is observed in pentacene thin film transistors. This behavior is interpreted as being due to a transition from hopping transport in static localized states to bandlike transport, occurring at temperatures below ˜250K. Such a transition can be expected for organic materials in which both static energetic disorder and dynamic positional disorder are important. While clearly visible in the temperature and density dependent Seebeck coefficient, the transition hardly shows up in the charge carrier mobility.

Charge migration and charge transfer in molecular systems

PubMed Central

Wörner, Hans Jakob; Arrell, Christopher A.; Banerji, Natalie; Cannizzo, Andrea; Chergui, Majed; Das, Akshaya K.; Hamm, Peter; Keller, Ursula; Kraus, Peter M.; Liberatore, Elisa; Lopez-Tarifa, Pablo; Lucchini, Matteo; Meuwly, Markus; Milne, Chris; Moser, Jacques-E.; Rothlisberger, Ursula; Smolentsev, Grigory; Teuscher, Joël; van Bokhoven, Jeroen A.; Wenger, Oliver

2017-01-01

The transfer of charge at the molecular level plays a fundamental role in many areas of chemistry, physics, biology and materials science. Today, more than 60 years after the seminal work of R. A. Marcus, charge transfer is still a very active field of research. An important recent impetus comes from the ability to resolve ever faster temporal events, down to the attosecond time scale. Such a high temporal resolution now offers the possibility to unravel the most elementary quantum dynamics of both electrons and nuclei that participate in the complex process of charge transfer. This review covers recent research that addresses the following questions. Can we reconstruct the migration of charge across a molecule on the atomic length and electronic time scales? Can we use strong laser fields to control charge migration? Can we temporally resolve and understand intramolecular charge transfer in dissociative ionization of small molecules, in transition-metal complexes and in conjugated polymers? Can we tailor molecular systems towards specific charge-transfer processes? What are the time scales of the elementary steps of charge transfer in liquids and nanoparticles? Important new insights into each of these topics, obtained from state-of-the-art ultrafast spectroscopy and/or theoretical methods, are summarized in this review. PMID:29333473

Subgap time of flight: A spectroscopic study of deep levels in semi-insulating CdTe:Cl

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

Pousset, J.; Farella, I.; Cola, A., E-mail: adriano.cola@le.imm.cnr.it

2016-03-14

We report on a study of deep levels in semi-insulating CdTe:Cl by means of a time-of-flight spectral approach. By varying the wavelength of a pulsed optical source within the CdTe energy gap, transitions to/from localized levels generate free carriers which are analysed through the induced photocurrent transients. Both acceptor-like centers, related to the A-center, and a midgap level, 0.725 eV from the valence band, have been detected. The midgap level is close to the Fermi level and is possibly a recombination center responsible for the compensation mechanism. When the irradiance is varied, either linear or quadratic dependence of the electron andmore » hole collected charge are observed, depending on the dominant optical transitions. The analysis discloses the potentiality of such a novel approach exploitable in the field of photorefractive materials as well as for deep levels spectroscopy.« less

Extracting dielectric fixed charge density on highly doped crystalline-silicon surfaces using photoconductance measurements

NASA Astrophysics Data System (ADS)

To, A.; Hoex, B.

2017-11-01

A novel method for the extraction of fixed interface charge, Qf, and the surface recombination parameters, Sn0 and Sp0, from the injection-level dependent effective minority carrier lifetime measurements is presented. Unlike conventional capacitance-voltage measurements, this technique can be applied to highly doped surfaces provided the surface carrier concentration transitions into strong depletion or inversion with increased carrier injection. By simulating the injection level dependent Auger-corrected inverse lifetime curve of symmetrically passivated and diffused samples after sequential annealing and corona charging, it was revealed that Qf, Sn0, and Sp0 have unique signatures. Therefore, these important electronic parameters, in some instances, can independently be resolved. Furthermore, it was shown that this non-linear lifetime behaviour is exhibited on both p-type and n-type diffused inverted surfaces, by demonstrating the approach with phosphorous diffused n+pn+ structures and boron diffused p+np+ structures passivated with aluminium oxide (AlOx) and silicon nitride, respectively (SiNx). The results show that the approximation of a mid-gap Shockley-Read-Hall defect level with equal capture cross sections is able to, in the samples studied in this work, reproduce the observed injection level dependent lifetime behaviour.

Burning to Detonation Transition in Porous Beds of a High Energy Propellant

DTIC Science & Technology

1979-11-01

deflagration to detonation transition (DDT) behavior of porous charges of a high-energy propellant (VL-U) has been stualed at both high and low...transition (DDT) behavior of porous charges of a high-eneryy propellant (VLU) has been studied at both high confinement (steel tube) and low confinement...plastic tube). The physical nature of thet propellant ised to construct the porous beds was varied: shredded, powdered CI ,-: and cuboid materials were

Optical properties of two-dimensional charge density wave materials

NASA Astrophysics Data System (ADS)

Sayers, Charles; Karbassi, Sara; Friedemann, Sven; da Como, Enrico

Titanium diselenide (TiSe2) is a member of the layered transition metal dichalcogenide (TMD) materials. It exhibits unusual chiral charge ordering below 190 K after undergoing an initial phase transition to a commensurate (2 x 2 x 2) charge density wave (CDW) at 200 K which is enhanced further in the monolayer. Recently, the first evidence of chirality in a CDW system was discovered in this material by scanning tunneling microscopy and time-resolved reflectivity experiments, where separate left and right handed charge-ordered domains were found to exist within a single sample. We have prepared single crystals of 1T-TiSe2 using iodine vapour transport, and confirmed their quality by x-ray analysis and charge transport measurements. Using a combination of polarised optical spectroscopy techniques in the mid to far infrared (4 to 700 meV photon energy), we have measured an anisotropy relating to the CDW gap. We discuss the results on the basis of chiral domains with different handedness and the nature of the CDW transition.

Dissociation of methane on the surface of charged defective carbon nanotubes

NASA Astrophysics Data System (ADS)

Guo, Z. H.; Yan, X. H.; Xiao, Y.

2010-03-01

Based on the framework of density functional theory (CASTEP and DMOL 3 codes), we simulate the dissociation of methane (CH 4) molecule on the surface of charged defective carbon nanotubes (CNTs). The results display that a charged CNT with carbon (C) and molybdenum (Mo) dopants can effectively dissociate CH 4 molecule, and the adsorption strength of H and CH 3 can be controlled by the injected negative charges. Moreover, the barrier between the transition state (TS) and the reactant is 0.1014 eV, and a single imaginary frequency of -0.3 cm is found for the transition state structure.

Evolution of Xe spectrum and ion charge under sudden incoming radiation

NASA Astrophysics Data System (ADS)

Klapisch, Marcel; Busquet, Michel

2012-06-01

Experiments [1] and simulations of Xe at high temperature were recently reported, due to the possible scaling of astrophysical radiative shocks [2]. We used the newest version of HULLAC [3] to compute energy levels, radiative and collisional transition rates and level populations in a Coronal Radiative Model for the ions Xe9+ to Xe44+ (36263 configurations), at electron temperature of 100 eV and electron density of 10^19 -- 10^21 e/cm^3, in the presence of an external Planckian radiation field. Static and time dependent influence of the radiation on ion charge and spectrum is described. We show an effect of shell structure on relaxation of ion charge when the radiation field is suddenly turn on.[4pt] [1] Busquet, M., Thais, F., Gonzalez, M., et al., J. App. Phys. 107, 083302 (2010).[0pt] [2] Ryutov, D., Drake, R. P., Kane, J., et al., Astrophys. J. 518, 821 (1999).[0pt] [3] Klapisch, M. and Busquet, M., High Ener. Dens. Phys. 7, 98 (2011).

Phase diagram of the underdoped cuprates at high magnetic field

NASA Astrophysics Data System (ADS)

Chakraborty, Debmalya; Morice, Corentin; Pépin, Catherine

2018-06-01

The experimentally measured phase diagram of cuprate superconductors in the temperature-applied magnetic field plane illuminates key issues in understanding the physics of these materials. At low temperature, the superconducting state gives way to a long-range charge order with increasing magnetic field; both the orders coexist in a small intermediate region. The charge order transition is strikingly insensitive to temperature and quickly reaches a transition temperature close to the zero-field superconducting Tc. We argue that such a transition along with the presence of the coexisting phase is difficult to obtain in a weak coupling competing orders formalism. We demonstrate that for some range of parameters there is an enlarged symmetry of the strongly coupled charge and superconducting orders in the system depending on their relative masses and the coupling strength of the two orders. We establish that this sharp switch from the superconducting phase to the charge order phase can be understood in the framework of a composite SU(2) order parameter comprising the charge and superconducting orders. Finally, we illustrate that there is a possibility of the coexisting phase of the competing charge and superconducting orders only when the SU(2) symmetry between them is weakly broken due to biquadratic terms in the free energy. The relation of this sharp transition to the proximity to the pseudogap quantum critical doping is also discussed.

Charge-regulation phase transition on surface lattices of titratable sites adjacent to electrolyte solutions: An analog of the Ising antiferromagnet in a magnetic field

PubMed Central

Shore, Joel D.; Thurston, George M.

2018-01-01

We report a charge-patterning phase transition on two-dimensional square lattices of titratable sites, here regarded as protonation sites, placed in a low-dielectric medium just below the planar interface between this medium and a salt solution. We calculate the work-of-charging matrix of the lattice with use of a linear Debye-Hückel model, as input to a grand-canonical partition function for the distribution of occupancy patterns. For a large range of parameter values, this model exhibits an approximate inverse cubic power-law decrease of the voltage produced by an individual charge, as a function of its in-lattice separation from neighboring titratable sites. Thus, the charge coupling voltage biases the local probabilities of proton binding as a function of the occupancy of sites for many neighbors beyond the nearest ones. We find that even in the presence of these longer-range interactions, the site couplings give rise to a phase transition in which the site occupancies exhibit an alternating, checkerboard pattern that is an analog of antiferromagnetic ordering. The overall strength W of this canonical charge coupling voltage, per unit charge, is a function of the Debye length, the charge depth, the Bjerrum length, and the dielectric coefficients of the medium and the solvent. The alternating occupancy transition occurs above a curve of thermodynamic critical points in the (pH-pK,W) plane, the curve representing a charge-regulation analog of variation of the Néel temperature of an Ising antiferromagnet as a function of an applied, uniform magnetic field. The analog of a uniform magnetic field in the antiferromagnet problem is a combination of pH-pK and W, and 1/W is the analog of the temperature in the antiferromagnet problem. We use Monte Carlo simulations to study the occupancy patterns of the titratable sites, including interactions out to the 37th nearest-neighbor category (a distance of 74 lattice constants), first validating simulations through comparison with exact and approximate results for the nearest-neighbor case. We then use the simulations to map the charge-patterning phase boundary in the (pH-pK,W) plane. The physical parameters that determine W provide a framework for identifying and designing real surfaces that could exhibit charge-patterning phase transitions. PMID:26764648

Charge-regulation phase transition on surface lattices of titratable sites adjacent to electrolyte solutions: An analog of the Ising antiferromagnet in a magnetic field.

PubMed

Shore, Joel D; Thurston, George M

2015-12-01

We report a charge-patterning phase transition on two-dimensional square lattices of titratable sites, here regarded as protonation sites, placed in a low-dielectric medium just below the planar interface between this medium and a salt solution. We calculate the work-of-charging matrix of the lattice with use of a linear Debye-Hückel model, as input to a grand-canonical partition function for the distribution of occupancy patterns. For a large range of parameter values, this model exhibits an approximate inverse cubic power-law decrease of the voltage produced by an individual charge, as a function of its in-lattice separation from neighboring titratable sites. Thus, the charge coupling voltage biases the local probabilities of proton binding as a function of the occupancy of sites for many neighbors beyond the nearest ones. We find that even in the presence of these longer-range interactions, the site couplings give rise to a phase transition in which the site occupancies exhibit an alternating, checkerboard pattern that is an analog of antiferromagnetic ordering. The overall strength W of this canonical charge coupling voltage, per unit charge, is a function of the Debye length, the charge depth, the Bjerrum length, and the dielectric coefficients of the medium and the solvent. The alternating occupancy transition occurs above a curve of thermodynamic critical points in the (pH-pK,W) plane, the curve representing a charge-regulation analog of variation of the Néel temperature of an Ising antiferromagnet as a function of an applied, uniform magnetic field. The analog of a uniform magnetic field in the antiferromagnet problem is a combination of pH-pK and W, and 1/W is the analog of the temperature in the antiferromagnet problem. We use Monte Carlo simulations to study the occupancy patterns of the titratable sites, including interactions out to the 37th nearest-neighbor category (a distance of √74 lattice constants), first validating simulations through comparison with exact and approximate results for the nearest-neighbor case. We then use the simulations to map the charge-patterning phase boundary in the (pH-pK,W) plane. The physical parameters that determine W provide a framework for identifying and designing real surfaces that could exhibit charge-patterning phase transitions.

Charge-regulation phase transition on surface lattices of titratable sites adjacent to electrolyte solutions: An analog of the Ising antiferromagnet in a magnetic field

NASA Astrophysics Data System (ADS)

Shore, Joel D.; Thurston, George M.

2015-12-01

We report a charge-patterning phase transition on two-dimensional square lattices of titratable sites, here regarded as protonation sites, placed in a low-dielectric medium just below the planar interface between this medium and a salt solution. We calculate the work-of-charging matrix of the lattice with use of a linear Debye-Hückel model, as input to a grand-canonical partition function for the distribution of occupancy patterns. For a large range of parameter values, this model exhibits an approximate inverse cubic power-law decrease of the voltage produced by an individual charge, as a function of its in-lattice separation from neighboring titratable sites. Thus, the charge coupling voltage biases the local probabilities of proton binding as a function of the occupancy of sites for many neighbors beyond the nearest ones. We find that even in the presence of these longer-range interactions, the site couplings give rise to a phase transition in which the site occupancies exhibit an alternating, checkerboard pattern that is an analog of antiferromagnetic ordering. The overall strength W of this canonical charge coupling voltage, per unit charge, is a function of the Debye length, the charge depth, the Bjerrum length, and the dielectric coefficients of the medium and the solvent. The alternating occupancy transition occurs above a curve of thermodynamic critical points in the (p H-p K ,W ) plane, the curve representing a charge-regulation analog of variation of the Néel temperature of an Ising antiferromagnet as a function of an applied, uniform magnetic field. The analog of a uniform magnetic field in the antiferromagnet problem is a combination of p H-p K and W , and 1 /W is the analog of the temperature in the antiferromagnet problem. We use Monte Carlo simulations to study the occupancy patterns of the titratable sites, including interactions out to the 37th nearest-neighbor category (a distance of √{74 } lattice constants), first validating simulations through comparison with exact and approximate results for the nearest-neighbor case. We then use the simulations to map the charge-patterning phase boundary in the (p H-p K ,W ) plane. The physical parameters that determine W provide a framework for identifying and designing real surfaces that could exhibit charge-patterning phase transitions.

A hybrid density functional study of silicon and phosphorus doped hexagonal boron nitride monolayer

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Igumbor, E.; Chetty, N.

2016-10-01

We present a hybrid density functional study of silicon (Si) and phosphorus (P) doped hexagonal boron nitride (h-BN). The local geometry, electronic structure and thermodynamic stability of Si B , Si N , P B and P N are examined using hybrid Heyd-Scuseria- Ernzerhof (HSE) functional. The defect induced buckling and the local bond distances around the defect are sensitive to charge state modulation q = -2, -1, 0, +1 and +2. The +1 charge state is found to be the most energetically stable state and significantly reduces the buckling. Based on the charge state thermodynamic transition levels, we noted that the Si N , Si N and P B defects are too deep to be ionized, and can alter the optical properties of h-BN material.

Electrostatic effects in the collapse transition of phospholiquid monolayer

NASA Astrophysics Data System (ADS)

Nguyen, Toan T.; Gopal, Ajaykumar; Lee, Ka Yee C.; Witten, Thomas A.

2004-03-01

We study the collapse transition of fluidic phospholipid surfactant monolayers under lateral compression. DMPC, DPPC or POPG surfactants and their binary mixtures are used. Various collapsed structures (circular discs, cylinderical tubes and pearls-on-a-string) were observed during the transition. We show that electrostatics plays an important role in the formation of these structures. By changing the composition of charged surfactant (POGP) or the screening condition of the solution, one can change the dominant collapsed structure from discs to tubes to pearls in the order of increasing the strength of electrostatic interactions, in accordance with theoretical estimates. We also study a complimentary electrostatic effect due charge relaxation in the transitions between these structures. It is shown that free energy gained from relaxations of charge molecule is small and can be neglected when considering electrostatics of these systems.

Nuclear Spin Nanomagnet in an Optically Excited Quantum Dot

NASA Astrophysics Data System (ADS)

Korenev, V. L.

2007-12-01

Linearly polarized light tuned slightly below the optical transition of the negatively charged exciton (trion) in a single quantum dot causes the spontaneous nuclear spin polarization (self-polarization) at a level close to 100%. The effective magnetic field of spin-polarized nuclei shifts the optical transition energy close to resonance with photon energy. The resonantly enhanced Overhauser effect sustains the stability of the nuclear self-polarization even in the absence of spin polarization of the quantum dot electron. As a result the optically selected single quantum dot represents a tiny magnet with the ferromagnetic ordering of nuclear spins—the nuclear spin nanomagnet.

Nuclear spin nanomagnet in an optically excited quantum dot.

PubMed

Korenev, V L

2007-12-21

Linearly polarized light tuned slightly below the optical transition of the negatively charged exciton (trion) in a single quantum dot causes the spontaneous nuclear spin polarization (self-polarization) at a level close to 100%. The effective magnetic field of spin-polarized nuclei shifts the optical transition energy close to resonance with photon energy. The resonantly enhanced Overhauser effect sustains the stability of the nuclear self-polarization even in the absence of spin polarization of the quantum dot electron. As a result the optically selected single quantum dot represents a tiny magnet with the ferromagnetic ordering of nuclear spins-the nuclear spin nanomagnet.

Infrared and visible laser spectroscopy for highly-charged Ni-like ions

NASA Astrophysics Data System (ADS)

Ralchenko, Yuri

2017-10-01

Application of visible or infrared (IR) lasers for spectroscopy of highly-charged ions (HCI) has not been particularly extensive so far due to a mismatch in typical energies. We show here that the energy difference between the two lowest levels within the first excited configuration 3d9 4 s in Ni-like ions of heavy elements from ZN = 60 to ZN = 92 is within the range of visible or near-IR lasers. The wavelengths of these transitions are calculated within the relativistic model potential formalism and compared with other theoretical and limited experimental data. Detailed collisional-radiative simulations of non-Maxwellian and thermal plasmas are performed showing that photopumping between these levels using relatively moderate lasers is sufficient to provide a two-order of magnitude increase of the pumped level population. This accordingly results in a similar rise of the X-ray line intensity thereby allowing control of X-ray emission with visible/IR lasers.

Decoupling of the antiferromagnetic and insulating states in Tb-doped Sr 2IrO 4

DOE PAGES

Wang, J. C.; Aswartham, S.; Ye, Feng; ...

2015-12-08

Sr 2IrO 4 is a spin-orbit coupled insulator with an antiferromagnetic (AFM) transition at T N = 240 K. We report results of a comprehensive study of single-crystal Sr 2Ir 1-xTb xO 4 (0≤x≤0.03). This study found that mere 3% (x=0.03) tetravalent Tb 4+(4f 7) substituting for Ir 4+ (rather than Sr 2+) completely suppresses the long-range collinear AFM transition but retains the insulating state, leading to a phase diagram featuring a decoupling of magnetic interactions and charge gap. The insulating state at x = 0.03 is characterized by an unusually large specific heat at low temperatures and an incommensuratemore » magnetic state having magnetic peaks at (0.95, 0, 0) and (0, 0.95, 0) in the neutron diffraction, suggesting a spiral or spin density wave order. It is apparent that Tb doping effectively changes the relative strength of the SOI and the tetragonal CEF and enhances the Hund’s rule coupling that competes with the SOI, and destabilizes the AFM state. However, the disappearance of the AFM accompanies no metallic state chiefly because an energy level mismatch for the Ir and Tb sites weakens charge carrier hopping and renders a persistent insulating state. Furthermore, this work highlights an unconventional correlation between the AFM and insulating states in which the magnetic transition plays no critical role in the formation of the charge gap in the iridate.« less

Effective scheme to determine accurate defect formation energies and charge transition levels of point defects in semiconductors

NASA Astrophysics Data System (ADS)

Yao, Cang Lang; Li, Jian Chen; Gao, Wang; Tkatchenko, Alexandre; Jiang, Qing

2017-12-01

We propose an effective method to accurately determine the defect formation energy Ef and charge transition level ɛ of the point defects using exclusively cohesive energy Ecoh and the fundamental band gap Eg of pristine host materials. We find that Ef of the point defects can be effectively separated into geometric and electronic contributions with a functional form: Ef=χ Ecoh+λ Eg , where χ and λ are dictated by the geometric and electronic factors of the point defects (χ and λ are defect dependent). Such a linear combination of Ecoh and Eg reproduces Ef with an accuracy better than 5% for electronic structure methods ranging from hybrid density-functional theory (DFT) to many-body random-phase approximation (RPA) and experiments. Accordingly, ɛ is also determined by Ecoh/Eg and the defect geometric/electronic factors. The identified correlation is rather general for monovacancies and interstitials, which holds in a wide variety of semiconductors covering Si, Ge, phosphorenes, ZnO, GaAs, and InP, and enables one to obtain reliable values of Ef and ɛ of the point defects for RPA and experiments based on semilocal DFT calculations.

Sequence charge decoration dictates coil-globule transition in intrinsically disordered proteins.

PubMed

Firman, Taylor; Ghosh, Kingshuk

2018-03-28

We present an analytical theory to compute conformations of heteropolymers-applicable to describe disordered proteins-as a function of temperature and charge sequence. The theory describes coil-globule transition for a given protein sequence when temperature is varied and has been benchmarked against the all-atom Monte Carlo simulation (using CAMPARI) of intrinsically disordered proteins (IDPs). In addition, the model quantitatively shows how subtle alterations of charge placement in the primary sequence-while maintaining the same charge composition-can lead to significant changes in conformation, even as drastic as a coil (swelled above a purely random coil) to globule (collapsed below a random coil) and vice versa. The theory provides insights on how to control (enhance or suppress) these changes by tuning the temperature (or solution condition) and charge decoration. As an application, we predict the distribution of conformations (at room temperature) of all naturally occurring IDPs in the DisProt database and notice significant size variation even among IDPs with a similar composition of positive and negative charges. Based on this, we provide a new diagram-of-states delineating the sequence-conformation relation for proteins in the DisProt database. Next, we study the effect of post-translational modification, e.g., phosphorylation, on IDP conformations. Modifications as little as two-site phosphorylation can significantly alter the size of an IDP with everything else being constant (temperature, salt concentration, etc.). However, not all possible modification sites have the same effect on protein conformations; there are certain "hot spots" that can cause maximal change in conformation. The location of these "hot spots" in the parent sequence can readily be identified by using a sequence charge decoration metric originally introduced by Sawle and Ghosh. The ability of our model to predict conformations (both expanded and collapsed states) of IDPs at a high-throughput level can provide valuable insights into the different mechanisms by which phosphorylation/charge mutation controls IDP function.

Sequence charge decoration dictates coil-globule transition in intrinsically disordered proteins

NASA Astrophysics Data System (ADS)

Firman, Taylor; Ghosh, Kingshuk

2018-03-01

We present an analytical theory to compute conformations of heteropolymers—applicable to describe disordered proteins—as a function of temperature and charge sequence. The theory describes coil-globule transition for a given protein sequence when temperature is varied and has been benchmarked against the all-atom Monte Carlo simulation (using CAMPARI) of intrinsically disordered proteins (IDPs). In addition, the model quantitatively shows how subtle alterations of charge placement in the primary sequence—while maintaining the same charge composition—can lead to significant changes in conformation, even as drastic as a coil (swelled above a purely random coil) to globule (collapsed below a random coil) and vice versa. The theory provides insights on how to control (enhance or suppress) these changes by tuning the temperature (or solution condition) and charge decoration. As an application, we predict the distribution of conformations (at room temperature) of all naturally occurring IDPs in the DisProt database and notice significant size variation even among IDPs with a similar composition of positive and negative charges. Based on this, we provide a new diagram-of-states delineating the sequence-conformation relation for proteins in the DisProt database. Next, we study the effect of post-translational modification, e.g., phosphorylation, on IDP conformations. Modifications as little as two-site phosphorylation can significantly alter the size of an IDP with everything else being constant (temperature, salt concentration, etc.). However, not all possible modification sites have the same effect on protein conformations; there are certain "hot spots" that can cause maximal change in conformation. The location of these "hot spots" in the parent sequence can readily be identified by using a sequence charge decoration metric originally introduced by Sawle and Ghosh. The ability of our model to predict conformations (both expanded and collapsed states) of IDPs at a high-throughput level can provide valuable insights into the different mechanisms by which phosphorylation/charge mutation controls IDP function.

Invalidity of the Fermi liquid theory and magnetic phase transition in quasi-1D dopant-induced armchair-edged graphene nanoribbons

NASA Astrophysics Data System (ADS)

Hoi, Bui Dinh; Davoudiniya, Masoumeh; Yarmohammadi, Mohsen

2018-04-01

Based on theoretically tight-binding calculations considering nearest neighbors and Green's function technique, we show that the magnetic phase transition in both semiconducting and metallic armchair graphene nanoribbons with width ranging from 9.83 Å to 69.3 Å would be observed in the presence of injecting electrons by doping. This transition is explained by the temperature-dependent static charge susceptibility through calculation of the correlation function of charge density operators. This work showed that charge concentration of dopants in such system plays a crucial role in determining the magnetic phase. A variety of multicritical points such as transition temperatures and maximum susceptibility are compared in undoped and doped cases. Our findings show that there exist two different transition temperatures and maximum susceptibility depending on the ribbon width in doped structures. Another remarkable point refers to the invalidity (validity) of the Fermi liquid theory in nanoribbons-based systems at weak (strong) concentration of dopants. The obtained interesting results of magnetic phase transition in such system create a new potential for magnetic graphene nanoribbon-based devices.

Molecular orbital (SCF-Xα-SW) theory of metal-metal charge transfer processes in minerals

USGS Publications Warehouse

Sherman, David M.

1987-01-01

Electronic transitions between the Fe-Fe bonding and Fe-Fe antibonding orbitals results in the optically-induced intervalence charge transfer bands observed in the electronic spectra of mixed valence minerals. Such transitions are predicted to be polarized along the metal-metal bond direction, in agreement with experimental observations.

Triple points and phase diagrams in the extended phase space of charged Gauss-Bonnet black holes in AdS space

NASA Astrophysics Data System (ADS)

Wei, Shao-Wen; Liu, Yu-Xiao

2014-08-01

We study the triple points and phase diagrams in the extended phase space of the charged Gauss-Bonnet black holes in d-dimensional anti-de Sitter space, where the cosmological constant appears as a dynamical pressure of the system and its conjugate quantity is the thermodynamic volume of the black holes. Employing the equation of state T=T(v,P), we demonstrate that the information of the phase transition and behavior of the Gibbs free energy are potential encoded in the T-v (T-rh) line with fixed pressure P. We get the phase diagrams for the charged Gauss-Bonnet black holes with different values of the charge Q and dimension d. The result shows that the small/large black hole phase transitions appear for any d, which is reminiscent of the liquid/gas transition of a Van der Waals type. Moreover, the interesting thermodynamic phenomena, i.e., the triple points and the small/intermediate/large black hole phase transitions are observed for d=6 and Q ∈(0.1705,0.1946).

Effect of Cation Rotation on Charge Dynamics in Hybrid Lead Halide Perovskites

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

Gélvez-Rueda, María C.; Cao, Duyen H.; Patwardhan, Sameer

Organic-inorganic hybrid halide perovskites are a promising class of materials for photovoltaic application with reported power efficiencies over similar to 22%. However, not much is known about the influence of the organic dipole rotation and phase transitions on charge carrier dynamics. Here, we report substantial changes in mobility and lifetime of charge carriers in CH 3NH 3PbI 3 after the low-temperature tetragonal (beta) to orthorhombic (gamma) phase transition. By using microwave conductivity measurements, we observed that the mobility and lifetime of ionized charge carriers increase as the temperature decreases and a sudden increment is seen after the beta-gamma phase transition.more » For CH 3NH 3PbI 3, the mobility and the half-lifetime increase by a factor of 36 compared with the values before the beta-gamma phase transition. We attribute the considerable change in the dynamics at low temperature to the decrease of the inherent dynamic disorder of the organic cation (CH 3NH 3+) inside the perovskite crystal structure.« less

EUV emission spectra in collisions of highly charged tantalum ions with nitrogen and oxygen molecules

NASA Astrophysics Data System (ADS)

Tanuma, Hajime; Numadate, Naoki; Uchikura, Yoshiyuki; Shimada, Kento; Akutsu, Takuto; Long, Elaine; O'Sullivan, Gerry

2017-10-01

We have performed ion beam collision experiments using multiply charged tantalum ions and observed EUV (extreme ultra-violet) emission spectra in collisions of ions with molecular targets, N2 and O2. Broad UTAs (un-resolved transition arrays) from multiply charged Ta ions were observed, and the mean wavelengths of the UTAs shifted and became shorter at higher charge statea of Ta ions. These UTAs may be attributed to the 4f-5d and 4f-5g transitions. Not only the UTA emission from incident ions, but also the sharp emission lines from multiply charged fragment atomic ions were observed. Production of temporary highly charged molecular ions, their kinetic energy and fragmentation processes have been investigated with coincident detection technique. However, the observation of emission from the fragments might be for the first time. The formation mechanisms of the multiply charged fragment atomic ions from target molecules are discussed.

Experimental exploration of the Mulliken-Hush relationship for intramolecular electron transfer reactions.

PubMed

Mukherjee, Tamal; Ito, Naoki; Gould, Ian R

2011-03-17

The Mulliken-Hush (M-H) relationship provides the critical link between optical and thermal electron transfer processes, and yet very little direct experimental support for its applicability has been provided. Dicyanovinylazaadamantane (DCVA) represents a simple two-state (neutral/charge-transfer) intramolecular electron transfer system that exhibits charge-transfer absorption and emission spectra that are readily measurable in solvents with a wide range of polarities. In this regard it represents an ideal model system for studying the factors that control both optical charge separation (absorption) and recombination (emission) processes in solution. Here we explore the applicability of the M-H relation to quantitative descriptions of the optical charge-transfer processes in DCVA. For DCVA, the measured radiative rate constants exhibit a linear dependence on transition energy, and transition dipole moments exhibit an inverse dependence on transition energy, consistent with the M-H relationship.

Electrohydrodynamic simulation of an electrospray in a colloid thruster

NASA Astrophysics Data System (ADS)

Jugroot, Manish; Forget, Martin; Malardier-Jugroot, Cecile

2012-02-01

A precise understanding of electrosprays is highly interesting as the complexity of micro-technology (such as nano-material processing, spacecraft propulsion and mass-spectrometers) systems increases. A multi-component CFD-based model coupling fluid dynamics, charged species dynamics and electric field is developed. The simulations describe the charged fluid interface with emphasis on the Taylor cone formation and cone-jet transition under the effect of a electric field. The goal is to recapture this transition from a rounded liquid interface into a Taylor cone from an initial uniform distribution, without making assumptions on the behaviour, geometry or charge distribution of the system. The time evolution of the interface highlights the close interaction among space charge, coulombic forces and the surface tension, which appear as governing and competing processes in the transition. The results from the coupled formalism provide valuable insights on the physical phenomena and will be applied to a colloid thruster for small spacecrafts.

Charge ordering in two-dimensional ionic liquids

NASA Astrophysics Data System (ADS)

Perera, Aurélien; Urbic, Tomaz

2018-04-01

The structural properties of model two-dimensional (2D) ionic liquids are examined, with a particular focus on the charge ordering process, with the use of computer simulation and integral equation theories. The influence of the logarithmic form of the Coulomb interaction, versus that of a 3D screened interaction form, is analysed. Charge order is found to hold and to be analogous for both interaction models, despite their very different form. The influence of charge ordering in the low density regime is discussed in relation to well known properties of 2D Coulomb fluids, such as the Kosterlitz-Thouless transition and criticality. The present study suggests the existence of a stable thermodynamic labile cluster phase, implying the existence of a liquid-liquid "transition" above the liquid-gas binodal. The liquid-gas and Kosterlitz-Thouless transitions would then take place inside the predicted cluster phase.

Spatial distribution of transferred charges across the heterointerface between perovskite transition metal oxides LaNiO{sub 3} and LaMnO{sub 3}

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

Kitamura, Miho; Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization; Horiba, Koji

2016-03-14

To investigate the interfacial charge-transfer phenomena between perovskite transition metal oxides LaNiO{sub 3} (LNO) and LaMnO{sub 3} (LMO), we have performed in situ x-ray absorption spectroscopy (XAS) measurements on LNO/LMO multilayers. The Ni-L{sub 2,3} and Mn-L{sub 2,3} XAS spectra clearly show the occurrence of electron transfer from Mn to Ni ions in the interface region. Detailed analysis of the thickness dependence of these XAS spectra has revealed that the spatial distribution of the transferred charges across the interface is significantly different between the two constituent layers. The observed spatial distribution is presumably described by the charge spreading model that treatsmore » the transfer integral between neighboring transition metal ions and the Coulomb interaction, rather than the Thomas–Fermi screening model.« less

Correlating melting and collapse of charge ordering with magnetic transitions in La{sub 0.5-x}Pr{sub x}Ca{sub 0.5}MnO{sub 3}

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

Nadeem, M., E-mail: mnadeemsb@gmail.com; Iqbal, M. Javid; Farhan, M. Arshad

2016-08-15

Highlights: • Concept of normalized magnetization is introduced to explain relative magnetic transitions. • Coexistence of two magnetic modes is correlated with the magnetic transitions and MIT. • Field induced melting and collapse of charge ordered antiferromagnetic (CO-AFM) state into ferromagnetic (FM) state is conferred. - Abstract: The magnetic properties of polycrystalline La{sub 0.5-x}Pr{sub x}Ca{sub 0.5}MnO{sub 3} material are investigated at different temperatures. The existence of magnetically diverse phases associated with various relaxation modes and their modulation with temperature and doping is analyzed. La{sub 0.5}Ca{sub 0.5}MnO{sub 3} exhibited field induced melting and collapse of charge ordered antiferromagnetic (CO-AFM) phase intomore » ferromagnetic (FM) state. This phenomenon results in lowering of Neel’s temperature (T{sub N}) along with changes in the slope of magnetic moment with temperature. Using normalized M(T) curves, the variation and interplay of charge ordered temperature (T{sub CO}), Curie temperature (T{sub C}) and T{sub N} is conferred. The coexistence of two magnetic modes is explained as major ingredient for the magnetic transitions as well as metal to insulator transition (MIT); where melting and collapse of charge ordering is conversed as basic feature in these Praseodymium (Pr) doped La{sub 0.5}Ca{sub 0.5}MnO{sub 3} materials.« less

Energetics of bacterial photosynthesis.

PubMed

Lebard, David N; Matyushov, Dmitry V

2009-09-10

We report the results of extensive numerical simulations and theoretical calculations of electronic transitions in the reaction center of Rhodobacter sphaeroides photosynthetic bacterium. The energetics and kinetics of five electronic transitions related to the kinetic scheme of primary charge separation have been analyzed and compared to experimental observations. Nonergodic formulation of the reaction kinetics is required for the calculation of the rates due to a severe breakdown of the system ergodicity on the time scale of primary charge separation, with the consequent inapplicability of the standard canonical prescription to calculate the activation barrier. Common to all reactions studied is a significant excess of the charge-transfer reorganization energy from the width of the energy gap fluctuations over that from the Stokes shift of the transition. This property of the hydrated proteins, breaking the linear response of the thermal bath, allows the reaction center to significantly reduce the reaction free energy of near-activationless electron hops and thus raise the overall energetic efficiency of the biological charge-transfer chain. The increase of the rate of primary charge separation with cooling is explained in terms of the temperature variation of induction solvation, which dominates the average donor-acceptor energy gap for all electronic transitions in the reaction center. It is also suggested that the experimentally observed break in the Arrhenius slope of the primary recombination rate, occurring near the temperature of the dynamical transition in proteins, can be traced back to a significant drop of the solvent reorganization energy close to that temperature.

Battery capacity and recharging needs for electric buses in city transit service

DOE PAGES

Gao, Zhiming; Lin, Zhenhong; LaClair, Tim J.; ...

2017-01-27

Our paper evaluates the energy consumption and battery performance of city transit electric buses operating on real day-to-day routes and standardized bus drive cycles, based on a developed framework tool that links bus electrification feasibility with real-world vehicle performance, city transit bus service reliability, battery sizing and charging infrastructure. The impacts of battery capacity combined with regular and ultrafast charging over different routes have been analyzed in terms of the ability to maintain city transit bus service reliability like conventional buses. These results show that ultrafast charging via frequent short-time boost charging events, for example at a designated bus stopmore » after completing each circuit of an assigned route, can play a significant role in reducing the battery size and can eliminate the need for longer duration charging events that would cause schedule delays. Furthermore, the analysis presented shows that significant benefits can be realized by employing multiple battery configurations and flexible battery swapping practices in electric buses. These flexible design and use options will allow electric buses to service routes of varying city driving patterns and can therefore enable meaningful reductions to the cost of the vehicle and battery while ensuring service that is as reliable as conventional buses.« less

Battery capacity and recharging needs for electric buses in city transit service

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

Gao, Zhiming; Lin, Zhenhong; LaClair, Tim J.

Our paper evaluates the energy consumption and battery performance of city transit electric buses operating on real day-to-day routes and standardized bus drive cycles, based on a developed framework tool that links bus electrification feasibility with real-world vehicle performance, city transit bus service reliability, battery sizing and charging infrastructure. The impacts of battery capacity combined with regular and ultrafast charging over different routes have been analyzed in terms of the ability to maintain city transit bus service reliability like conventional buses. These results show that ultrafast charging via frequent short-time boost charging events, for example at a designated bus stopmore » after completing each circuit of an assigned route, can play a significant role in reducing the battery size and can eliminate the need for longer duration charging events that would cause schedule delays. Furthermore, the analysis presented shows that significant benefits can be realized by employing multiple battery configurations and flexible battery swapping practices in electric buses. These flexible design and use options will allow electric buses to service routes of varying city driving patterns and can therefore enable meaningful reductions to the cost of the vehicle and battery while ensuring service that is as reliable as conventional buses.« less

Coloration of tyrosine by organic-semiconductor interfacial charge-transfer transitions

NASA Astrophysics Data System (ADS)

Fujisawa, Jun-ichi; Kikuchi, Natsumi; Hanaya, Minoru

2016-11-01

L-tyrosine (Tyr) plays a crucial role as a proteinogenic amino acid and also as a precursor to several neurotransmitters and hormones. Here we demonstrate coloration of Tyr based on organic-semiconductor interfacial charge-transfer (ICT) transitions. The ICT transitions from Tyr to TiO2 are induced by the chemisorption of Tyr on TiO2 surfaces via the hydroxy group of the phenol moiety. Because other amino acids possess no chemical group to induce ICT transitions, this coloration method enables to detect Tyr selectively without drastic structural change in contrast to the conventional coloration methods.

Charge-density study on layered oxyarsenides (LaO)MAs (M = Mn, Fe, Ni, Zn)

NASA Astrophysics Data System (ADS)

Takase, Kouichi; Hiramoto, Shozo; Fukushima, Tetsuya; Sato, Kazunori; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2017-12-01

Using synchrotron X-ray powder diffraction, we investigate the charge-density distributions of the layered oxypnictides (LaO)MnAs, (LaO)FeAs, (LaO)NiAs, and (LaO)ZnAs, which are an antiferromagnetic semiconductor, a parent material of an iron-based superconductor, a low-temperature superconductor, and a non-magnetic semiconductor, respectively. For the metallic samples, clear charge densities are observed in both the transition-metal pnictide layers and the rare-earth-oxide layers. However, in the semiconducting samples, there is no finite charge density between the transition-metal element and As. These differences in charge density reflect differences in physical properties. First-principles calculations using density functional theory reproduce the experimental results reasonably well.

Critical behavior and microscopic structure of charged AdS black holes via an alternative phase space

NASA Astrophysics Data System (ADS)

Dehyadegari, Amin; Sheykhi, Ahmad; Montakhab, Afshin

2017-05-01

It has been argued that charged Anti-de Sitter (AdS) black holes have similar thermodynamic behavior as the Van der Waals fluid system, provided one treats the cosmological constant as a thermodynamic variable (pressure) in an extended phase space. In this paper, we disclose the deep connection between charged AdS black holes and Van der Waals fluid system from an alternative point of view. We consider the mass of an AdS black hole as a function of square of the charge Q2 instead of the standard Q, i.e. M = M (S ,Q2 , P). We first justify such a change of view mathematically and then ask if a phase transition can occur as a function of Q2 for fixed P. Therefore, we write the equation of state as Q2 =Q2 (T , Ψ) where Ψ (conjugate of Q2) is the inverse of the specific volume, Ψ = 1 / v. This allows us to complete the analogy of charged AdS black holes with Van der Waals fluid system and derive the phase transition as well as critical exponents of the system. We identify a thermodynamic instability in this new picture with real analogy to Van der Waals fluid with physically relevant Maxwell construction. We therefore study the critical behavior of isotherms in Q2- Ψ diagram and deduce all the critical exponents of the system and determine that the system exhibits a small-large black hole phase transition at the critical point (Tc , Qc2 ,Ψc). This alternative view is important as one can imagine such a change for a given single black hole i.e. acquiring charge which induces the phase transition. Finally, we disclose the microscopic properties of charged AdS black holes by using thermodynamic geometry. Interestingly, we find that scalar curvature has a gap between small and large black holes, and this gap becomes exceedingly large as one moves away from the critical point along the transition line. Therefore, we are able to attribute the sudden enlargement of the black hole to the strong repulsive nature of the internal constituents at the phase transition.

Temperature dependent charge transport in poly(3-hexylthiophene) diodes

NASA Astrophysics Data System (ADS)

Rahaman, Abdulla Bin; Sarkar, Atri; Banerjee, Debamalya

2018-04-01

In this work, we present charge transport properties of poly(3-hexylthiophene) (P3HT) diodes under dark conditions. Temperature dependent current-voltage (J-V) characteristics shows that charge transport represents a transition from ohomic to trap limited current. The forward current density obeys a power law J˜Vm, m>2 represents the space charge limited current region in presence of traps within the band gap. Frequency dependent conductivity has been studied in a temperature range 150K-473K. The dc conductivity values show Arrhenius like behavior and it gives conductivity activation energy 223 meV. Temperature dependent conductivity indicates a thermodynamic transition of our system.

Highly tunable charge and spin transport in silicene junctions: phase transitions and half-metallic states.

PubMed

Mahdavifar, Maryam; Khoeini, Farhad

2018-08-10

We report peculiar charge and spin transport properties in S-shaped silicene junctions with the Kane-Mele tight-binding model. In this work, we investigate the effects of electric and exchange fields on the charge and spin transport properties. Our results show that by applying a perpendicular electric field, metal-semiconductor and also semimetal-semiconductor phase transitions occur in our systems. Furthermore, full spin current can be obtained in the structures, so the half-metallic states are observable. Our results enable us to control charge and spin currents and provide new opportunities and applications in silicene-based electronics, optoelectronics, and spintronics.

Ab initio computation of the transition temperature of the charge density wave transition in TiS e2

NASA Astrophysics Data System (ADS)

Duong, Dinh Loc; Burghard, Marko; Schön, J. Christian

2015-12-01

We present a density functional perturbation theory approach to estimate the transition temperature of the charge density wave transition of TiS e2 . The softening of the phonon mode at the L point where in TiS e2 a giant Kohn anomaly occurs, and the energy difference between the normal and distorted phase are analyzed. Both features are studied as functions of the electronic temperature, which corresponds to the Fermi-Dirac distribution smearing value in the calculation. The transition temperature is found to be 500 and 600 K by phonon and energy analysis, respectively, in reasonable agreement with the experimental value of 200 K.

Canonical Schottky barrier heights of transition metal dichalcogenide monolayers in contact with a metal

NASA Astrophysics Data System (ADS)

Szcześniak, Dominik; Hoehn, Ross D.; Kais, Sabre

2018-05-01

The transition metal dichalcogenide (M X2 , where M =Mo , W and X =S , Se, Te) monolayers are of high interest for semiconducting applications at the nanoscale level; this interest is due to both their direct band gaps and high charge mobilities. In this regard, an in-depth understating of the related Schottky barrier heights, associated with the incorporation of M X2 sheets into novel low-dimensional metal-semiconductor junctions, is of crucial importance. Herein, we generate and provide analysis of the Schottky barrier heights behavior to account for the metal-induced gap states concept as its explanation. In particular, the present investigations concentrate on the estimation of the charge neutrality levels directly by employing the primary theoretical model, i.e., the cell-averaged Green's function formalism combined with the complex band structure technique. The results presented herein place charge neutrality levels in the vicinity of the midgap; this is in agreement with previous reports and analogous to the behavior of three-dimensional semiconductors. The calculated canonical Schottky barrier heights are also found to be in agreement with other computational and experimental values in cases where the difference between electronegativities of the semiconductor and metal contact is small. Moreover, the influence of the spin-orbit effects is herein considered and supports that Schottky barrier heights have metal-induced gap state-derived character, regardless whether spin-orbit coupling interactions are considered. The results presented within this report constitute a direct and vital verification of the importance of metal-induced gap states in explaining the behavior of observed Schottky barrier heights at M X2 -metal junctions.

Pseudo-direct bandgap transitions in silicon nanocrystals: effects on optoelectronics and thermoelectrics.

PubMed

Singh, Vivek; Yu, Yixuan; Sun, Qi-C; Korgel, Brian; Nagpal, Prashant

2014-12-21

While silicon nanostructures are extensively used in electronics, the indirect bandgap of silicon poses challenges for optoelectronic applications like photovoltaics and light emitting diodes (LEDs). Here, we show that size-dependent pseudo-direct bandgap transitions in silicon nanocrystals dominate the interactions between (photoexcited) charge carriers and phonons, and hence the optoelectronic properties of silicon nanocrystals. Direct measurements of the electronic density of states (DOS) for different sized silicon nanocrystals reveal that these pseudo-direct transitions, likely arising from the nanocrystal surface, can couple with the quantum-confined silicon states. Moreover, we demonstrate that since these transitions determine the interactions of charge carriers with phonons, they change the light emission, absorption, charge carrier diffusion and phonon drag (Seebeck coefficient) in nanoscaled silicon semiconductors. Therefore, these results can have important implications for the design of optoelectronics and thermoelectric devices based on nanostructured silicon.

Phase transition detection by surface photo charge effect in liquid crystals

NASA Astrophysics Data System (ADS)

Ivanov, O.; Petrov, M.; Naradikian, H.; Perez-Diaz, J. L.

2018-05-01

The surface photo charge effect (SPCE) was applied for the first time at structure and phase transitions study of hydrogen bonded in dimer liquid crystals (HBDLCs). Due to the high sensitivity of this method, besides first-order phase transitions, characteristic for the p,n-octyloxibenzoic acids (8OBA), an order transition was definitely detected within the nematic range. We state that the SPCE, arising at the solid-HBDLCs interface due to the double electrical layer, is invariably concomitant with solid surface-liquid interfaces, and indicates that the changes of the characteristics of this layer, under incident optical irradiation, induce surface charge rearrangement and alternating potential difference. A mechanism of induction of the SPCE at the interface of solid surface-anisotropic liquids is proposed. We also indicate that this mechanism can be adapted for solid surface-isotropic liquid interface, including colloids (milk) and fog (aerosols)-condensed medium.

Superconductor to Mott insulator transition in YBa2Cu3O7/LaCaMnO3 heterostructures.

PubMed

Gray, B A; Middey, S; Conti, G; Gray, A X; Kuo, C-T; Kaiser, A M; Ueda, S; Kobayashi, K; Meyers, D; Kareev, M; Tung, I C; Liu, Jian; Fadley, C S; Chakhalian, J; Freeland, J W

2016-09-15

The superconductor-to-insulator transition (SIT) induced by means such as external magnetic fields, disorder or spatial confinement is a vivid illustration of a quantum phase transition dramatically affecting the superconducting order parameter. In pursuit of a new realization of the SIT by interfacial charge transfer, we developed extremely thin superlattices composed of high Tc superconductor YBa2Cu3O7 (YBCO) and colossal magnetoresistance ferromagnet La0.67Ca0.33MnO3 (LCMO). By using linearly polarized resonant X-ray absorption spectroscopy and magnetic circular dichroism, combined with hard X-ray photoelectron spectroscopy, we derived a complete picture of the interfacial carrier doping in cuprate and manganite atomic layers, leading to the transition from superconducting to an unusual Mott insulating state emerging with the increase of LCMO layer thickness. In addition, contrary to the common perception that only transition metal ions may respond to the charge transfer process, we found that charge is also actively compensated by rare-earth and alkaline-earth metal ions of the interface. Such deterministic control of Tc by pure electronic doping without any hindering effects of chemical substitution is another promising route to disentangle the role of disorder on the pseudo-gap and charge density wave phases of underdoped cuprates.

Cross sections and rate coefficients for inner-shell excitation of Li-like ions with 6 < Z < 42

NASA Astrophysics Data System (ADS)

Safronova, U. I.; Safronova, M. S.; Kato, T.

1996-07-01

Excitation cross sections and rate coefficients by electron impact were calculated for the 1s22s-1s2s2p, 1s22s-1s2s2 and 1s22s-1s2p2 transitions of the Li-like ions (C IV, N V, O VI, Ne VIII, Mg X, Al XI, Si XII, S XIV, Ar XVI, Ca XVIII, Ti XX, Fe XXIV, Ni XXVI, Zn XXVIII, Ge XXX, Se XXXII, Kr XXXIV and Mo XXXX) in the Coulomb-Born approximation with exchange including relativistic effects and configuration interaction. Level energies, mixing coefficients and transition wavelengths and probabilities were also computed. Calculations performed by the 1/Z perturbation theory and Coulomb-Born approximation are compared with the R-matrix method and the distorted-wave approximation were Z is the nuclear charge. Formulae obtained for the angular factors of n-electron atomic system allow one to generalize this method to an arbitrary system of highly charged ions.

Emergence of superconductivity from the dynamically heterogeneous insulating state in La(2-x)Sr(x)CuO4.

PubMed

Shi, Xiaoyan; Logvenov, G; Bollinger, A T; Božović, I; Panagopoulos, C; Popović, Dragana

2013-01-01

A central issue for copper oxides is the nature of the insulating ground state at low carrier densities and the emergence of high-temperature superconductivity from that state with doping. Even though this superconductor-insulator transition (SIT) is a zero-temperature transition, measurements are not usually carried out at low temperatures. Here we use magnetoresistance to probe both the insulating state at very low temperatures and the presence of superconducting fluctuations in La(2-x)Sr(x)CuO(4) films, for doping levels that range from the insulator to the superconductor (x  =  0.03-0.08). We observe that the charge glass behaviour, characteristic of the insulating state, is suppressed with doping, but it coexists with superconducting fluctuations that emerge already on the insulating side of the SIT. The unexpected quenching of the superconducting fluctuations by the competing charge order at low temperatures provides a new perspective on the mechanism for the SIT.

Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

NASA Astrophysics Data System (ADS)

Lucovsky, Gerry; Wu, Kun; Pappas, Brian; Whitten, Jerry

2013-04-01

Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9>=n>3, and (TiO2)x(HfO2)1-x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii} local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding defects in TM nano-grain oxides are qualitatively similar to vacant-site defects in non-crystalline SiO2 and GeO2 for ulta-thin films, < 0.2 nm thick, and yield similar performance in MOSCAPs on Ge substrates heralding applications in aggressively-scale CMOS devices.

Correlation, Breit and Quantum Electrodynamics effects on energy level and transition properties of W54+ ion

NASA Astrophysics Data System (ADS)

Ding, Xiaobin; Sun, Rui; Koike, Fumihiro; Kato, Daiji; Murakami, Izumi; Sakaue, Hiroyuki A.; Dong, Chenzhong

2017-03-01

The electron correlation effects and Breit interaction as well as Quantum Electro-Dynamics (QED) effects were expected to have important contribution to the energy level and transition properties of heavy highly charged ions. The ground states [Ne]3s23p63d2 and first excited states [Ne]3s23p53d3 of W54+ ion have been studied by using Multi-Configuration Dirac-Fock method with the implementation of Grasp2K package. A restricted active space method was employed to investigate the correlation contribution from different models. The Breit interaction and QED effects were taken into account in the relativistic configuration interaction calculation with the converged wavefunction. It is found that the correlation contribution from 3s and 3p orbital have important contribution to the energy level, transition wavelength and probability of the ground and the first excited state of W54+ ion. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Photoluminescence properties of Eu3+ doped HfO2 coatings formed by plasma electrolytic oxidation of hafnium

NASA Astrophysics Data System (ADS)

Stojadinović, Stevan; Tadić, Nenad; Ćirić, Aleksandar; Vasilić, Rastko

2018-03-01

Plasma electrolytic oxidation was used for synthesis of Eu3+ doped monoclinic HfO2 coatings on hafnium substrate. Results of photoluminescence (PL) measurements show the existence of two distinct regions: one that is related to the blue emission originating from oxygen vacancy defects in HfO2 and the other one characterized with a series of sharp orange-red emission peaks related to f-f transitions of Eu3+ from excited level 5D0 to lower levels 7FJ (J = 0, 1, 2, 3, and 4). PL peaks appearing in excitation spectra of obtained coatings are attributed either to charge transfer state of Eu3+ or to direct excitation of the Eu3+ ground state 7F0 into higher levels of the 4f-manifold. PL of formed coatings increases with PEO time due to an increase of oxygen vacancy defects and the content of Eu3+. Acquired experimental data suggest that hypersensitive electrical dipole transition is much more intense than the magnetic dipole transition, indicating that Eu3+ ions occupy a non-inversion symmetry sites.

High Pressure Optical Studies of the Thallous Halides and of Charge-Transfer Complexes

NASA Astrophysics Data System (ADS)

Jurgensen, Charles Willard

High pressure was used to study the insulator -to-metal transition in sulfur and the thallous halides and to study the intermolecular interactions in charge -transfer complexes. The approach to the band overlap insulator -to-metal transition was studied in three thallous halides and sulfur by optical absorption measurements of the band gap as a function of pressure. The band gap of sulfur continuously decreases with pressure up to the insulator -to-metal transition which occurs between 450 and 485 kbars. The results on the thallous halides indicate that the indirect gap decreases more rapidly than the direct gap; the closing of the indirect gap is responsible for the observed insulator -to-metal transitions. High pressure electronic and vibrational spectroscopic measurements on the solid-state complexes of HMB-TCNE were used to study the intermolecular interactions of charge -transfer complexes. The vibrational frequency shifts indicate that the degree of charge transfer increases with pressure which is independently confirmed by an increase in the molar absorptivity of the electronic charge-transfer peak. Induction and dispersion forces contribute towards a red shift of the charge-transfer peak; however, charge-transfer resonance contributes toward a blue shift and this effect is dominant for the HMB-TCNE complexes. High pressure electronic spectra were used to study the effect of intermolecular interactions on the electronic states of TCNQ and its complexes. The red shifts with pressure of the electronic spectra of TCNQ and (TCNQ)(' -) in polymer media and of crystalline TCNQ can be understood in terms of Van der Waals interactions. None of the calculations which considered intradimer distance obtained the proper behavior for either the charge-transfer of the locally excited states of the complexes. The qualitative behavior of both states can be interpreted as the effect of increased mixing of the locally excited and charge transfer states.

Measurement of the transition probability of the C III 190.9 nanometer intersystem line

NASA Technical Reports Server (NTRS)

Kwong, Victor H. S.; Fang, Z.; Gibbons, T. T.; Parkinson, W. H.; Smith, Peter L.

1993-01-01

A radio-frequency ion trap has been used to store C(2+) ions created by electron bombardment of CO. The transition probability for the 2s2p 3Po1-2s2 1S0 intersystem line of C m has been measured by recording the radiative decay at 190.9 nm. The measured A-value is 121 +/- 7/s and agrees, within mutual uncertainty limits, with that of Laughlin et al. (1978), but is 20 percent larger than that of Nussbaumer and Storey (1978). The effective collision mixing rate coefficient among the fine structure levels of 3Po and the combined quenching and charge transfer rate coefficients out of the 3Po1 level with the CO source gas have also been measured.

Simulating the thermodynamics of charging in weak polyelectrolytes: the Debye-Hückel limit

NASA Astrophysics Data System (ADS)

Rathee, Vikramjit S.; Sikora, Benjamin J.; Sidky, Hythem; Whitmer, Jonathan K.

2018-01-01

The coil-globule transition in weak (annealed) polyelectrolytes involves a subtle balance of pH, charge strength, and solvation forces. In this work, we utilize a coarse-grained hybrid grand-canonical Monte Carlo and molecular dynamics approach to explore the swelling behavior of weak linear and star polyelectrolytes under different ionic screening conditions and pH. Importantly, we are able to quantify topology-dependent effects in charging which arise at the core of star polymers. Our results are suggestive of suppression of charging in star weak polyelectrolytes in comparison to linear weak polyelectrolytes. Furthermore, we characterize the coil-globule transition in linear and star weak polyelectrolyte through expanded ensemble density-of-states simulations which suggest a change from a first order to second order phase transition moving from linear to star polyelectrolytes. Lastly, we characterize the inhomogeneous charging across the weak star polyelectrolyte through observed shifts in {{Δ }}{{{pK}}}{{o}}, and compare with experimental work. We discuss these results in relation to surfaces functionalized by weak polyelectrolyte brushes and weak polyelectrolyte-based drug delivery applications.

Ordering transition in salt-doped diblock copolymers

DOE PAGES

Qin, Jian; de Pablo, Juan J.

2016-04-26

Lithium salt-doped block copolymers offer promise for applications as solid electrolytes in lithium ion batteries. Control of the conductivity and mechanical properties of these materials, for membrane applications relies critically on the ability to predict and manipulate their microphase separation temperature. Past attempts to predict the so-called "order-disorder transition temperature" of copolymer electrolytes have relied on approximate treatments of electrostatic interactions. In this work, we introduce a coarse-grained simulation model that treats Coulomb interactions explicitly, and we use it to investigate the ordering transition of charged block copolymers. The order-disorder transition temperature is determined from the ordering free energy, whichmore » we calculate with a high level of precision using a density-of-states approach. Our calculations allow us to discern a delicate competition between two physical effects: ion association, which raises the transition temperature, and solvent dilution, which lowers the transition temperature. Lastly, in the intermediate salt concentration regime, our results predict that the order-disorder transition temperature increases with salt content, in agreement with available experimental data.« less

Applications of Charge Transfer Devices in Spectroscopy.

DTIC Science & Technology

1988-02-04

Langmuir - Blodgett films deposited on glass and silicon substrates. A direct comparison by Pemberton and Sobocinski (18) of the Raman spectra obtained...wavelength. The measurements are then repeated with an uncoated sheet of poly - ester serving as the reference blank. The double monochromator...give the best sensitivity at trace concentration levels. The less intense lines resulting from non-reson- -’ ance and ionic transitions are used for

Interplay of local structure, charge, and spin in bilayered manganese perovskites

NASA Astrophysics Data System (ADS)

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; Kapusta, Czesław; Mitchell, John F.

2018-03-01

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. Here, we show results of high-energy resolution x-ray absorption and emission spectroscopies on a La2 -2 xSr1 +2 xMn2O7 family of bilayered manganites in a broad doping range (0.5 ≤x ≤1 ). We established a relation between local Mn charge and Mn-O distances as a function of doping. Based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.

Transition probability of the Si III 189.2-nm intersystem line

NASA Technical Reports Server (NTRS)

Kwong, H. S.; Johnson, B. C.; Smith, P. L.; Parkinson, W. H.

1983-01-01

Measurement of the lifetime of the metastable 3s3p(3)P(0)1 level of Si(2+) (Si III), which decays by photon emission at 189.2 nm to the 3s2(1)S0 state, is reported. The data were taken from spontaneous emission from metastable Si III stored in an RF ion trap. The Si III ions were produced through electron bombardment of SiH4 and SiF4 at pressures of 1/100,000,000-1/10,000,000 Torr. A photomultiplier was employed to count the photon emissions from the transitions. A total of 11 decay curves were generated for analysis, with Poisson statistics used to set the uncertainties at within 8 pct. Significant systematic effects were controlled, and the lifetime was found to be within 3.6 microsec of 59.9 microsec. The method used is concluded valid for determining the lifetimes of metastable levels of low-Z ions with low charge, and thereby the transition probabilities.

Entanglement contour perspective for "strong area-law violation" in a disordered long-range hopping model

NASA Astrophysics Data System (ADS)

Roy, Nilanjan; Sharma, Auditya

2018-03-01

We numerically investigate the link between the delocalization-localization transition and entanglement in a disordered long-range hopping model of spinless fermions by studying various static and dynamical quantities. This includes the inverse participation ratio, level statistics, entanglement entropy, and number fluctuations in the subsystem along with quench and wave-packet dynamics. Finite systems show delocalized, quasilocalized, and localized phases. The delocalized phase shows strong area-law violation, whereas the (quasi)localized phase adheres to (for large subsystems) the strict area law. The idea of "entanglement contour" nicely explains the violation of area law and its relationship with "fluctuation contour" reveals a signature at the transition point. The relationship between entanglement entropy and number fluctuations in the subsystem also carries signatures for the transition in the model. Results from the Aubry-Andre-Harper model are compared in this context. The propagation of charge and entanglement are contrasted by studying quench and wave-packet dynamics at the single-particle and many-particle levels.

Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system

NASA Astrophysics Data System (ADS)

Kong, Fantai; Longo, Roberto C.; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

2017-11-01

To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO2. A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li2CoO2 and Li-deficient LiCo2O4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

Charge-transfer modified embedded atom method dynamic charge potential for Li-Co-O system.

PubMed

Kong, Fantai; Longo, Roberto C; Liang, Chaoping; Nie, Yifan; Zheng, Yongping; Zhang, Chenxi; Cho, Kyeongjae

2017-11-29

To overcome the limitation of conventional fixed charge potential methods for the study of Li-ion battery cathode materials, a dynamic charge potential method, charge-transfer modified embedded atom method (CT-MEAM), has been developed and applied to the Li-Co-O ternary system. The accuracy of the potential has been tested and validated by reproducing a variety of structural and electrochemical properties of LiCoO 2 . A detailed analysis on the local charge distribution confirmed the capability of this potential for dynamic charge modeling. The transferability of the potential is also demonstrated by its reliability in describing Li-rich Li 2 CoO 2 and Li-deficient LiCo 2 O 4 compounds, including their phase stability, equilibrium volume, charge states and cathode voltages. These results demonstrate that the CT-MEAM dynamic charge potential could help to overcome the challenge of modeling complex ternary transition metal oxides. This work can promote molecular dynamics studies of Li ion cathode materials and other important transition metal oxides systems that involve complex electrochemical and catalytic reactions.

Defect physics in intermediate-band materials: Insights from an optimized hybrid functional

NASA Astrophysics Data System (ADS)

Han, Miaomiao; Zeng, Zhi; Frauenheim, Thomas; Deák, Peter

2017-10-01

Despite the efforts to implement the idea of a deep level impurity intermediate band (IB) into bulk solar cell materials, a breakthrough in efficiency increase has not yet been achieved. Taking Sn-doped CuGaS2 as an example, we investigate the problem here from the perspective of defect physics, considering all possible charge states of the dopant and its interaction with native defects. Using an optimized hybrid functional, we find that SnGa has not only a donor-type (+/0), but also an acceptor-type (0 /- ) charge transition level. We estimate the probability of the optical transition of an electron from/to the neutral defect to/from the conduction-band edge to be about equal, therefore, the lifetimes of the excited carriers are probably quite short, limiting the enhancement of the photocurrent. In addition, we find that doping with SnGa leads to the spontaneous formation of the intrinsic acceptor CuGa defects which passivate the donor SnGa and pin the Fermi level to a position (1.4 eV above the valence-band edge) where both defects are ionized. As a result, the possibility of absorption in the middle of the visible range gets lost. These two recombination and passivation mechanisms appear to be quite likely the case for other donors and other similar host materials as well, explaining some of the experimental bottlenecks with IB solar cells based on deep level impurities.

Phase transitions and spatially ordered counterion association in ionic-lipid membranes: a statistical model.

PubMed

Tamashiro, M N; Barbetta, C; Germano, R; Henriques, V B

2011-09-01

We propose a statistical model to account for the gel-fluid anomalous phase transitions in charged bilayer- or lamellae-forming ionic lipids. The model Hamiltonian comprises effective attractive interactions to describe neutral-lipid membranes as well as the effect of electrostatic repulsions of the discrete ionic charges on the lipid headgroups. The latter can be counterion dissociated (charged) or counterion associated (neutral), while the lipid acyl chains may be in gel (low-temperature or high-lateral-pressure) or fluid (high-temperature or low-lateral-pressure) states. The system is modeled as a lattice gas with two distinct particle types--each one associated, respectively, with the polar-headgroup and the acyl-chain states--which can be mapped onto an Ashkin-Teller model with the inclusion of cubic terms. The model displays a rich thermodynamic behavior in terms of the chemical potential of counterions (related to added salt concentration) and lateral pressure. In particular, we show the existence of semidissociated thermodynamic phases related to the onset of charge order in the system. This type of order stems from spatially ordered counterion association to the lipid headgroups, in which charged and neutral lipids alternate in a checkerboard-like order. Within the mean-field approximation, we predict that the acyl-chain order-disorder transition is discontinuous, with the first-order line ending at a critical point, as in the neutral case. Moreover, the charge order gives rise to continuous transitions, with the associated second-order lines joining the aforementioned first-order line at critical end points. We explore the thermodynamic behavior of some physical quantities, like the specific heat at constant lateral pressure and the degree of ionization, associated with the fraction of charged lipid headgroups.

Molecular Effects on Coacervate-Driven Block Copolymer Self Assembly

NASA Astrophysics Data System (ADS)

Lytle, Tyer; Radhakrishna, Mithun; Sing, Charles

Two oppositely charged polymers can undergo associative phase separation in a salt solution in a process known as \\x98complex coacervation. Recent work has used this as a motif to control the self-assembly behavior of a mixture of oppositely-charged block copolymers which form nanoscale structures. The materials formed from these complex coacervate-block copolymers (BCPs) have potential use as drug delivery systems, gels, and sensors. We have developed a hybrid Monte Carlo-Single Chain in a Mean Field (MC-SCMF) simulation method that is able to determine morphological phase diagrams for BCPs. This technique is an efficient way to calculate morphological phase diagrams and provides a clear link between molecular level features and self-assembly behaviors. Morphological phase diagrams showing the effects of polymer concentration, salt concentration, chain length, and charge-block fraction at large charge densities on self-assembly behavior have been determined. An unexpected phase transition from disorder to hexagonal packing at large salt concentrations has been observed for charge-block fractions equal to and larger than 0.5. This is attributed to the salt filling space stabilizing the morphology of the BCP.

Frenkel and Charge-Transfer Excitations in Donor-acceptor Complexes from Many-Body Green's Functions Theory.

PubMed

Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

2012-08-14

Excited states of donor-acceptor dimers are studied using many-body Green's functions theory within the GW approximation and the Bethe-Salpeter equation. For a series of prototypical small-molecule based pairs, this method predicts energies of local Frenkel and intermolecular charge-transfer excitations with the accuracy of tens of meV. Application to larger systems is possible and allowed us to analyze energy levels and binding energies of excitons in representative dimers of dicyanovinyl-substituted quarterthiophene and fullerene, a donor-acceptor pair used in state of the art organic solar cells. In these dimers, the transition from Frenkel to charge transfer excitons is endothermic and the binding energy of charge transfer excitons is still of the order of 1.5-2 eV. Hence, even such an accurate dimer-based description does not yield internal energetics favorable for the generation of free charges either by thermal energy or an external electric field. These results confirm that, for qualitative predictions of solar cell functionality, accounting for the explicit molecular environment is as important as the accurate knowledge of internal dimer energies.

Surface correlation effects in two-band strongly correlated slabs.

PubMed

Esfahani, D Nasr; Covaci, L; Peeters, F M

2014-02-19

Using an extension of the Gutzwiller approximation for an inhomogeneous system, we study the two-band Hubbard model with unequal band widths for a slab geometry. The aim is to investigate the mutual effect of individual bands on the spatial distribution of quasi-particle weight and charge density, especially near the surface of the slab. The main effect of the difference in band width is the presence of two different length scales corresponding to the quasi-particle profile of each band. This is enhanced in the vicinity of the critical interaction of the narrow band where an orbitally selective Mott transition occurs and a surface dead layer forms for the narrow band. For the doped case, two different regimes of charge transfer between the surface and the bulk of the slab are revealed. The charge transfer from surface/center to center/surface depends on both the doping level and the average relative charge accumulated in each band. Such effects could also be of importance when describing the accumulation of charges at the interface between structures made of multi-band strongly correlated materials.

Traversing the folding pathway of proteins using temperature-aided cascade molecular dynamics with conformation-dependent charges.

PubMed

Jani, Vinod; Sonavane, Uddhavesh; Joshi, Rajendra

2016-07-01

Protein folding is a multi-micro second time scale event and involves many conformational transitions. Crucial conformational transitions responsible for biological functions of biomolecules are difficult to capture using current state-of-the-art molecular dynamics (MD) simulations. Protein folding, being a stochastic process, witnesses these transitions as rare events. Many new methodologies have been proposed for observing these rare events. In this work, a temperature-aided cascade MD is proposed as a technique for studying the conformational transitions. Folding studies for Engrailed homeodomain and Immunoglobulin domain B of protein A have been carried out. Using this methodology, the unfolded structures with RMSD of 20 Å were folded to a structure with RMSD of 2 Å. Three sets of cascade MD runs were carried out using implicit solvation, explicit solvation, and charge updation scheme. In the charge updation scheme, charges based on the conformation obtained are calculated and are updated in the topology file. In all the simulations, the structure of 2 Å was reached within a few nanoseconds using these methods. Umbrella sampling has been performed using snapshots from the temperature-aided cascade MD simulation trajectory to build an entire conformational transition pathway. The advantage of the method is that the possible pathways for a particular reaction can be explored within a short duration of simulation time and the disadvantage is that the knowledge of the start and end state is required. The charge updation scheme adds the polarization effects in the force fields. This improves the electrostatic interaction among the atoms, which may help the protein to fold faster.

Population Switching and Charge Sensing in Quantum Dots: A Case for a Quantum Phase Transition

NASA Astrophysics Data System (ADS)

Goldstein, Moshe; Berkovits, Richard; Gefen, Yuval

2010-06-01

A broad and a narrow level of a quantum dot connected to two external leads may swap their respective occupancies as a function of an external gate voltage. By mapping this problem onto a multiflavored Coulomb gas we show that such population switching is not abrupt. However, trying to measure it by adding a third electrostatically coupled lead may render this switching an abrupt first order quantum phase transition. This is related to the interplay of the Mahan mechanism versus the Anderson orthogonality catastrophe, in similitude to the Fermi edge singularity. A concrete setup for experimental observation of this effect is also suggested.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces.

PubMed

Limmer, David T

2015-12-18

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

Interfacial Ordering and Accompanying Divergent Capacitance at Ionic Liquid-Metal Interfaces

NASA Astrophysics Data System (ADS)

Limmer, David T.

2015-12-01

A theory is constructed for dense ionic solutions near charged planar walls that is valid for strong interionic correlations. This theory predicts a fluctuation-induced, first-order transition and spontaneous charge density ordering at the interface, in the presence of an otherwise disordered bulk solution. The surface ordering is driven by applied voltage and results in an anomalous differential capacitance, in agreement with recent simulation results and consistent with experimental observations of a wide array of systems. Explicit forms for the charge density profile and capacitance are given. The theory is compared with numerical results for the charge frustrated Ising model, which is also found to exhibit a voltage driven first-order transition.

Enhanced coherent oscillations in the superconducting state of underdoped YB a 2 C u 3 O 6 + x induced via ultrafast terahertz excitation

DOE PAGES

Dakovski, Georgi L.; Lee, Wei -Sheng; Hawthorn, David G.; ...

2015-06-24

We utilize intense, single-cycle terahertz pulses to induce collective excitations in the charge-density-wave-ordered underdoped cuprate YBa 2Cu 3O 6+x. These excitations manifest themselves as pronounced coherent oscillations of the optical reflectivity in the transient state, accompanied by minimal incoherent quasiparticle relaxation dynamics. The oscillations occur at frequencies consistent with soft phonon energies associated with the charge-density-wave, but vanish above the superconducting transition temperature rather than that at the charge-density-wave transition. These results indicate an intimate relationship of the terahertz excitation with the underlying charge-density-wave and the superconducting condensate itself.

Phonon-Assisted Ultrafast Charge Transfer at van der Waals Heterostructure Interface.

PubMed

Zheng, Qijing; Saidi, Wissam A; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V; Petek, Hrvoje; Zhao, Jin

2017-10-11

The van der Waals (vdW) interfaces of two-dimensional (2D) semiconductor are central to new device concepts and emerging technologies in light-electricity transduction where the efficient charge separation is a key factor. Contrary to general expectation, efficient electron-hole separation can occur in vertically stacked transition-metal dichalcogenide heterostructure bilayers through ultrafast charge transfer between the neighboring layers despite their weak vdW bonding. In this report, we show by ab initio nonadiabatic molecular dynamics calculations, that instead of direct tunneling, the ultrafast interlayer hole transfer is strongly promoted by an adiabatic mechanism through phonon excitation occurring on 20 fs, which is in good agreement with the experiment. The atomic level picture of the phonon-assisted ultrafast mechanism revealed in our study is valuable both for the fundamental understanding of ultrafast charge carrier dynamics at vdW heterointerfaces as well as for the design of novel quasi-2D devices for optoelectronic and photovoltaic applications.

Monolayer optical memory cells based on artificial trap-mediated charge storage and release

NASA Astrophysics Data System (ADS)

Lee, Juwon; Pak, Sangyeon; Lee, Young-Woo; Cho, Yuljae; Hong, John; Giraud, Paul; Shin, Hyeon Suk; Morris, Stephen M.; Sohn, Jung Inn; Cha, Seungnam; Kim, Jong Min

2017-03-01

Monolayer transition metal dichalcogenides are considered to be promising candidates for flexible and transparent optoelectronics applications due to their direct bandgap and strong light-matter interactions. Although several monolayer-based photodetectors have been demonstrated, single-layered optical memory devices suitable for high-quality image sensing have received little attention. Here we report a concept for monolayer MoS2 optoelectronic memory devices using artificially-structured charge trap layers through the functionalization of the monolayer/dielectric interfaces, leading to localized electronic states that serve as a basis for electrically-induced charge trapping and optically-mediated charge release. Our devices exhibit excellent photo-responsive memory characteristics with a large linear dynamic range of ~4,700 (73.4 dB) coupled with a low OFF-state current (<4 pA), and a long storage lifetime of over 104 s. In addition, the multi-level detection of up to 8 optical states is successfully demonstrated. These results represent a significant step toward the development of future monolayer optoelectronic memory devices.

Emergent ultrafast phenomena in correlated oxides and heterostructures

NASA Astrophysics Data System (ADS)

Gandolfi, M.; Celardo, G. L.; Borgonovi, F.; Ferrini, G.; Avella, A.; Banfi, F.; Giannetti, C.

2017-03-01

The possibility of investigating the dynamics of solids on timescales faster than the thermalization of the internal degrees of freedom has disclosed novel non-equilibrium phenomena that have no counterpart at equilibrium. Transition metal oxides (TMOs) provide an interesting playground in which the correlations among the charges in the metal d-orbitals give rise to a wealth of intriguing electronic and thermodynamic properties involving the spin, charge, lattice and orbital orders. Furthermore, the physical properties of TMOs can be engineered at the atomic level, thus providing the platform to investigate the transport phenomena on timescales of the order of the intrinsic decoherence time of the charge excitations. Here, we review and discuss three paradigmatic examples of transient emerging properties that are expected to open new fields of research: (i) the creation of non-thermal magnetic states in spin-orbit Mott insulators; (ii) the possible exploitation of quantum paths for the transport and collection of charge excitations in heterostructures; (iii) the transient wave-like behavior of the temperature field in strongly anisotropic TMOs.

23 CFR 810.212 - Use to be without charge.

Code of Federal Regulations, 2011 CFR

2011-04-01

... Highways FEDERAL HIGHWAY ADMINISTRATION, DEPARTMENT OF TRANSPORTATION PUBLIC TRANSPORTATION MASS TRANSIT AND SPECIAL USE HIGHWAY PROJECTS Making Highway Rights-of-Way Available for Mass Transit Projects... available for mass transit shall be borne by the publicly-owned mass transit authority. ...

Image Charge and Electric Field Effects on Hydrogen-like Impurity-bound Polaron Energies and Oscillator Strengths in a Quantum Dot

NASA Astrophysics Data System (ADS)

Vardanyan, L. A.; Vartanian, A. L.; Asatryan, A. L.; Kirakosyan, A. A.

2016-11-01

By using Landau-Pekar variational method, the ground and the first excited state energies and the transition frequencies between the ground and the first excited states of a hydrogen-like impurity-bound polaron in a spherical quantum dot (QD) have been studied by taking into account the image charge effect (ICE). We employ the dielectric continuum model to describe the phonon confinement effects. The oscillator strengths (OSs) of transitions from the 1 s-like state to excited states of 2 s, 2 p x , and 2 p z symmetries are calculated as functions of the applied electric field and strength of the confinement potential. We have shown that with and without image charge effect, the increase of the strength of the parabolic confinement potential leads to the increase of the oscillator strengths of 1 s - 2 p x and 1 s - 2 p z transitions. This indicates that the energy differences between 1 s- and 2 p x - as well as 1 s- and 2 p z -like states have a dominant role determining the oscillator strength. Although there is almost no difference in the oscillator strengths for transitions 1 s - 2 p x and 1 s -2 p z when the image charge effect is not taken into account, it becomes significant with the image charge effect.

Voltage-induced Metal-Insulator Transitions in Perovskite Oxide Thin Films Doped with Strongly Correlelated Electrons

NASA Astrophysics Data System (ADS)

Wang, Yudi; Gil Kim, Soo; Chen, I.-Wei

2007-03-01

We have observed a reversible metal-insulator transition in perovskite oxide thin films that can be controlled by charge trapping pumped by a bipolar voltage bias. In the as-fabricated state, the thin film is metallic with a very low resistance comparable to that of the metallic bottom electrode, showing decreasing resistance with decreasing temperature. This metallic state switches to a high-resistance state after applying a voltage bias: such state is non-ohmic showing a negative temperature dependence of resistance. Switching at essentially the same voltage bias was observed down to 2K. The metal-insulator transition is attributed to charge trapping that disorders the energy of correlated electron states in the conduction band. By increasing the amount of charge trapped, which increases the disorder relative to the band width, increasingly more insulating states with a stronger temperature dependence of resistivity are accessed. This metal-insulator transition provides a platform to engineer new nonvolatile memory that does not require heat (as in phase transition) or dielectric breakdown (as in most other oxide resistance devices).

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

Li, Yan; Sun, Zhao; Cai, Jia -Wei

Here, the mixed-valent Pbmore » $${}_{3}$$Rh $${}_{7}$$O$${}_{15}$$ undergoes a Verwey-type transition at $${T}_{{\\rm{v}}}\\approx 180$$ K, below which the development of Rh$${}^{3+}$$ /Rh$${}^{4+}$$ charge order induces an abrupt conductor-to-insulator transition in resistivity. Here we investigate the effect of pressure on the Verwey-type transition of Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ by measuring its electrical resistivity under hydrostatic pressures up to 8 GPa with a cubic anvil cell apparatus. We find that the application of high pressure can suppress the Verwey-type transition around 3 GPa, above which a metallic state is realized at temperatures below ~70 K, suggesting the melting of charge order by pressure. Interestingly, the low-temperature metallic region shrinks gradually upon further increasing pressure and disappears completely at P > 7 GPa, which indicates that the charge carriers in Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ undergo a reentrant localization under higher pressures. We have constructed a temperature-pressure phase diagram for Pb$${}_{3}$$Rh$${}_{7}$$O$${}_{15}$$ and compared to that of Fe$${}_{3}$$O$${}_{4}$$, showing an archetype Verwey transition.« less

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates.

PubMed

Middey, S; Meyers, D; Kareev, M; Cao, Yanwei; Liu, X; Shafer, P; Freeland, J W; Kim, J-W; Ryan, P J; Chakhalian, J

2018-04-13

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO_{3}. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

NASA Astrophysics Data System (ADS)

Middey, S.; Meyers, D.; Kareev, M.; Cao, Yanwei; Liu, X.; Shafer, P.; Freeland, J. W.; Kim, J.-W.; Ryan, P. J.; Chakhalian, J.

2018-04-01

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO3 . Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions. Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. This designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.

Pure electronic metal-insulator transition at the interface of complex oxides

DOE PAGES

Meyers, D.; Liu, Jian; Freeland, J. W.; ...

2016-06-21

We observed complex materials in electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. We demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. Furthermore, these findings illustrate the utility of heterointerfaces as amore » powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.« less

An optimization framework for workplace charging strategies

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

Huang, Yongxi; Zhou, Yan

2015-03-01

The workplace charging (WPC) has been recently recognized as the most important secondary charging point next to residential charging for plug-in electric vehicles (PEVs). The current WPC practice is spontaneous and grants every PEV a designated charger, which may not be practical or economic when there are a large number of PEVs present at workplace. This study is the first research undertaken that develops an optimization framework for WPC strategies to satisfy all charging demand while explicitly addressing different eligible levels of charging technology and employees’ demographic distributions. The optimization model is to minimize the lifetime cost of equipment, installations,more » and operations, and is formulated as an integer program. We demonstrate the applicability of the model using numerical examples based on national average data. The results indicate that the proposed optimization model can reduce the total cost of running a WPC system by up to 70% compared to the current practice. The WPC strategies are sensitive to the time windows and installation costs, and dominated by the PEV population size. The WPC has also been identified as an alternative sustainable transportation program to the public transit subsidy programs for both economic and environmental advantages.« less

The ice VII-ice X phase transition with implications for planetary interiors

NASA Astrophysics Data System (ADS)

Aarestad, B.; Frank, M. R.; Scott, H.; Bricker, M.; Prakapenka, V.

2008-12-01

A significant amount of research on the high pressure polymorphs of H2O have detailed the lattice structure and density of these phases, namely ice VI, ice VII, and ice X. These high pressure ices are noteworthy as they may comprise a considerable part of the interior of large icy planets and satellites. However, there is a dearth of data on how the incorporation of an impurity, charged or non-charged, affects the ice VII-ice X transition. This study examined the ice VII-ice X transition that occurs at approximately 62 GPa with a pure system and two select impure systems. Solutions of pure H2O, 1.6 mole percent NaCl in H2O, and 1.60 mole percent CH3OH in H2O were compressed in a diamond anvil cell (DAC). The experiments were performed at the GSECARS 13-BM-D beam line at the Advanced Photon Source at Argonne National Laboratory. Powder diffraction data of the ice samples were collected using monochromatic X-ray radiation, 0.2755 Å, and a MAR 345 online imaging system at intervals of approximately 2 GPa up to ~71.5, ~74.5, and ~68 GPa, respectively. Analyses of the data provided volume-pressure relations (at 298 K) which were used to detail the ice VII-ice X phase transition. The pressure of the phase transition, based upon an interpretation of the X-ray diffraction data, was found to vary as a function of the impurity type. Thus, the depth of the ice VII-ice X phase transition within an ice-rich planetary body can be influenced by trace-level impurities.

Gate-tunable electron interaction in high-κ dielectric films

DOE PAGES

Kondovych, Svitlana; Luk’yanchuk, Igor; Baturina, Tatyana I.; ...

2017-02-20

The two-dimensional (2D) logarithmic character of Coulomb interaction between charges and the resulting logarithmic confinement is a remarkable inherent property of high dielectric constant (high-k) thin films with far reaching implications. Most and foremost, this is the charge Berezinskii-Kosterlitz-Thouless transition with the notable manifestation, low-temperature superinsulating topological phase. Here we show that the range of the confinement can be tuned by the external gate electrode and unravel a variety of electrostatic interactions in high-k films. Lastly, our findings open a unique laboratory for the in-depth study of topological phase transitions and a plethora of related phenomena, ranging from criticality ofmore » quantum metal- and superconductor-insulator transitions to the effects of charge-trapping and Coulomb scalability in memory nanodevices.« less

Superconductor to Mott insulator transition in YBa 2Cu 3O 7/LaCaMnO 3 heterostructures

DOE PAGES

Gray, B. A.; Middey, S.; Conti, G.; ...

2016-09-15

The superconductor-to-insulator transition (SIT) induced by means such as external magnetic fields, disorder or spatial confinement is a vivid illustration of a quantum phase transition dramatically affecting the superconducting order parameter. In this paper, in pursuit of a new realization of the SIT by interfacial charge transfer, we developed extremely thin superlattices composed of high Tc superconductor YBa 2Cu 3O 7 (YBCO) and colossal magnetoresistance ferromagnet La 0.67Ca 0.33MnO 3 (LCMO). By using linearly polarized resonant X-ray absorption spectroscopy and magnetic circular dichroism, combined with hard X-ray photoelectron spectroscopy, we derived a complete picture of the interfacial carrier doping inmore » cuprate and manganite atomic layers, leading to the transition from superconducting to an unusual Mott insulating state emerging with the increase of LCMO layer thickness. In addition, contrary to the common perception that only transition metal ions may respond to the charge transfer process, we found that charge is also actively compensated by rare-earth and alkaline-earth metal ions of the interface. Finally, such deterministic control of Tc by pure electronic doping without any hindering effects of chemical substitution is another promising route to disentangle the role of disorder on the pseudo-gap and charge density wave phases of underdoped cuprates.« less

Glass transition of charged particles in two-dimensional confinement.

PubMed

Yazdi, Anoosheh; Heinen, Marco; Ivlev, Alexei; Löwen, Hartmut; Sperl, Matthias

2015-05-01

The glass transition of mesoscopic charged particles in two-dimensional confinement is studied by mode-coupling theory. We consider two types of effective interactions between the particles, corresponding to two different models for the distribution of surrounding ions that are integrated out in coarse-grained descriptions. In the first model, a planar monolayer of charged particles is immersed in an unbounded isotropic bath of ions, giving rise to an isotropically screened Debye-Hückel (Yukawa)-type effective interaction. The second, experimentally more relevant system is a monolayer of negatively charged particles that levitate atop a flat horizontal electrode, as frequently encountered in laboratory experiments with complex (dusty) plasmas. A steady plasma current toward the electrode gives rise to an anisotropic effective interaction potential between the particles, with an algebraically long-ranged in-plane decay. In a comprehensive parameter scan that covers the typical range of experimentally accessible plasma conditions, we calculate and compare the mode-coupling predictions for the glass transition in both kinds of systems.

Photocarrier generation from interlayer charge-transfer transitions in WS2-graphene heterostructures

PubMed Central

Yuan, Long; Chung, Ting-Fung; Kuc, Agnieszka; Wan, Yan; Xu, Yang; Chen, Yong P.; Heine, Thomas; Huang, Libai

2018-01-01

Efficient interfacial carrier generation in van der Waals heterostructures is critical for their electronic and optoelectronic applications. We demonstrate broadband photocarrier generation in WS2-graphene heterostructures by imaging interlayer coupling–dependent charge generation using ultrafast transient absorption microscopy. Interlayer charge-transfer (CT) transitions and hot carrier injection from graphene allow carrier generation by excitation as low as 0.8 eV below the WS2 bandgap. The experimentally determined interlayer CT transition energies are consistent with those predicted from the first-principles band structure calculation. CT interactions also lead to additional carrier generation in the visible spectral range in the heterostructures compared to that in the single-layer WS2 alone. The lifetime of the charge-separated states is measured to be ~1 ps. These results suggest that interlayer interactions make graphene–two-dimensional semiconductor heterostructures very attractive for photovoltaic and photodetector applications because of the combined benefits of high carrier mobility and enhanced broadband photocarrier generation. PMID:29423439

General Trends of Dihedral Conformational Transitions in a Globular Protein

PubMed Central

Miao, Yinglong; Baudry, Jerome; Smith, Jeremy C.; McCammon, J. Andrew

2017-01-01

Dihedral conformational transitions are analyzed systematically in a model globular protein, cytochrome P450cam, to examine their structural and chemical dependences through combined conventional molecular dynamics (cMD), accelerated molecular dynamics (aMD) and Adaptive Biasing Force (ABF) simulations. The aMD simulations are performed at two acceleration levels, using dihedral and dual boost, respectively. In comparison with cMD, aMD samples protein dihedral transitions ~2 times faster on average using dihedral boost, and ~3.5 times faster using dual boost. In the protein backbone, significantly higher dihedral transition rates are observed in the Bend, Coil and Turn flexible regions, followed by the β bridge and β sheet, and then the helices. Moreover, protein sidechains of greater length exhibit higher transition rates on average in the aMD-enhanced sampling. Sidechains of the same length (particularly Nχ = 2) exhibit decreasing transition rates with residues when going from hydrophobic to polar, then charged and aromatic chemical types. The reduction of dihedral transition rates is found to be correlated with increasing energy barriers as identified through ABF free energy calculations. These general trends of dihedral conformational transitions provide important insights into the hierarchical dynamics and complex free energy landscapes of functional proteins. PMID:26799251

Phonon-coupled ultrafast interlayer charge oscillation at van der Waals heterostructure interfaces

NASA Astrophysics Data System (ADS)

Zheng, Qijing; Xie, Yu; Lan, Zhenggang; Prezhdo, Oleg V.; Saidi, Wissam A.; Zhao, Jin

2018-05-01

Van der Waals (vdW) heterostructures of transition-metal dichalcogenide (TMD) semiconductors are central not only for fundamental science, but also for electro- and optical-device technologies where the interfacial charge transfer is a key factor. Ultrafast interfacial charge dynamics has been intensively studied, however, the atomic scale insights into the effects of the electron-phonon (e-p) coupling are still lacking. In this paper, using time dependent ab initio nonadiabatic molecular dynamics, we study the ultrafast interfacial charge transfer dynamics of two different TMD heterostructures MoS2/WS2 and MoSe2/WSe2 , which have similar band structures but different phonon frequencies. We found that MoSe2/WSe2 has softer phonon modes compared to MoS2/WS2 , and thus phonon-coupled charge oscillation can be excited with sufficient phonon excitations at room temperature. In contrast, for MoS2/WS2 , phonon-coupled interlayer charge oscillations are not easily excitable. Our study provides an atomic level understanding on how the phonon excitation and e-p coupling affect the interlayer charge transfer dynamics, which is valuable for both the fundamental understanding of ultrafast dynamics at vdW hetero-interfaces and the design of novel quasi-two-dimensional devices for optoelectronic and photovoltaic applications.

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

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

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

DOE PAGES

Pace, Natalie A.; Reid, Obadiah G.; Rumbles, Garry

2018-02-19

We demonstrate that the product of photoinduced electron transfer between a conjugated polymer host and a dilute molecular sensitizer is controlled by the structural state of the polymer. Ordered semicrystalline solids exhibit free charge generation, while disordered polymers in the melt phase do not. We use photoluminescence (PL) and time-resolved microwave conductivity (TRMC) measurements to sweep through polymer melt transitions in situ. Free charge generation measured by TRMC turns off upon melting, whereas PL quenching of the molecular sensitizers remains constant, implying unchanged electron transfer efficiency. The key difference is the intermolecular order of the polymer host in the solidmore » state compared to the melt. We propose that this order-disorder transition modulates the localization length of the initial charge-transfer state, which controls the probability of free charge formation.« less

High-Fidelity Rapid Initialization and Read-Out of an Electron Spin via the Single Donor D(-) Charge State.

PubMed

Watson, T F; Weber, B; House, M G; Büch, H; Simmons, M Y

2015-10-16

We demonstrate high-fidelity electron spin read-out of a precision placed single donor in silicon via spin selective tunneling to either the D(+) or D(-) charge state of the donor. By performing read-out at the stable two electron D(0)↔D(-) charge transition we can increase the tunnel rates to a nearby single electron transistor charge sensor by nearly 2 orders of magnitude, allowing faster qubit read-out (1 ms) with minimum loss in read-out fidelity (98.4%) compared to read-out at the D(+)↔D(0) transition (99.6%). Furthermore, we show that read-out via the D(-) charge state can be used to rapidly initialize the electron spin qubit in its ground state with a fidelity of F(I)=99.8%.

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

Cadiz, Fabian, E-mail: cadiz@insa-toulouse.fr; Tricard, Simon; Gay, Maxime

Developments in optoelectronics and spin-optronics based on transition metal dichalcogenide monolayers (MLs) need materials with efficient optical emission and well-defined transition energies. In as-exfoliated MoS{sub 2} MLs, the photoluminescence (PL) spectra even at low temperature consist typically of broad, overlapping contributions from neutral, charged excitons (trions) and localized states. Here, we show that in superacid treated MoS{sub 2} MLs, the PL intensity increases by up to 60 times at room temperature. The neutral and charged exciton transitions are spectrally well separated in PL and reflectivity at T = 4 K, with linewidth for the neutral exciton of 15 meV, but both transitions have similarmore » intensities compared to the ones in as-exfoliated MLs at the same temperature. Time resolved experiments uncover picoseconds recombination dynamics analyzed separately for charged and neutral exciton emissions. Using the chiral interband selection rules, we demonstrate optically induced valley polarization for both complexes and valley coherence for only the neutral exciton.« less

Temperature Dependence of Magnetically Active Charge Excitations in Magnetite across the Verwey Transition

NASA Astrophysics Data System (ADS)

Taguchi, M.; Chainani, A.; Ueda, S.; Matsunami, M.; Ishida, Y.; Eguchi, R.; Tsuda, S.; Takata, Y.; Yabashi, M.; Tamasaku, K.; Nishino, Y.; Ishikawa, T.; Daimon, H.; Todo, S.; Tanaka, H.; Oura, M.; Senba, Y.; Ohashi, H.; Shin, S.

2015-12-01

We study the electronic structure of bulk single crystals and epitaxial films of Fe3 O4 . Fe 2 p core level spectra show clear differences between hard x-ray (HAX) and soft x-ray photoemission spectroscopy (PES). The bulk-sensitive spectra exhibit temperature (T ) dependence across the Verwey transition, which is missing in the surface-sensitive spectra. By using an extended impurity Anderson full-multiplet model—and in contrast to an earlier peak assignment—we show that the two distinct Fe species (A and B site) and the charge modulation at the B site are responsible for the newly found double peaks in the main peak above TV and its T -dependent evolution. The Fe 2 p HAXPES spectra show a clear magnetic circular dichroism (MCD) in the metallic phase of magnetized 100-nm-thick films. The model calculations also reproduce the MCD and identify the contributions from magnetically distinct A and B sites. Valence band HAXPES shows a finite density of states at EF for the polaronic half metal with a remnant order above TV and a clear gap formation below TV. The results indicate that the Verwey transition is driven by changes in the strongly correlated and magnetically active B -site electronic states, consistent with resistivity and optical spectra.

The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson-Crick Pairs.

PubMed

Raeber, Alexandra E; Wong, Bryan M

2015-05-12

We present a detailed analysis of several time-dependent DFT (TD-DFT) methods, including conventional hybrid functionals and two types of nonempirically tuned range-separated functionals, for predicting a diverse set of electronic excitations in DNA nucleobase monomers and dimers. This large and extensive set of excitations comprises a total of 50 different transitions (for each tested DFT functional) that includes several n → π and π → π* valence excitations, long-range charge-transfer excitations, and extended Rydberg transitions (complete with benchmark calculations from high-level EOM-CCSD(T) methods). The presence of localized valence excitations as well as extreme long-range charge-transfer excitations in these systems poses a serious challenge for TD-DFT methods that allows us to assess the importance of both short- and long-range exchange contributions for simultaneously predicting all of these various transitions. In particular, we find that functionals that do not have both short- and full long-range exchange components are unable to predict the different types of nucleobase excitations with the same accuracy. Most importantly, the current study highlights the importance of both short-range exchange and a nonempirically tuned contribution of long-range exchange for accurately predicting the diverse excitations in these challenging nucleobase systems.

Electronic structure of charge-density-wave state in quasi-2D KMo6O17 purple bronze characterized by angle resolved photoemission spectroscopy

NASA Astrophysics Data System (ADS)

Valbuena, M. A.; Avila, J.; Drouard, S.; Guyot, H.; Asensio, M. C.

2006-01-01

We report on an angle-resolved-photoemission spectroscopy (ARPES) investigation of layered quasi-two dimensional (2D) Molybdenum purple bronze KMo6O17 in order to study and characterizes the transition to a charge-density-wave (CDW) state. We have performed photoemission temperature dependent measurements cooling down from room temperature (RT) to 32 K, well below the Peierls transition for this material, with CDW transition temperature Tc =110 K. The spectra have been taken at a selected kF point of the Fermi surface (FS) that satisfies the nesting condition of the FS, looking for the characteristic pseudo-gap opening in this kind of materials. The pseudogap has been estimated and it result to be in agreement with our previous works. The shift to lower binding energy of crossing Fermi level ARPES feature have been also confirmed and studied as a function of temperature, showing a rough like BCS behaviour. Finally we have also focused on ARPES measurements along ΓM¯ high symmetry direction for both room and low temperature states finding some insight for ‘shadow’ or back folded bands indicating the new periodicity of real lattice after the CDW lattice distortion.

Temporal behavior of unresolved transition array emission in water window soft x-ray spectral region from multiply charged ions

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

Dinh, Thanh-Hung, E-mail: dinh@cc.utsunomiya-u.ac.jp; Suzuki, Yuhei; Arai, Goki

2015-09-21

We have characterized the spectral structure and the temporal history of the laser-produced high-Z multi-charged ion plasmas for the efficient water window soft x-ray sources. Strong unresolved transition array emission was observed due to 4d–4f and 4f–5g transitions from Au, Pb, and Bi plasmas in the 280–700 eV photon energy region. The temporal behavior of the emission was essentially similar of that of the laser pulse with a slight delay between different transitions. These results provide feedback for accurate modeling of the atomic processes with the radiative hydrodynamic simulations.

Composition-related structural transition of random peptides: insight into the boundary between intrinsically disordered proteins and folded proteins.

PubMed

Kang, Wen-Bin; He, Chuan; Liu, Zhen-Xing; Wang, Jun; Wang, Wei

2018-05-16

Previous studies based on bioinformatics showed that there is a sharp distinction of structural features and residue composition between the intrinsically disordered proteins and the folded proteins. What induces such a composition-related structural transition? How do various kinds of interactions work in such processes? In this work, we investigate these problems based on a survey on peptides randomly composed of charged residues (including glutamic acids and lysines) and the residues with different hydrophobicity, such as alanines, glycines, or phenylalanines. Based on simulations using all-atom model and replica-exchange Monte Carlo method, a coil-globule transition is observed for each peptide. The corresponding transition temperature is found to be dependent on the contents of the hydrophobic and charged residues. For several cases, when the mean hydrophobicity is larger than a certain threshold, the transition temperature is higher than the room temperature, and vise versa. These thresholds of hydrophobicity and net charge are quantitatively consistent with the border line observed from the study of bioinformatics. These results outline the basic physical reasons for the compositional distinction between the intrinsically disordered proteins and the folded proteins. Furthermore, the contributions of various interactions to the structural variation of peptides are analyzed based on the contact statistics and the charge-pattern dependence of the gyration radii of the peptides. Our observations imply that the hydrophobicity contributes essentially to such composition-related transitions. Thus, we achieve a better understanding on composition-structure relation of the natural proteins and the underlying physics.

Change of electric dipole moment in charge transfer transitions of ferrocene oligomers studied by ultrafast two-photon absorption

NASA Astrophysics Data System (ADS)

Mikhaylov, Alexander; Arias, Eduardo; Moggio, Ivana; Ziolo, Ronald; Uudsemaa, Merle; Trummal, Aleksander; Cooper, Thomas; Rebane, Aleksander

2017-02-01

Change of permanent electric dipole moment in the lower-energy charge transfer transitions for a series of symmetrical and non-symmetrical ferrocene-phenyleneethynylene oligomers were studied by measuring the corresponding femtosecond two-photon absorption cross section spectra, and were determined to be in the range Δμ = 3 - 10 D. Quantum-chemical calculations of Δμ for the non-symmetrical oligomers show good quantitative agreement with the experimental results, thus validating two-photon absorption spectroscopy as a viable experimental approach to study electrostatic properties of organometallics and other charge transfer systems.

Interplay of local structure, charge, and spin in bilayered manganese perovskites

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

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Interplay of local structure, charge, and spin in bilayered manganese perovskites

DOE PAGES

Rybicki, Damian; Sikora, Marcin; Przewoznik, Janusz; ...

2018-03-27

Chemical doping is a reliable method of modification of the electronic properties of transition metal compounds. In manganese perovskites, it leads to charge transfer and peculiar ordering phenomena. However, depending on the interplay of the local crystal structure and electronic properties, synthesis of stable compounds in the entire doping range is often impossible. In this paper, we show results of high-energy resolution x-ray absorption and emission spectroscopies on amore » $${\\mathrm{La}}_{2{-}2x}{\\mathrm{Sr}}_{1+2x}{\\mathrm{Mn}}_{2}{\\mathrm{O}}_{7}$$ family of bilayered manganites in a broad doping range $$(0.5{\\le}x{\\le}1)$$. We established a relation between local Mn charge and Mn-O distances as a function of doping. Finally, based on a comparison of such relation with other manganites, we suggest why stable structures cannot be realized for certain doping levels of bilayered compounds.« less

Quantum chemical characterization of N-(2-hydroxybenzylidene)acetohydrazide (HBAH): a detailed vibrational and NLO analysis.

PubMed

Tamer, Ömer; Avcı, Davut; Atalay, Yusuf

2014-01-03

The molecular modeling of N-(2-hydroxybenzylidene)acetohydrazide (HBAH) was carried out using B3LYP, CAMB3LYP and PBE1PBE levels of density functional theory (DFT). The molecular structure of HBAH was solved by means of IR, NMR and UV-vis spectroscopies. In order to find the stable conformers, conformational analysis was performed based on B3LYP level. A detailed vibrational analysis was made on the basis of potential energy distribution (PED). HOMO and LUMO energies were calculated, and the obtained energies displayed that charge transfer occurs in HBAH. NLO analysis indicated that HBAH can be used as an effective NLO material. NBO analysis also proved that charge transfer, conjugative interactions and intramolecular hydrogen bonding interactions occur through HBAH. Additionally, major contributions from molecular orbitals to the electronic transitions were investigated theoretically. Copyright © 2013 Elsevier B.V. All rights reserved.

Experimental and computational analysis of the transition state for ribonuclease A-catalyzed RNA 2′-O-transphosphorylation

PubMed Central

Gu, Hong; Zhang, Shuming; Wong, Kin-Yiu; Radak, Brian K.; Dissanayake, Thakshila; Kellerman, Daniel L.; Dai, Qing; Miyagi, Masaru; Anderson, Vernon E.; York, Darrin M.; Piccirilli, Joseph A.; Harris, Michael E.

2013-01-01

Enzymes function by stabilizing reaction transition states; therefore, comparison of the transition states of enzymatic and nonenzymatic model reactions can provide insight into biological catalysis. Catalysis of RNA 2′-O-transphosphorylation by ribonuclease A is proposed to involve electrostatic stabilization and acid/base catalysis, although the structure of the rate-limiting transition state is uncertain. Here, we describe coordinated kinetic isotope effect (KIE) analyses, molecular dynamics simulations, and quantum mechanical calculations to model the transition state and mechanism of RNase A. Comparison of the 18O KIEs on the 2′O nucleophile, 5′O leaving group, and nonbridging phosphoryl oxygens for RNase A to values observed for hydronium- or hydroxide-catalyzed reactions indicate a late anionic transition state. Molecular dynamics simulations using an anionic phosphorane transition state mimic suggest that H-bonding by protonated His12 and Lys41 stabilizes the transition state by neutralizing the negative charge on the nonbridging phosphoryl oxygens. Quantum mechanical calculations consistent with the experimental KIEs indicate that expulsion of the 5′O remains an integral feature of the rate-limiting step both on and off the enzyme. Electrostatic interactions with positively charged amino acid site chains (His12/Lys41), together with proton transfer from His119, render departure of the 5′O less advanced compared with the solution reaction and stabilize charge buildup in the transition state. The ability to obtain a chemically detailed description of 2′-O-transphosphorylation transition states provides an opportunity to advance our understanding of biological catalysis significantly by determining how the catalytic modes and active site environments of phosphoryl transferases influence transition state structure. PMID:23878223

Two-dimensional vibrational-electronic spectroscopy

NASA Astrophysics Data System (ADS)

Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.; Khalil, Munira

2015-10-01

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([FeIII(CN)6]3- dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5FeIICNRuIII(NH3)5]- dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

Two-dimensional vibrational-electronic spectroscopy.

PubMed

Courtney, Trevor L; Fox, Zachary W; Slenkamp, Karla M; Khalil, Munira

2015-10-21

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE) to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (νCN) and either a ligand-to-metal charge transfer transition ([Fe(III)(CN)6](3-) dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN)5Fe(II)CNRu(III)(NH3)5](-) dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific νCN modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.

Charge-induced geometrical reorganization of DNA oligonucleotides studied by tandem mass spectrometry and ion mobility.

PubMed

Ickert, Stefanie; Hofmann, Johanna; Riedel, Jens; Beck, Sebastian; Pagel, Kevin; Linscheid, Michael W

2018-04-01

Mass spectrometry is applied as a tool for the elucidation of molecular structures. This premises that gas-phase structures reflect the original geometry of the analytes, while it requires a thorough understanding and investigation of the forces controlling and affecting the gas-phase structures. However, only little is known about conformational changes of oligonucleotides in the gas phase. In this study, a series of multiply charged DNA oligonucleotides (n = 15-40) has been subjected to a comprehensive tandem mass spectrometric study to unravel transitions between different ionic gas-phase structures. The nucleobase sequence and the chain length were varied to gain insights into their influence on the geometrical oligonucleotide organization. Altogether, 23 oligonucleotides were analyzed using collision-induced fragmentation. All sequences showed comparable correlation regarding the characteristic collision energy. This value that is also a measure for stability, strongly correlates with the net charge density of the precursor ions. With decreasing charge of the oligonucleotides, an increase in the fragmentation energy was observed. At a distinct charge density, a deviation from linearity was observed for all studied species, indicating a structural reorganization. To corroborate the proposed geometrical change, collisional cross-sections of the oligonucleotides at different charge states were determined using ion mobility-mass spectrometry. The results clearly indicate that an increase in charge density and thus Coulomb repulsion results in the transition from a folded, compact form to elongated structures of the precursor ions. Our data show this structural transition to depend mainly on the charge density, whereas sequence and size do not have an influence.

Effect of chemical pressure on the electronic phase transition in Ca 1-x Sr x Mn 7 O 12 films

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

Huon, A.; Lee, D.; Herklotz, A.

Here, we demonstrate how chemical pressure affects the structural and electronic phase transitions of the quadruple perovskite CaMn 7O 12 by Sr doping, a compound that exhibits a charge-ordering transition above room temperature making it a candidate for oxide electronics. We also have synthesized Ca 1-xSr xMn 7O 12 (0 ≤ x ≤ 0.6) thin films by oxide molecular beam epitaxy on (LaAlO 3) 0.3(SrAl 0.5Ta 0.5O 3) 0.7 (LSAT) substrates. The substitution of Sr for Ca results in a linear expansion of the lattice, as revealed by X-ray diffraction. Temperature-dependent resistivity and X-ray diffraction measurements are used to demonstratemore » that the coupled charge-ordering and structural phase transitions can be tuned with Sr doping. An increase in Sr concentration acts to decrease the phase transition temperature (T*) from 426 K at x = 0 to 385 K at x = 0.6. Furthemore, the presence of a tunable electronic phase transition, above room temperature, points to the potential applicability of Ca 1-xSr xMn 7O 12 in sensors or oxide electronics, for example, via charge doping.« less

Effect of chemical pressure on the electronic phase transition in Ca 1-x Sr x Mn 7 O 12 films

DOE PAGES

Huon, A.; Lee, D.; Herklotz, A.; ...

2017-09-18

Here, we demonstrate how chemical pressure affects the structural and electronic phase transitions of the quadruple perovskite CaMn 7O 12 by Sr doping, a compound that exhibits a charge-ordering transition above room temperature making it a candidate for oxide electronics. We also have synthesized Ca 1-xSr xMn 7O 12 (0 ≤ x ≤ 0.6) thin films by oxide molecular beam epitaxy on (LaAlO 3) 0.3(SrAl 0.5Ta 0.5O 3) 0.7 (LSAT) substrates. The substitution of Sr for Ca results in a linear expansion of the lattice, as revealed by X-ray diffraction. Temperature-dependent resistivity and X-ray diffraction measurements are used to demonstratemore » that the coupled charge-ordering and structural phase transitions can be tuned with Sr doping. An increase in Sr concentration acts to decrease the phase transition temperature (T*) from 426 K at x = 0 to 385 K at x = 0.6. Furthemore, the presence of a tunable electronic phase transition, above room temperature, points to the potential applicability of Ca 1-xSr xMn 7O 12 in sensors or oxide electronics, for example, via charge doping.« less

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

Meyers, D.; Liu, Jian; Freeland, J. W.

We observed complex materials in electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. We demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. Furthermore, these findings illustrate the utility of heterointerfaces as amore » powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.« less

Nuclear structure properties of the double-charge-exchange transition amplitudes

NASA Astrophysics Data System (ADS)

Auerbach, N.; Zheng, D. C.

1992-03-01

Nuclear structure aspects of the double-charge-exchange (DCX) reaction on nuclei are studied. Using a variety of DCX-type two-body transition operators, we explore the influence of two-body correlations among valence nucleons on the DCX transition amplitudes to the isobaric analog state and to other nonanalog J π=0+ states. In particular, the question of the spin dependence and of the range of the DCX transition operators is explored and the behavior of the transition amplitudes as a function of the valence nucleon number is studied. It is shown that the two-amplitude DCX formula derived by Auerbach, Gibbs, and Piasetzky for a single j n configuration holds also in some cases when configuration mixing is strong. DCX-type transitions from the Ca and Ni isotopes to the Ti and Zn isotopes and from 56Fe to 56Ni are the subject of this study.

Spin-current probe for phase transition in an insulator

DOE PAGES

Qiu, Zhiyong; Li, Jia; Hou, Dazhi; ...

2016-08-30

Spin fluctuation and transition have always been one of the central topics of magnetism and condensed matter science. Experimentally, the spin fluctuation is found transcribed onto scattering intensity in the neutron-scattering process, which is represented by dynamical magnetic susceptibility and maximized at phase transitions. Importantly, a neutron carries spin without electric charge, and therefore it can bring spin into a sample without being disturbed by electric energy. However, large facilities such as a nuclear reactor are necessary. Here we present that spin pumping, frequently used in nanoscale spintronic devices, provides a desktop microprobe for spin transition; spin current is amore » flux of spin without an electric charge and its transport reflects spin excitation. Additionally, we demonstrate detection of antiferromagnetic transition in ultra-thin CoO films via frequency-dependent spin-current transmission measurements, which provides a versatile probe for phase transition in an electric manner in minute devices.« less

La 139 and Cu 63 NMR investigation of charge order in La 2 CuO 4 + y ( T c = 42 K)

DOE PAGES

Imai, T.; Lee, Y. S.

2018-03-14

Here, we report 139La and 63Cu NMR investigation of the successive charge order, spin order, and superconducting transitions in superoxygenated La 2CuO 4+y single crystal with stage-4 excess oxygen order at T stage≃290 K. We show that the stage-4 order induces tilting of CuO 6 octahedra below T stage, which in turn causes 139La NMR line broadening. The structural distortion continues to develop far below Tstage, and completes at T charge≃60 K, where charge order sets in. This sequence is reminiscent of the the charge-order transition in Nd codoped La 1.88Sr 0.12CuO 4 that sets in once the low-temperature tetragonalmore » phase is established. We also show that the paramagnetic 63Cu NMR signals are progressively wiped out below T charge due to enhanced low-frequency spin fluctuations in charge-ordered domains, but the residual 63Cu NMR signals continue to exhibit the characteristics expected for optimally doped superconducting CuO 2 planes. This indicates that charge order in La 2CuO 4+y does not take place uniformly in space. In addition, unlike the typical second-order magnetic phase transitions, low-frequency Cu spin fluctuations as probed by 139La nuclear spin-lattice relaxation rate do not exhibit critical divergence at T spin(≃T c) =42 K. These findings, including the spatially inhomogeneous nature of the charge-ordered state, are qualitatively similar to the case of La 1.885Sr 0.115CuO 4, but both charge and spin order take place more sharply in the present case.« less

La 139 and Cu 63 NMR investigation of charge order in La 2 CuO 4 + y ( T c = 42 K)

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

Imai, T.; Lee, Y. S.

Here, we report 139La and 63Cu NMR investigation of the successive charge order, spin order, and superconducting transitions in superoxygenated La 2CuO 4+y single crystal with stage-4 excess oxygen order at T stage≃290 K. We show that the stage-4 order induces tilting of CuO 6 octahedra below T stage, which in turn causes 139La NMR line broadening. The structural distortion continues to develop far below Tstage, and completes at T charge≃60 K, where charge order sets in. This sequence is reminiscent of the the charge-order transition in Nd codoped La 1.88Sr 0.12CuO 4 that sets in once the low-temperature tetragonalmore » phase is established. We also show that the paramagnetic 63Cu NMR signals are progressively wiped out below T charge due to enhanced low-frequency spin fluctuations in charge-ordered domains, but the residual 63Cu NMR signals continue to exhibit the characteristics expected for optimally doped superconducting CuO 2 planes. This indicates that charge order in La 2CuO 4+y does not take place uniformly in space. In addition, unlike the typical second-order magnetic phase transitions, low-frequency Cu spin fluctuations as probed by 139La nuclear spin-lattice relaxation rate do not exhibit critical divergence at T spin(≃T c) =42 K. These findings, including the spatially inhomogeneous nature of the charge-ordered state, are qualitatively similar to the case of La 1.885Sr 0.115CuO 4, but both charge and spin order take place more sharply in the present case.« less

Chloride Anions Regulate Kinetics but Not Voltage-Sensor Qmax of the Solute Carrier SLC26a5.

PubMed

Santos-Sacchi, Joseph; Song, Lei

2016-06-07

In general, SLC26 solute carriers serve to transport a variety of anions across biological membranes. However, prestin (SLC26a5) has evolved, now serving as a motor protein in outer hair cells (OHCs) of the mammalian inner ear and is required for cochlear amplification, a mechanical feedback mechanism to boost auditory performance. The mechanical activity of the OHC imparted by prestin is driven by voltage and controlled by anions, chiefly intracellular chloride. Current opinion is that chloride anions control the Boltzmann characteristics of the voltage sensor responsible for prestin activity, including Qmax, the total sensor charge moved within the membrane, and Vh, a measure of prestin's operating voltage range. Here, we show that standard narrow-band, high-frequency admittance measures of nonlinear capacitance (NLC), an alternate representation of the sensor's charge-voltage (Q-V) relationship, is inadequate for assessment of Qmax, an estimate of the sum of unitary charges contributed by all voltage sensors within the membrane. Prestin's slow transition rates and chloride-binding kinetics adversely influence these estimates, contributing to the prevalent concept that intracellular chloride level controls the quantity of sensor charge moved. By monitoring charge movement across frequency, using measures of multifrequency admittance, expanded displacement current integration, and OHC electromotility, we find that chloride influences prestin kinetics, thereby controlling charge magnitude at any particular frequency of interrogation. Importantly, however, this chloride dependence vanishes as frequency decreases, with Qmax asymptoting at a level irrespective of the chloride level. These data indicate that prestin activity is significantly low-pass in the frequency domain, with important implications for cochlear amplification. We also note that the occurrence of voltage-dependent charge movements in other SLC26 family members may be hidden by inadequate interrogation timescales, and that revelation of such activity could highlight an evolutionary means for kinetic modifications within the family to address hearing requirements in mammals. Copyright © 2016 Biophysical Society. Published by Elsevier Inc. All rights reserved.

``Making the Molecular Movie'': First Frames

NASA Astrophysics Data System (ADS)

Miller, R. J. Dwayne

2011-03-01

Femtosecond Electron Diffraction has enabled atomic resolution to structural changes as they occur, essentially watching atoms move in real time--directly observe transition states. This experiment has been referred to as ``making the molecular movie'' and has been previously discussed in the context of a gedanken experiment. With the recent development of femtosecond electron pulses with sufficient number density to execute single shot structure determinations, this experiment has been finally realized. A new concept in electron pulse generation was developed based on a solution to the N-body electron propagation problem involving up to 10,000 interacting electrons that has led to a new generation of extremely bright electron pulsed sources that minimizes space charge broadening effects. Previously thought intractable problems of determining t=0 and fully characterizing electron pulses on the femtosecond time scale have now been solved through the use of the laser pondermotive potential to provide a time dependent scattering source. Synchronization of electron probe and laser excitation pulses is now possible with an accuracy of 10 femtoseconds to follow even the fastest nuclear motions. The camera for the ``molecular movie'' is well in hand based on high bunch charge electron sources. Several movies depicting atomic motions during passage through structural transitions will be shown. Atomic level views of the simplest possible structural transition, melting, will be presented for a number of systems in which both thermal and purely electronically driven atomic displacements can be correlated to the degree of directional bonding. Optical manipulation of charge distributions and effects on interatomic forces/bonding can be directly observed through the ensuing atomic motions. New phenomena involving strongly correlated electron systems will be presented in which an exceptionally cooperative phase transitions has been observed. The primitive origin of molecular cooperativity has also been discovered in recent studies of molecular crystals. These new developments will be discussed in the context of developing the necessary technology to directly observe the structure-function correlation in biomolecules--the fundamental molecular basis of biological systems.

Matter antimatter domains: A possible solution to the CP domain wall problem in the early universe

NASA Technical Reports Server (NTRS)

Mohanty, A. K.; Stecker, F. W.

1984-01-01

An SU(5) grand unified theory model is used to show how the degeneracy between vacua with different spontaneously broken charge parity can be dynamically lifted by a condensate of heavy fermion pairs. This drives a phase transition to a unique vacuum state with definite charge parity. The transition eliminates the domain walls in a matter antimatter symmetric domain cosmology.

TOPICAL REVIEW: The shallow-to-deep instability of hydrogen and muonium in II VI and III V semiconductors

NASA Astrophysics Data System (ADS)

Cox, S. F. J.

2003-11-01

The structure and electrical activity of monatomic hydrogen defect centres are inferred from the spectroscopy and charge-state transitions of muonium, the light pseudo-isotope of hydrogen. Introductions are given to all these topics. Special attention is paid to the shallow-donor behaviour recently established in a number of II VI compounds and one III nitride. This contrasts with trapped-atom states suggestive of an acceptor function in other members of the II VI family as well as with the deep-level amphoteric behaviour which has long been known in the elemental group-IV semiconductors and certain III V compounds. The systematics of this remarkable shallow-to-deep instability are examined in terms of simple chemical considerations, as well as current theoretical and computational models. The muonium data appear to confirm predictions that the switch from shallow to deep behaviour is governed primarily by the depth of the conduction-band minimum below the vacuum continuum. The threshold electron affinity is around 3.5 eV, which compares favourably with computational estimates of a so-called pinning level for hydrogen (+/-) charge-state transitions of between -3 and -4.5 eV. A purely ionic model gives some intuitive understanding of this behaviour as well as the invariance of the threshold. Another current description applies equally to covalent materials and relates the threshold to the origin of the electrochemical scale. At the present level of approximation, zero-point energy corrections to the transition levels are small, so that muonium data should provide a reliable guide to the behaviour of hydrogen. Muonium spectroscopy proves to be more sensitive to the (0/+) donor level than to the (+/-) pinning level but, as a tool which does not rely on favourable hydrogen solubility, it looks set to test further predictions of these models in a large number of other materials, notably oxides. Certain candidate thin-film insulators and high-permittivity gate dielectrics appear to be uncomfortably close to conditions in which hydrogen impurity may cause electronic conduction.

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals.

PubMed

Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-28

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H(+)/H2 level defining the standard hydrogen electrode, the OH(-)/OH(∗) level corresponding to the oxidation of the hydroxyl ion, and the H2O/OH(∗) level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

NASA Astrophysics Data System (ADS)

Ambrosio, Francesco; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-01

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subject to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H+/H2 level defining the standard hydrogen electrode, the OH-/OH∗ level corresponding to the oxidation of the hydroxyl ion, and the H2O/OH∗ level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.

Critical behaviour in charging of electric vehicles

NASA Astrophysics Data System (ADS)

Carvalho, Rui; Buzna, Lubos; Gibbens, Richard; Kelly, Frank

2015-09-01

The increasing penetration of electric vehicles over the coming decades, taken together with the high cost to upgrade local distribution networks and consumer demand for home charging, suggest that managing congestion on low voltage networks will be a crucial component of the electric vehicle revolution and the move away from fossil fuels in transportation. Here, we model the max-flow and proportional fairness protocols for the control of congestion caused by a fleet of vehicles charging on two real-world distribution networks. We show that the system undergoes a continuous phase transition to a congested state as a function of the rate of vehicles plugging to the network to charge. We focus on the order parameter and its fluctuations close to the phase transition, and show that the critical point depends on the choice of congestion protocol. Finally, we analyse the inequality in the charging times as the vehicle arrival rate increases, and show that charging times are considerably more equitable in proportional fairness than in max-flow.

Stark tuning and electrical charge state control of single divacancies in silicon carbide

NASA Astrophysics Data System (ADS)

de las Casas, Charles F.; Christle, David J.; Ul Hassan, Jawad; Ohshima, Takeshi; Son, Nguyen T.; Awschalom, David D.

2017-12-01

Neutrally charged divacancies in silicon carbide (SiC) are paramagnetic color centers whose long coherence times and near-telecom operating wavelengths make them promising for scalable quantum communication technologies compatible with existing fiber optic networks. However, local strain inhomogeneity can randomly perturb their optical transition frequencies, which degrades the indistinguishability of photons emitted from separate defects and hinders their coupling to optical cavities. Here, we show that electric fields can be used to tune the optical transition frequencies of single neutral divacancy defects in 4H-SiC over a range of several GHz via the DC Stark effect. The same technique can also control the charge state of the defect on microsecond timescales, which we use to stabilize unstable or non-neutral divacancies into their neutral charge state. Using fluorescence-based charge state detection, we show that both 975 nm and 1130 nm excitation can prepare their neutral charge state with near unity efficiency.

Elucidation of band structure of charge storage in conducting polymers using a redox reaction.

PubMed

Contractor, Asfiya Q; Juvekar, Vinay A

2014-07-01

A novel technique to investigate charge storage characteristics of intrinsically conducting polymer films has been developed. A redox reaction is conducted on a polymer film on a rotating disk electrode under potentiostatic condition so that the rate of charging of the film equals the rate of removal of the charge by the reaction. The voltammogram obtained from the experiment on polyaniline film using Fe(2+)/Fe(3+) in HCl as the redox system shows five distinct linear segments (bands) with discontinuity in the slope at specific transition potentials. These bands are the same as those indicated by electron spin resonance (ESR)/Raman spectroscopy with comparable transition potentials. From the dependence of the slopes of the bands on concentration of ferrous and ferric ions, it was possible to estimate the energies of the charge carriers in different bands. The film behaves as a redox capacitor and does not offer resistance to charge transfer and electronic conduction.

Role of the Muon in Semiconductor Research

NASA Astrophysics Data System (ADS)

Mengyan, Rick (P. W.)

Muons are used in semiconductor research as an experimentally accessible analog to the isolated Hydrogen (H) impurity - a complex that is very difficult (or impossible) to study by other means. Hydrogen impurities of any concentration can modify the electrical, optical or magnetic properties of the host. For instance, H can be incorporated to remove electrically active levels from the energy gap (i.e. passivation) while some can form isolated centers that tend to be responsible for the trap and release of charge carriers and participate in site and charge-state dynamics which certainly affect the electrical properties of the host. Therefore, it can be quite useful to characterize these impurities in semiconducting materials that are of interest for use in devices. A muon has the same charge and spin as a proton but a mass that is nine times lighter. When implanted in a target material, a positively charged muon can behave as a light proton or bind with an electron to form a complex known as Muonium (Mu) with properties that are very similar to that of ionic or neutral H, respectively. A result of these similarities and direct non-destructive implantation is that Mu provides a direct measure of local electronic structure, thermal stability and charge-state transitions of these impurity centers. Since any material can be subjected to muon implantation and it is the muons themselves that mimic the H impurity centers, these measurements do not depend (at all) on the host's solubility of hydrogen nor do they require some minimum concentration; unlike many other techniques, such as EPR, ENDOR, NMR, or IR vibrational spectroscopy. Here we summarize major contributions muons have made to the field of semiconductor research followed by a few case studies to demonstrate the technique and detailed knowledge of the physical and electronic structures as well as dynamics (e.g.: charge-state and site transitions; local motion; long-range diffusion) of Mu/H that can be obtained.

Charge-compensation in 3d-transition-metal-oxide intercalation cathodes through the generation of localized electron holes on oxygen.

PubMed

Luo, Kun; Roberts, Matthew R; Hao, Rong; Guerrini, Niccoló; Pickup, David M; Liu, Yi-Sheng; Edström, Kristina; Guo, Jinghua; Chadwick, Alan V; Duda, Laurent C; Bruce, Peter G

2016-07-01

During the charging and discharging of lithium-ion-battery cathodes through the de- and reintercalation of lithium ions, electroneutrality is maintained by transition-metal redox chemistry, which limits the charge that can be stored. However, for some transition-metal oxides this limit can be broken and oxygen loss and/or oxygen redox reactions have been proposed to explain the phenomenon. We present operando mass spectrometry of (18)O-labelled Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2, which demonstrates that oxygen is extracted from the lattice on charging a Li1.2[Ni0.13(2+)Co0.13(3+)Mn0.54(4+)]O2 cathode, although we detected no O2 evolution. Combined soft X-ray absorption spectroscopy, resonant inelastic X-ray scattering spectroscopy, X-ray absorption near edge structure spectroscopy and Raman spectroscopy demonstrates that, in addition to oxygen loss, Li(+) removal is charge compensated by the formation of localized electron holes on O atoms coordinated by Mn(4+) and Li(+) ions, which serve to promote the localization, and not the formation, of true O2(2-) (peroxide, O-O ~1.45 Å) species. The quantity of charge compensated by oxygen removal and by the formation of electron holes on the O atoms is estimated, and for the case described here the latter dominates.

Charge ordering transition in GdBaCo2O5: Evidence of reentrant behavior

NASA Astrophysics Data System (ADS)

Allieta, M.; Scavini, M.; Lo Presti, L.; Coduri, M.; Loconte, L.; Cappelli, S.; Oliva, C.; Ghigna, P.; Pattison, P.; Scagnoli, V.

2013-12-01

We present a detailed study on the charge ordering transition in a GdBaCo2O5.0 system by combining high-resolution synchrotron powder/single-crystal diffraction with electron paramagnetic resonance experiments as a function of temperature. We found a second-order structural phase transition at TCO = 247 K (Pmmm to Pmma) associated with the onset of long-range charge ordering. At Tmin ≈ 1.2TCO, the electron paramagnetic resonance linewidth rapidly broadens, providing evidence of antiferromagnetic spin fluctuations. This likely indicates that, analogously to manganites, the long-range antiferromagnetic order in GdBaCo2O5.0 sets in at ≈TCO. Pair distribution function analysis of diffraction data revealed signatures of structural inhomogeneities at low temperature. By comparing the average and local bond valences, we found that above TCO the local structure is consistent with a fully random occupation of Co2+ and Co3+ in a 1:1 ratio and with a complete charge ordering below TCO. Below T ≈ 100 K the charge localization is partially melted at the local scale, suggesting a reentrant behavior of charge ordering. This result is supported by the weakening of superstructure reflections and the temperature evolution of electron paramagnetic resonance linewidth that is consistent with paramagnetic reentrant behavior reported in the GdBaCo2O5.5 parent compound.

Theoretical investigation on the soft X-ray spectrum of the highly-charged W54+ ions

NASA Astrophysics Data System (ADS)

Ding, Xiaobin; Yang, Jiaoxia; Koike, Fumihiro; Murakami, Izumi; Kato, Daiji; Sakaue, Hiroyuki A.; Nakamura, Nobuyuki; Dong, Chenzhong

2018-01-01

A detailed level collisional-radiative model of the E1 transition spectrum of Ca-like W54+ ion has been constructed. All the necessary atomic data has been calculated by relativistic configuration interaction (RCI) method with the implementation of Flexible Atomic Code (FAC). The results are in reasonable agreement with the available experimental and previous theoretical data. The synthetic spectrum has explained the EBIT spectrum in 29.5-32.5 Å , while several new strong transitions has been predicted to be observed in 18.5-19.6 Å for the future EBIT experiment with electron density ne = 1012 cm-3 and electron beam energy Ee = 18.2 keV.

Bending and breaking of stripes in a charge ordered manganite.

PubMed

Savitzky, Benjamin H; El Baggari, Ismail; Admasu, Alemayehu S; Kim, Jaewook; Cheong, Sang-Wook; Hovden, Robert; Kourkoutis, Lena F

2017-12-01

In charge-ordered phases, broken translational symmetry emerges from couplings between charge, spin, lattice, or orbital degrees of freedom, giving rise to remarkable phenomena such as colossal magnetoresistance and metal-insulator transitions. The role of the lattice in charge-ordered states remains particularly enigmatic, soliciting characterization of the microscopic lattice behavior. Here we directly map picometer scale periodic lattice displacements at individual atomic columns in the room temperature charge-ordered manganite Bi 0.35 Sr 0.18 Ca 0.47 MnO 3 using aberration-corrected scanning transmission electron microscopy. We measure transverse, displacive lattice modulations of the cations, distinct from existing manganite charge-order models. We reveal locally unidirectional striped domains as small as ~5 nm, despite apparent bidirectionality over larger length scales. Further, we observe a direct link between disorder in one lattice modulation, in the form of dislocations and shear deformations, and nascent order in the perpendicular modulation. By examining the defects and symmetries of periodic lattice displacements near the charge ordering phase transition, we directly visualize the local competition underpinning spatial heterogeneity in a complex oxide.

The phase transitions between Z n × Z n bosonic topological phases in 1 + 1D, and a constraint on the central charge for the critical points between bosonic symmetry protected topological phases

DOE PAGES

Tsui, Lokman; Huang, Yen-Ta; Jiang, Hong-Chen; ...

2017-03-27

The study of continuous phase transitions triggered by spontaneous symmetry breaking has brought revolutionary ideas to physics. Recently, through the discovery of symmetry protected topological phases, it is realized that continuous quantum phase transition can also occur between states with the same symmetry but different topology. Here in this paper we study a specific class of such phase transitions in 1+1 dimensions – the phase transition between bosonic topological phases protected by Z n × Z n. We find in all cases the critical point possesses two gap opening relevant operators: one leads to a Landau-forbidden symmetry breaking phase transitionmore » and the other to the topological phase transition. We also obtained a constraint on the central charge for general phase transitions between symmetry protected bosonic topological phases in 1+1D.« less

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

DOE PAGES

Middey, S.; Meyers, D.; Kareev, M.; ...

2018-04-09

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO 3. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions.more » Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. In conclusion, this designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.« less

The phase transitions between Z n × Z n bosonic topological phases in 1 + 1D, and a constraint on the central charge for the critical points between bosonic symmetry protected topological phases

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

Tsui, Lokman; Huang, Yen-Ta; Jiang, Hong-Chen

The study of continuous phase transitions triggered by spontaneous symmetry breaking has brought revolutionary ideas to physics. Recently, through the discovery of symmetry protected topological phases, it is realized that continuous quantum phase transition can also occur between states with the same symmetry but different topology. Here in this paper we study a specific class of such phase transitions in 1+1 dimensions – the phase transition between bosonic topological phases protected by Z n × Z n. We find in all cases the critical point possesses two gap opening relevant operators: one leads to a Landau-forbidden symmetry breaking phase transitionmore » and the other to the topological phase transition. We also obtained a constraint on the central charge for general phase transitions between symmetry protected bosonic topological phases in 1+1D.« less

Temperature-dependent vibrational spectroscopy to study order-disorder transitions in charge transfer complexes

NASA Astrophysics Data System (ADS)

Isaac, Rohan; Goetz, Katelyn P.; Roberts, Drew; Jurchescu, Oana D.; McNeil, L. E.

2018-02-01

Charge-transfer (CT) complexes are a promising class of materials for the semiconductor industry because of their versatile properties. This class of compounds shows a variety of phase transitions, which are of interest because of their potential impact on the electronic characteristics. Here temperature-dependent vibrational spectroscopy is used to study structural phase transitions in a set of organic CT complexes. Splitting and broadening of infrared-active phonons in the complex formed between pyrene and pyromellitic dianhydride (PMDA) confirm the structural transition is of the order-disorder type and complement previous x-ray diffraction (XRD) results. We show that this technique is a powerful tool to characterize transitions, and apply it to a range of binary CT complexes composed of polyaromatic hyrdocarbons (anthracene, perylene, phenanthrene, pyrene, and stilbene) and PMDA. We extend the understanding of transitions in perylene-PMDA and pyrene-PMDA, and show that there are no order-disorder transitions present in anthracene-PMDA, stilbene-PMDA and phenanthrene-PMDA in the temperature range investigated here.

Disentangled Cooperative Orderings in Artificial Rare-Earth Nickelates

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

Middey, S.; Meyers, D.; Kareev, M.

Coupled transitions between distinct ordered phases are important aspects behind the rich phase complexity of correlated oxides that hinder our understanding of the underlying phenomena. For this reason, fundamental control over complex transitions has become a leading motivation of the designer approach to materials. We have devised a series of new superlattices by combining a Mott insulator and a correlated metal to form ultrashort period superlattices, which allow one to disentangle the simultaneous orderings in RENiO 3. Tailoring an incommensurate heterostructure period relative to the bulk charge ordering pattern suppresses the charge order transition while preserving metal-insulator and antiferromagnetic transitions.more » Such selective decoupling of the entangled phases resolves the long-standing puzzle about the driving force behind the metal-insulator transition and points to the site-selective Mott transition as the operative mechanism. In conclusion, this designer approach emphasizes the potential of heterointerfaces for selective control of simultaneous transitions in complex materials with entwined broken symmetries.« less

Quasi-continuous transition from a Fermi liquid to a spin liquid in κ-(ET)2Cu2(CN)3.

PubMed

Furukawa, Tetsuya; Kobashi, Kazuhiko; Kurosaki, Yosuke; Miyagawa, Kazuya; Kanoda, Kazushi

2018-01-22

The Mott metal-insulator transition-a manifestation of Coulomb interactions among electrons-is known as a discontinuous transition. Recent theoretical studies, however, suggest that the transition is continuous if the Mott insulator carries a spin liquid with a spinon Fermi surface. Here, we demonstrate the case of a quasi-continuous Mott transition from a Fermi liquid to a spin liquid in an organic triangular-lattice system κ-(ET) 2 Cu 2 (CN) 3 . Transport experiments performed under fine pressure tuning have found that as the Mott transition is approached, the Fermi liquid coherence temperature continuously falls to the scale of kelvins, with a divergent quasi-particle decay rate on the metal side, and the charge gap continuously closes on the insulator side. A Clausius-Clapeyron analysis provides thermodynamic evidence for the extremely weak first-order nature of the transition. These results provide additional support for the existence of a spinon Fermi surface, which becomes an electron Fermi surface when charges are delocalized.

Transition from the adiabatic to the sudden limit in core-level photoemission: A model study of a localized system

NASA Astrophysics Data System (ADS)

Lee, J. D.; Gunnarsson, O.; Hedin, L.

1999-09-01

We consider core electron photoemission in a localized system, where there is a charge transfer excitation. Examples are transition metal and rare earth compounds, chemisorption systems, and high-Tc compounds. The system is modeled by three electron levels, one core level, and two outer levels. In the initital state the core level and one outer level is filled (a spinless two-electron problem). This model system is embedded in a solid state environment, and the implications of our model system results for solid state photoemission are discussed. When the core hole is created, the more localized outer level (d) is pulled below the less localized level (L). The spectrum has a leading peak corresponding to a charge transfer between L and d (``shakedown''), and a satellite corresponding to no charge transfer. The model has a Coulomb interaction between these levels and the continuum states into which the core electron is emitted. The model is simple enough to allow an exact numerical solution, and with a separable potential an analytic solution. Analytic results are also obtained in lowest order perturbation theory, and in the high-energy limit of the semiclassical approximation. We calculate the ratio r(ω) between the weights of the satellite and the main peak as a function of the photon energy ω. The transition from the adiabatic to the sudden limit is found to take place for quite small kinetic energies of the photoelectron. For such small energies, the variation of the dipole matrix elements is substantial and described by the energy scale E~d. Without the coupling to the photoelectron, the corresponding ratio r0(ω) shows a smooth turn-on of the satellite intensity, due to the turn on of the dipole matrix element. The characteristic energy scales are E~d and the satellite excitation energy δE. When the interaction potential with the continuum states is introduced an energy scale E~s=1/(2R~2s) enters, where R~s is a length scale of the interaction (scattering) potential. At threshold there is typically a (weak) constructive interference between intrinsic and extrinsic contributions, and the ratio r(ω)/r0(ω) is larger than its limiting value for large ω. The interference becomes small or weakly destructive for photoelectron energies of the order E~s. For larger photoelectron energies r(ω)/r0(ω) therefore typically has a weak undershoot. If this undershoot is neglected, r(ω)/r0(ω) reaches its limiting value on the energy scale E~s for the parameter range considered here. In a ``shake-up'' scenario, where the two outer levels do not cross as the core hole is created, we instead find that r(ω)/r0(ω) is typically reduced for small ω by interference effects, as in the case of plasmon excitation. Even for this shake-down case, however, the results are very different from those for a simple metal, where plasmons dominate the picture. In particular, the adiabatic to sudden transition takes place at much lower energies in the case of a localized excitation. The reasons for the differences are briefly discussed.

Local entanglement entropy of fermions as a marker of quantum phase transition in the one-dimensional Hubbard model

NASA Astrophysics Data System (ADS)

Cha, Min-Chul; Chung, Myung-Hoon

2018-05-01

We study quantum phase transition of interacting fermions by measuring the local entanglement entropy in the one-dimensional Hubbard model. The reduced density matrices for blocks of a few sites are constructed from the ground state wave function in infinite systems by adopting the matrix product state representation where time-evolving block decimations are performed to obtain the lowest energy states. The local entanglement entropy, constructed from the reduced density matrices, as a function of the chemical potential shows clear signatures of the Mott transition. The value of the central charge, numerically determined from the universal properties of the local entanglement entropy, confirms that the transition is caused by the suppression of the charge degrees of freedom.

Disorder induced semiconductor to metal transition and modifications of grain boundaries in nanocrystalline zinc oxide thin film

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

Singh, Fouran; Kumar, Vinod; Chaudhary, Babloo

2012-10-01

This paper report on the disorder induced semiconductor to metal transition (SMT) and modifications of grain boundaries in nanocrystalline zinc oxide thin film. Disorder is induced using energetic ion irradiation. It eliminates the possibility of impurities induced transition. However, it is revealed that some critical concentration of defects is needed for inducing such kind of SMT at certain critical temperature. Above room temperature, the current-voltage characteristics in reverse bias attributes some interesting phenomenon, such as electric field induced charge transfer, charge trapping, and diffusion of defects. The transition is explained by the defects induced disorder and strain in ZnO crystallitesmore » created by high density of electronic excitations.« less

Battery-Charge-State Model

NASA Technical Reports Server (NTRS)

Vivian, H. C.

1985-01-01

Charge-state model for lead/acid batteries proposed as part of effort to make equivalent of fuel gage for battery-powered vehicles. Models based on equations that approximate observable characteristics of battery electrochemistry. Uses linear equations, easier to simulate on computer, and gives smooth transitions between charge, discharge, and recuperation.

The adsorption-desorption transition of double-stranded DNA interacting with an oppositely charged dendrimer induced by multivalent anions.

PubMed

Jiang, Yangwei; Zhang, Dong; Zhang, Yaoyang; Deng, Zhenyu; Zhang, Linxi

2014-05-28

The adsorption-desorption transition of DNA in DNA-dendrimer solutions is observed when high-valence anions, such as hexavalent anions, are added to the DNA-dendrimer solutions. In the DNA-dendrimer solutions with low-valence anions, dendrimers bind tightly with the V-shaped double-stranded DNA. When high-valence anions, such as pentavalent or hexavalent anions, are added to the DNA-dendrimer solutions, the double-stranded DNA chains can be stretched straightly and the dendrimers are released from the double-stranded DNA chains. In fact, adding high-valence anions to the solutions can change the charge spatial distribution in the DNA-dendrimer solutions, and weaken the electrostatic interactions between the positively charged dendrimers and the oppositely charged DNA chains. Adsorption-desorption transition of DNA is induced by the overcharging of dendrimers. This investigation is capable of helping us understand how to control effectively the release of DNA in gene/drug delivery because an effective gene delivery for dendrimers includes non-covalent DNA-dendrimer binding and the effective release of DNA in gene therapy.

Development of a ferromagnetic component in the superconducting state of Fe-excess Fe1.12Te1-xSex by electronic charge redistribution

NASA Astrophysics Data System (ADS)

Li, Wen-Hsien; Karna, Sunil K.; Hsu, Han; Li, Chi-Yen; Lee, Chi-Hung; Sankar, Raman; Cheng Chou, Fang

2015-06-01

The general picture established so far for the links between superconductivity and magnetic ordering in iron chalcogenide Fe1+y(Te1-xSex) is that the substitution of Se for Te directly drives the system from the antiferromagnetic end into the superconducting regime. Here, we report on the observation of a ferromagnetic component that developed together with the superconducting transition in Fe-excess Fe1.12Te1-xSex crystals using neutron and x-ray diffractions, resistivity, magnetic susceptibility and magnetization measurements. The superconducting transition is accompanied by a negative thermal expansion of the crystalline unit cell and an electronic charge redistribution, where a small portion of the electronic charge flows from around the Fe sites toward the Te/Se sites. First-principles calculations show consistent results, revealing that the excess Fe ions play a more significant role in affecting the magnetic property in the superconducting state than in the normal state and the occurrence of an electronic charge redistribution through the superconducting transition.

Investigation of the Presence of Charge Order in Magnetite by Measurement of the Sprin Wave Spectrum

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

McQueeny, R. J.; Yethiraj, Mohana; Montfrooij, W.

Inelastic neutron scattering results on magnetite (Fe{sub 3}O{sub 4}) show a large splitting in the acoustic spin wave branch, producing a 7 meV gap midway to the Brillouin zone boundary at q = (0,0,1/2) and {h_bar}{omega} = 43 meV. The splitting occurs below the Verwey transition temperature, where a metal-insulator transition occurs simultaneously with a structural transformation, supposedly caused by the charge ordering on the iron sublattice. The wavevector (0,0,1/2) corresponds to the superlattice peak in the low symmetry structure. The dependence of the magnetic superexchange on changes in the crystal structure and ionic configurations that occur below the Verweymore » transition affect the spin wave dispersion. To better understand the origin of the observed splitting, several Heisenberg models intended to reproduce the pair-wise variation of the magnetic superexchange arising from both small crystalline distortions and charge ordering were studied. None of the models studied predicts the observed splitting, whose origin may arise from charge-density wave formation or magnetoelastic coupling.« less

Extremal black holes, Stueckelberg scalars and phase transitions

NASA Astrophysics Data System (ADS)

Marrani, Alessio; Miskovic, Olivera; Leon, Paula Quezada

2018-02-01

We calculate the entropy of a static extremal black hole in 4D gravity, non-linearly coupled to a massive Stueckelberg scalar. We find that the scalar field does not allow the black hole to be magnetically charged. We also show that the system can exhibit a phase transition due to electric charge variations. For spherical and hyperbolic horizons, the critical point exists only in presence of a cosmological constant, and if the scalar is massive and non-linearly coupled to electromagnetic field. On one side of the critical point, two extremal solutions coexist: Reissner-Nordström (A)dS black hole and the charged hairy (A)dS black hole, while on the other side of the critical point the black hole does not have hair. A near-critical analysis reveals that the hairy black hole has larger entropy, thus giving rise to a zero temperature phase transition. This is characterized by a discontinuous second derivative of the entropy with respect to the electric charge at the critical point. The results obtained here are analytical and based on the entropy function formalism and the second law of thermodynamics.

Theory of the polarization of highly charged ions in storage rings: Production, preservation, observation and application to the search for a violation of the fundamental symmetries

NASA Astrophysics Data System (ADS)

Bondarevskaya, A.; Prozorov, A.; Labzowsky, L.; Plunien, G.; Liesen, D.; Bosch, F.

2011-10-01

Theoretical concepts for the production, preservation and control of polarized highly charged ion beams in storage rings are investigated. It is argued that hydrogen-like ions can be polarized efficiently by optical pumping of the Zeeman sublevels of ground state hyperfine levels and that the maximum achievable nuclear polarization exceeds 90%. In order to study the preservation of the polarization during the ion motion through the magnetic system of the ring, the concept of the instantaneous quantization axis is introduced. It is suggested that the employment of “Siberian snakes” may help to preserve the ion beam polarization in the ring. The control of the beam polarization can be achieved by different methods: by measuring the Stokes parameters for the emitted photons or by observing the angular dependence of the transition rates for polarized ions. The important motivation for the production of polarized ion beams is the possibility to observe parity nonconservation effects in the hyperfine-quenched transitions in helium-like highly charged ions, where these effects can reach an unprecedented high value for atomic physics. The possible observation of parity nonconservation effects connected with the nuclear anapole moment is also discussed. A method for the observation of the electric dipole moment of an electron in a storage ring with a polarized highly charged ion beam is proposed. This method allows, in principle, to improve the existing boundaries for the electric dipole moment of an electron. However, the requirements of the corresponding experiment are very stringent.

Internal transitions of neutral (X) and negatively charged (X(-)) magneto-excitons investigated by optically detected resonance (ODR) spectroscopy

NASA Astrophysics Data System (ADS)

Nickel, Hans Andreas

Optically detected resonance (ODR) spectroscopy, an experimental technique combining spectroscopy in the far-infrared and visible regimes of the spectrum, has been applied to non-intentionally- and modulation-doped, quasi-2D GaAs/AlGaAs heterostructures at low temperatures and high magnetic fields to study internal transitions of neutral (X) and negatively charged (X--) magneto-excitons. In quasi-2D GaAs/AlGaAs heterostructures with a low density of free carriers, such as undoped multiple-quantum-wells, the ground state of optical excitations is the neutral exciton. This hydrogenic system was studied by far-infrared ODR spectroscopy, and internal excitonic transitions (IETs) 1s → np+/- from the ground state (1s) to excited states (np+/-) were found. Three samples of different well widths were studied systematically, and the behavior of the observed transitions as a function of the sample well-width was as expected. A predicted consequence of an inherent symmetry to the system was verified experimentally for the first time by the simultaneous observation of IETs and electron and hole cyclotron resonance in one sample in one experiment. In addition, it was also found, that the observability of IETs is destroyed as soon as there is a sign of X---recombination in the photoluminescence spectrum. In quantum wells with a small number of excess electrons the ground state of the system under optical excitation is the negatively charged exciton, X--. This mobile system of a hole binding two electrons differs significantly in certain aspects from its immobile impurity analogue, the negatively charged donor ion D-- . The mobility of the charged complex is tied to a hidden symmetry of magnetic translations, which leads to a new selection rule, that forbids X-- bound-to-bound transitions, in contrast to the D -- system, in which these transitions are dominant. In this dissertation, several samples that show X-- recombination in photoluminescence measurements were studied with ODR spectroscopy, and internal singlet and triplet bound-to-continuum transitions were observed for the first time. The experimental results were found to agree well with theoretical numerical calculations. Furthermore, the theoretical predictions were verified: no bound-to-bound X-- internal transition was observed.

Characterization of the 1S-2S transition in antihydrogen.

PubMed

Ahmadi, M; Alves, B X R; Baker, C J; Bertsche, W; Capra, A; Carruth, C; Cesar, C L; Charlton, M; Cohen, S; Collister, R; Eriksson, S; Evans, A; Evetts, N; Fajans, J; Friesen, T; Fujiwara, M C; Gill, D R; Hangst, J S; Hardy, W N; Hayden, M E; Isaac, C A; Johnson, M A; Jones, J M; Jones, S A; Jonsell, S; Khramov, A; Knapp, P; Kurchaninov, L; Madsen, N; Maxwell, D; McKenna, J T K; Menary, S; Momose, T; Munich, J J; Olchanski, K; Olin, A; Pusa, P; Rasmussen, C Ø; Robicheaux, F; Sacramento, R L; Sameed, M; Sarid, E; Silveira, D M; Stutter, G; So, C; Tharp, T D; Thompson, R I; van der Werf, D P; Wurtele, J S

2018-05-01

In 1928, Dirac published an equation 1 that combined quantum mechanics and special relativity. Negative-energy solutions to this equation, rather than being unphysical as initially thought, represented a class of hitherto unobserved and unimagined particles-antimatter. The existence of particles of antimatter was confirmed with the discovery of the positron 2 (or anti-electron) by Anderson in 1932, but it is still unknown why matter, rather than antimatter, survived after the Big Bang. As a result, experimental studies of antimatter 3-7 , including tests of fundamental symmetries such as charge-parity and charge-parity-time, and searches for evidence of primordial antimatter, such as antihelium nuclei, have high priority in contemporary physics research. The fundamental role of the hydrogen atom in the evolution of the Universe and in the historical development of our understanding of quantum physics makes its antimatter counterpart-the antihydrogen atom-of particular interest. Current standard-model physics requires that hydrogen and antihydrogen have the same energy levels and spectral lines. The laser-driven 1S-2S transition was recently observed 8 in antihydrogen. Here we characterize one of the hyperfine components of this transition using magnetically trapped atoms of antihydrogen and compare it to model calculations for hydrogen in our apparatus. We find that the shape of the spectral line agrees very well with that expected for hydrogen and that the resonance frequency agrees with that in hydrogen to about 5 kilohertz out of 2.5 × 10 15 hertz. This is consistent with charge-parity-time invariance at a relative precision of 2 × 10 -12 -two orders of magnitude more precise than the previous determination 8 -corresponding to an absolute energy sensitivity of 2 × 10 -20 GeV.

New Measurement of the 1 S -3 S Transition Frequency of Hydrogen: Contribution to the Proton Charge Radius Puzzle

NASA Astrophysics Data System (ADS)

Fleurbaey, Hélène; Galtier, Sandrine; Thomas, Simon; Bonnaud, Marie; Julien, Lucile; Biraben, François; Nez, François; Abgrall, Michel; Guéna, Jocelyne

2018-05-01

We present a new measurement of the 1 S -3 S two-photon transition frequency of hydrogen, realized with a continuous-wave excitation laser at 205 nm on a room-temperature atomic beam, with a relative uncertainty of 9 ×10-13. The proton charge radius deduced from this measurement, rp=0.877 (13 ) fm , is in very good agreement with the current CODATA-recommended value. This result contributes to the ongoing search to solve the proton charge radius puzzle, which arose from a discrepancy between the CODATA value and a more precise determination of rp from muonic hydrogen spectroscopy.

Charge order-superfluidity transition in a two-dimensional system of hard-core bosons and emerging domain structures

NASA Astrophysics Data System (ADS)

Moskvin, A. S.; Panov, Yu. D.; Rybakov, F. N.; Borisov, A. B.

2017-11-01

We have used high-performance parallel computations by NVIDIA graphics cards applying the method of nonlinear conjugate gradients and Monte Carlo method to observe directly the developing ground state configuration of a two-dimensional hard-core boson system with decrease in temperature, and its evolution with deviation from a half-filling. This has allowed us to explore unconventional features of a charge order—superfluidity phase transition, specifically, formation of an irregular domain structure, emergence of a filamentary superfluid structure that condenses within of the charge-ordered phase domain antiphase boundaries, and formation and evolution of various topological structures.

Properties of jets measured from tracks in proton-proton collisions at center-of-mass energy s = 7 TeV with the ATLAS detector

DOE PAGES

Aad, G.; Abbott, B.; Abdallah, J.; ...

2011-09-20

Jets are identified and their properties studied in center-of-mass energy √s = 7 TeV proton-proton collisions at the Large Hadron Collider using charged particles measured by the ATLAS inner detector. Events are selected using a minimum bias trigger, allowing jets at very low transverse momentum to be observed and their characteristics in the transition to high-momentum fully perturbative jets to be studied. Jets are reconstructed using the anti-k t algorithm applied to charged particles with two radius parameter choices, 0.4 and 0.6. An inclusive charged jet transverse momentum cross section measurement from 4 GeV to 100 GeV is shown formore » four ranges in rapidity extending to 1.9 and corrected to charged particle-level truth jets. The transverse momenta and longitudinal momentum fractions of charged particles within jets are measured, along with the charged particle multiplicity and the particle density as a function of radial distance from the jet axis. Comparison of the data with the theoretical models implemented in existing tunings of Monte Carlo event generators indicates reasonable overall agreement between data and Monte Carlo. In conclusion, these comparisons are sensitive to Monte Carlo parton showering, hadronization, and soft physics models.« less

Vacancies and Vacancy-Mediated Self Diffusion in Cr 2 O 3 : A First-Principles Study

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

Medasani, Bharat; Sushko, Maria L.; Rosso, Kevin M.

Charged and neutral vacancies and vacancy mediated self diffusion in alpha-Cr2O3 were investigated using first principles density functional theory (DFT) and periodic supercell formalism. The vacancy formation energies of charged defects were calculated using the electrostatic finite-size corrections to account for electrostatic interactions between supercells and the corrections for the bandgap underestimation in DFT. Calculations predict that neutral oxygen (O) vacancies are predominant in chromium (Cr)-rich conditions and Cr vacancies with -2 charge state are the dominant defects in O-rich conditions. The charge transition levels of both O and Cr vacancies are deep within the bandgap indicating the stability ofmore » these defects. Transport calculations indicate that vacancy mediated diffusion along the basal plane has lower energy barriers for both O and Cr ions. The most favorable vacancy mediated self diffusion processes correspond to the diffusion of Cr ion in 3+ charge state and O ion in 2- state, respectively. Our calculations reveal that Cr triple defects comprised of Cr in octahedral interstitial sites with two adjacent Cr vacancies along the c-axis have a lower formation energy compared to that of charged Cr vacancies. The formation of such triple defects facilitate Cr self diffusion along the c-axis.« less

Thermodynamics and phase transition of charged AdS black holes with a global monopole

NASA Astrophysics Data System (ADS)

Deng, Gao-Ming; Fan, Jinbo; Li, Xinfei; Huang, Yong-Chang

2018-01-01

Thermodynamical properties of charged AdS black holes with a global monopole still remain obscure. In this paper, we investigate the thermodynamics and phase transition of the black holes in the extended phase space. It is shown that thermodynamical quantities of the black holes exhibit an interesting dependence on the internal global monopole, and they perfectly satisfy both the first law of thermodynamics and Smarr relation. Furthermore, analysis of the local and the global thermodynamical stability manifests that the charged AdS black hole undergoes an elegant phase transition at critical point. Of special interest, critical behaviors of the black holes resemble a Van der Waals liquid-gas system. Our results not only reveal the effect of a global monopole on thermodynamics of AdS black holes, but also further support that Van der Waals-like behavior of the black holes is a universal phenomenon.

Dimensional crossover of the charge density wave transition in thin exfoliated VSe2

NASA Astrophysics Data System (ADS)

Pásztor, Árpád; Scarfato, Alessandro; Barreteau, Céline; Giannini, Enrico; Renner, Christoph

2017-12-01

Isolating single unit-cell thin layers from the bulk matrix of layered compounds offers tremendous opportunities to design novel functional electronic materials. However, a comprehensive thickness dependence study is paramount to harness the electronic properties of such atomic foils and their stacking into synthetic heterostructures. Here we show that a dimensional crossover and quantum confinement with reducing thickness result in a striking non-monotonic evolution of the charge density wave transition temperature in VSe2. Our conclusion is drawn from a direct derivation of the local order parameter and transition temperature from the real space charge modulation amplitude imaged by scanning tunnelling microscopy. This study lifts the disagreement of previous independent transport measurements. We find that thickness can be a non-trivial tuning parameter and demonstrate the importance of considering a finite thickness range to accurately characterize its influence.

Enhancement of cold fusion in metal ``hydrides'' by screening of proton and deuteron charges

NASA Astrophysics Data System (ADS)

Burrows, Adam

1989-08-01

The production of fusion heat in a metal hydride (deuteride) lattice is problematic, since the reported ratio of power to neutron or γ-ray flux of some workers is much larger than that for any known conventional complement of fusion reactions. However, enhanced screening of the deuteron or proton charge in the lattice cages might enhance to modest levels the standard d+d-->3He+n,T+p and p+d-->3He+γ fusion reactions. By lowering the effective deuteron-deuteron and proton-deuteron Coulomb barriers, the effective Gamov penetration factor is increased substantially in metals in general, transition metals in particular, and perhaps enough to produce modest neutron fluxes and tritium yields.

Self-doping processes between planes and chains in the metal-to-superconductor transition of YBa2Cu3O6.9.

PubMed

Magnuson, M; Schmitt, T; Strocov, V N; Schlappa, J; Kalabukhov, A S; Duda, L-C

2014-11-12

The interplay between the quasi 1-dimensional CuO-chains and the 2-dimensional CuO2 planes of YBa(2)Cu(3)O(6+x) (YBCO) has been in focus for a long time. Although the CuO-chains are known to be important as charge reservoirs that enable superconductivity for a range of oxygen doping levels in YBCO, the understanding of the dynamics of its temperature-driven metal-superconductor transition (MST) remains a challenge. We present a combined study using x-ray absorption spectroscopy and resonant inelastic x-ray scattering (RIXS) revealing how a reconstruction of the apical O(4)-derived interplanar orbitals during the MST of optimally doped YBCO leads to substantial hole-transfer from the chains into the planes, i.e. self-doping. Our ionic model calculations show that localized divalent charge-transfer configurations are expected to be abundant in the chains of YBCO. While these indeed appear in the RIXS spectra from YBCO in the normal, metallic, state, they are largely suppressed in the superconducting state and, instead, signatures of Cu trivalent charge-transfer configurations in the planes become enhanced. In the quest for understanding the fundamental mechanism for high-Tc-superconductivity (HTSC) in perovskite cuprate materials, the observation of such an interplanar self-doping process in YBCO opens a unique novel channel for studying the dynamics of HTSC.

Computational analysis of molecular properties and spectral characteristics of cyano-containing liquid crystals: role of alkyl chains.

PubMed

Praveen, P Lakshmi; Ojha, Durga P

2011-05-01

The electronic transitions in the uv-visible range of 4'-n-alkyl-4-cyanobiphenyl (nCB) with propyl, pentyl, and heptyl groups, which are of commercial and application interests, have been studied. The uv-visible and circular dichroism spectra of nCB (n = 3,5,7) molecules have been simulated using the time dependent density functional theory Becke3-Lee-Yang-Parr hybrid functional-6-31 + G (d) method. Mulliken atomic charges for each molecule have been compared with Loewdin atomic charges to analyze the molecular charge distribution and phase stability. The highest occupied molecular orbital and lowest unoccupied molecular orbital energies corresponding to the electronic transitions in the uv-visible range have been reported. Excited states have been calculated via the configuration interaction single level with a semiempirical Hamiltonian (intermediate neglect of differential overlap method, as parametrized by Zerner and co-workers). Further, two types of calculations have been performed for model systems containing single and double molecules of nCB. Furthermore, the dimer complexes during the different modes of molecular interactions have also been studied. The interaction energies of dimer complexes have been taken into consideration in order to investigate the most energetically stable configuration. These studies are helpful for understanding the role and flexibility of end chains, in particular, phase behavior and stability.

Evidence for gain on the C VI 182 A transition in a radiation-cooled selenium/Formvar plasma

NASA Technical Reports Server (NTRS)

Seely, J. F.; Brown, C. M.; Feldman, U.; Richardson, M.; Behring, W. E.

1985-01-01

Thin plastic foils coated with selenium have been irradiated using from 4 to 8 beams of the OMEGA laser in a line focus configuration. Spectra were recorded using a 3 meter spectrograph that viewed the plasma along the line focus. Based on a comparison of the intensities of the spectral lines from plasmas with lengths of 1.7, 3.4, 6.8, and 13.6 mm, the C VI n = 3 to 2 transition at 182 A was anomalously intense in the spectra from the longer plasmas. Calculations indicate that the carbon plasma was cooled by radiation from the highly-charged selenium plasma in a time that was smaller than the expansion time of the plasma. These plasma conditions are favorable for the occurrence of population inversions between the n = 2 and 3 levels of C VI resulting from recombination and cascading from higher levels. The measured gain coefficient for the C VI 182 A transition is 3/cm, and this corresponds to a gain-length product of 4 in the longest plasma.

Atomic structure calculations for F-like tungsten

NASA Astrophysics Data System (ADS)

Sunny, Aggarwal

2014-09-01

Energy levels, wavefunction compositions and lifetimes have been computed for all levels of 1s22s22p5, 1s22s2p6, 1s22s22p43s, 1s22s22p43p, and 1s22s22p43d configurations in highly charged F-like tungsten ion. The multiconfigurational Dirac—Fock method (MCDF) is adopted to generate the wavefunctions. We have also presented the transition wavelengths, oscillator strengths, transition probabilities, and line strengths for the electric dipole (E1) and magnetic quadrupole (M2) transition from the 1s22s22p5 ground configuration. We have performed parallel calculations with the flexible atomic code (FAC) for comparing the atomic data. The reliability of present data is assessed by comparison with other theoretical and experimental data available in the literature. Good agreement is found between our results and those obtained using different approaches confirm the quality of our results. Additionally, we have predicted some new atomic data for F-like W that were not available so far and may be important for plasma diagnostic analysis in fusion plasma.

Extension of the quantum-kinetic model to lunar and Mars return physics

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

Liechty, D. S.; Lewis, M. J.

The ability to compute rarefied, ionized hypersonic flows is becoming more important as missions such as Earth reentry, landing high-mass payloads on Mars, and the exploration of the outer planets and their satellites are being considered. A recently introduced molecular-level chemistry model, the quantum-kinetic, or Q-K, model that predicts reaction rates for gases in thermal equilibrium and non-equilibrium using only kinetic theory and fundamental molecular properties, is extended in the current work to include electronic energy level transitions and reactions involving charged particles. Like the Q-K procedures for neutral species chemical reactions, these new models are phenomenological procedures that aimmore » to reproduce the reaction/transition rates but do not necessarily capture the exact physics. These engineering models are necessarily efficient due to the requirement to compute billions of simulated collisions in direct simulation Monte Carlo (DSMC) simulations. The new models are shown to generally agree within the spread of reported transition and reaction rates from the literature for near equilibrium conditions.« less

Fast-timing study of the l -forbidden 1 /2+→3 /2+ M 1 transition in 129Sn

NASA Astrophysics Data System (ADS)

Licǎ, R.; Mach, H.; Fraile, L. M.; Gargano, A.; Borge, M. J. G.; Mǎrginean, N.; Sotty, C. O.; Vedia, V.; Andreyev, A. N.; Benzoni, G.; Bomans, P.; Borcea, R.; Coraggio, L.; Costache, C.; De Witte, H.; Flavigny, F.; Fynbo, H.; Gaffney, L. P.; Greenlees, P. T.; Harkness-Brennan, L. J.; Huyse, M.; Ibáñez, P.; Judson, D. S.; Konki, J.; Korgul, A.; Kröll, T.; Kurcewicz, J.; Lalkovski, S.; Lazarus, I.; Lund, M. V.; Madurga, M.; Mǎrginean, R.; Marroquín, I.; Mihai, C.; Mihai, R. E.; Morales, A. I.; Nácher, E.; Negret, A.; Page, R. D.; Pakarinen, J.; Pascu, S.; Paziy, V.; Perea, A.; Pérez-Liva, M.; Picado, E.; Pucknell, V.; Rapisarda, E.; Rahkila, P.; Rotaru, F.; Swartz, J. A.; Tengblad, O.; Van Duppen, P.; Vidal, M.; Wadsworth, R.; Walters, W. B.; Warr, N.; IDS Collaboration

2016-04-01

The levels in 129Sn populated from the β- decay of 129In isomers were investigated at the ISOLDE facility of CERN using the newly commissioned ISOLDE Decay Station (IDS). The lowest 1 /2+ state and the 3 /2+ ground state in 129Sn are expected to have configurations dominated by the neutron s1 /2 (l =0 ) and d3 /2 (l =2 ) single-particle states, respectively. Consequently, these states should be connected by a somewhat slow l -forbidden M 1 transition. Using fast-timing spectroscopy we have measured the half-life of the 1 /2+ 315.3-keV state, T1 /2= 19(10) ps, which corresponds to a moderately fast M 1 transition. Shell-model calculations using the CD-Bonn effective interaction, with standard effective charges and g factors, predict a 4-ns half-life for this level. We can reconcile the shell-model calculations to the measured T1 /2 value by the renormalization of the M 1 effective operator for neutron holes.

Δ(1232) axial charge and form factors from lattice QCD.

PubMed

Alexandrou, Constantia; Gregory, Eric B; Korzec, Tomasz; Koutsou, Giannis; Negele, John W; Sato, Toru; Tsapalis, Antonios

2011-09-30

We present the first calculation on the Δ axial vector and pseudoscalar form factors using lattice QCD. Two Goldberger-Treiman relations are derived and examined. A combined chiral fit is performed to the nucleon axial charge, N to Δ axial transition coupling constant and Δ axial charge.

Higgs-mode radiance and charge-density-wave order in 2 H -NbSe2

NASA Astrophysics Data System (ADS)

Grasset, Romain; Cea, Tommaso; Gallais, Yann; Cazayous, Maximilien; Sacuto, Alain; Cario, Laurent; Benfatto, Lara; Méasson, Marie-Aude

2018-03-01

Despite being usually considered two competing phenomena, charge-density wave and superconductivity coexist in few systems, the most emblematic one being the transition-metal dichalcogenide 2 H -NbSe2 . This unusual condition is responsible for specific Raman signatures across the two phase transitions in this compound. While the appearance of a soft phonon mode is a well-established fingerprint of the charge-density-wave order, the nature of the sharp subgap mode emerging below the superconducting temperature is still under debate. In this work we use external pressure as a knob to unveil the delicate interplay between the two orders, and consequently the nature of the superconducting mode. Thanks to an advanced extreme-conditions Raman technique, we are able to follow the pressure evolution and the simultaneous collapse of the two intertwined charge-density-wave and superconducting modes. The comparison with microscopic calculations in a model system supports the Higgs-type nature of the superconducting mode and suggests that charge-density wave and superconductivity in 2 H -NbSe2 involve mutual electronic degrees of freedom. These findings fill the knowledge gap on the electronic mechanisms at play in transition-metal dichalcogenides, a crucial step to fully exploit their properties in few-layer systems optimized for device applications.

Stochastic charging of dust grains in planetary rings: Diffusion rates and their effects on Lorentz resonances

NASA Technical Reports Server (NTRS)

Schaffer, L.; Burns, J. A.

1995-01-01

Dust grains in planetary rings acquire stochastically fluctuating electric charges as they orbit through any corotating magnetospheric plasma. Here we investigate the nature of this stochastic charging and calculate its effect on the Lorentz resonance (LR). First we model grain charging as a Markov process, where the transition probabilities are identified as the ensemble-averaged charging fluxes due to plasma pickup and photoemission. We determine the distribution function P(t;N), giving the probability that a grain has N excess charges at time t. The autocorrelation function tau(sub q) for the strochastic charge process can be approximated by a Fokker-Planck treatment of the evolution equations for P(t; N). We calculate the mean square response to the stochastic fluctuations in the Lorentz force. We find that transport in phase space is very small compared to the resonant increase in amplitudes due to the mean charge, over the timescale that the oscillator is resonantly pumped up. Therefore the stochastic charge variations cannot break the resonant interaction; locally, the Lorentz resonance is a robust mechanism for the shaping of etheral dust ring systems. Slightly stronger bounds on plasma parameters are required when we consider the longer transit times between Lorentz resonances.

General trends of dihedral conformational transitions in a globular protein.

PubMed

Miao, Yinglong; Baudry, Jerome; Smith, Jeremy C; McCammon, J Andrew

2016-04-01

Dihedral conformational transitions are analyzed systematically in a model globular protein, cytochrome P450cam, to examine their structural and chemical dependences through combined conventional molecular dynamics (cMD), accelerated molecular dynamics (aMD) and adaptive biasing force (ABF) simulations. The aMD simulations are performed at two acceleration levels, using dihedral and dual boost, respectively. In comparison with cMD, aMD samples protein dihedral transitions approximately two times faster on average using dihedral boost, and ∼ 3.5 times faster using dual boost. In the protein backbone, significantly higher dihedral transition rates are observed in the bend, coil, and turn flexible regions, followed by the β bridge and β sheet, and then the helices. Moreover, protein side chains of greater length exhibit higher transition rates on average in the aMD-enhanced sampling. Side chains of the same length (particularly Nχ = 2) exhibit decreasing transition rates with residues when going from hydrophobic to polar, then charged and aromatic chemical types. The reduction of dihedral transition rates is found to be correlated with increasing energy barriers as identified through ABF free energy calculations. These general trends of dihedral conformational transitions provide important insights into the hierarchical dynamics and complex free energy landscapes of functional proteins. © 2016 Wiley Periodicals, Inc.

General trends of dihedral conformational transitions in a globular protein

DOE PAGES

Miao, Yinglong; Baudry, Jerome; Smith, Jeremy C.; ...

2016-02-15

In this paper, dihedral conformational transitions are analyzed systematically in a model globular protein, cytochrome P450cam, to examine their structural and chemical dependences through combined conventional molecular dynamics (cMD), accelerated molecular dynamics (aMD) and adaptive biasing force (ABF) simulations. The aMD simulations are performed at two acceleration levels, using dihedral and dual boost, respectively. In comparison with cMD, aMD samples protein dihedral transitions approximately two times faster on average using dihedral boost, and ~3.5 times faster using dual boost. In the protein backbone, significantly higher dihedral transition rates are observed in the bend, coil, and turn flexible regions, followed bymore » the β bridge and β sheet, and then the helices. Moreover, protein side chains of greater length exhibit higher transition rates on average in the aMD-enhanced sampling. Side chains of the same length (particularly Nχ = 2) exhibit decreasing transition rates with residues when going from hydrophobic to polar, then charged and aromatic chemical types. The reduction of dihedral transition rates is found to be correlated with increasing energy barriers as identified through ABF free energy calculations. In conclusion, these general trends of dihedral conformational transitions provide important insights into the hierarchical dynamics and complex free energy landscapes of functional proteins.« less

Identification of Mott insulators and Anderson insulators in self-assembled gold nanoparticles thin films

NASA Astrophysics Data System (ADS)

Jiang, Cheng-Wei; Ni, I.-Chih; Tzeng, Shien-Der; Wu, Cen-Shawn; Kuo, Watson

2014-05-01

How the interparticle tunnelling affects the charge conduction of self-assembled gold nanoparticles is studied by three means: tuning the tunnel barrier width by different molecule modification and by substrate bending, and tuning the barrier height by high-dose electron beam exposure. All approaches indicate that the metal-Mott insulator transition is governed predominantly by the interparticle coupling strength, which can be quantified by the room temperature sheet resistance. The Hubbard gap, following the prediction of quantum fluctuation theory, reduces to zero rapidly as the sheet resistance decreases to the quantum resistance. At very low temperature, the fate of devices near the Mott transition depends on the strength of disorder. The charge conduction is from nearest-neighbour hopping to co-tunnelling between nanoparticles in Mott insulators whereas it is from variable-range hopping through charge puddles in Anderson insulators. When the two-dimensional nanoparticle network is under a unidirectional strain, the interparticle coupling becomes anisotropic so the average sheet resistance is required to describe the charge conduction.How the interparticle tunnelling affects the charge conduction of self-assembled gold nanoparticles is studied by three means: tuning the tunnel barrier width by different molecule modification and by substrate bending, and tuning the barrier height by high-dose electron beam exposure. All approaches indicate that the metal-Mott insulator transition is governed predominantly by the interparticle coupling strength, which can be quantified by the room temperature sheet resistance. The Hubbard gap, following the prediction of quantum fluctuation theory, reduces to zero rapidly as the sheet resistance decreases to the quantum resistance. At very low temperature, the fate of devices near the Mott transition depends on the strength of disorder. The charge conduction is from nearest-neighbour hopping to co-tunnelling between nanoparticles in Mott insulators whereas it is from variable-range hopping through charge puddles in Anderson insulators. When the two-dimensional nanoparticle network is under a unidirectional strain, the interparticle coupling becomes anisotropic so the average sheet resistance is required to describe the charge conduction. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06627d

Cohesive Energies of Some Transition Metal Compounds Using Embedded Clusters

NASA Astrophysics Data System (ADS)

Press, Mehernosh Rustom

The molecular-clusters approach to electronic structure calculation is especially well-suited to the study of properties that depend primarily on the local environment of a system, especially those with no translational symmetry, e.g. systems with defects and structural deformations. The presence of the rest of the crystal environment can be accounted for approximately by embedding the cluster in a self-consistent crystal potential. This thesis makes a contribution in the area of investigating the capability of embedded molecular-clusters to yield reliable bulk structural properties. To this end, an algorithm for calculating the cohesive energies of clusters within the discrete-variational X(,(alpha)) LCAO-MO formulation is set up and verified on simple solids: Li, Na, Cu and LiF. We then use this formulation to study transition metal compounds, for which the interesting physics lies in local lattice defects, foreign impurities and structural deformations. In a self -consistent calculation of the lattice energies and stability of defect clusters in wustite, Fe(,1-x)O, corner-sharing aggregates of the 4:1 defect are identified as the most stable defect configurations due to efficient compensation of the cluster charge. The intercalation properties of layered-transition-metal-dichalcogenides continues to be a fertile experimental working area, backed by comparatively little theoretical study. We find that intercalation of ZrS(,2) with Na perturbs the valence energy level structure sufficiently to induce a more ionic Zr-S bond, a narrowing of the optical gap and filling of the lowest unoccupied host lattice orbitals with the electron donated by Na. Fe - intercalation in ZrS(,2) is accommodated via a strong Fe-S bond, impurity-like band levels in the optical gap of the host and hybridization-driven compression and lowering of the conduction band energy levels. The piezoelectric cuprous halides, CuCl and CuBr, exhibit a host of intriguing properties due to a filled and very active d('10) shell at the Fermi energy. A self-consistent calculation via energy minimization of the internal strain in these compounds shows both Cu-halide bonds to be very rigid with little charge delocalization under strain. Piezoelectric response is calculated in terms of effective charges and quadrupolar moments, e(,T) and (DELTA)Q.

Nonlinear ion dynamics in Hall thruster plasma source by ion transit-time instability

NASA Astrophysics Data System (ADS)

Lim, Youbong; Choe, Wonho; Mazouffre, Stéphane; Park, Jae Sun; Kim, Holak; Seon, Jongho; Garrigues, L.

2017-03-01

High-energy tail formation in an ion energy distribution function (IEDF) is explained in a Hall thruster plasma with the stationary crossed electric and magnetic fields whose discharge current is oscillated at the ion transit-time scale with a frequency of 360 kHz. Among ions in different charge states, singly charged Xe ions (Xe+) have an IEDF that is significantly broadened and shifted toward the high-energy side, which contributes to tail formation in the entire IEDF. Analytical and numerical investigations confirm that the IEDF tail is due to nonlinear ion dynamics in the ion transit-time oscillation.

Density functional tight-binding and infrequent metadynamics can capture entropic effects in intramolecular hydrogen transfer reactions

NASA Astrophysics Data System (ADS)

Oliveira, Luiz F. L.; Fu, Christopher D.; Pfaendtner, Jim

2018-04-01

Infrequent metadynamics uses biased simulations to estimate the unbiased kinetics of a system, facilitating the calculation of rates and barriers. Here the method is applied to study intramolecular hydrogen transfer reactions involving peroxy radicals, a class of reactions that is challenging to model due to the entropic contributions of the formation of ring structures in the transition state. Using the self-consistent charge density-functional based tight-binding (DFTB) method, we applied infrequent metadynamics to the study of four intramolecular H-transfer reactions, demonstrating that the method can qualitatively reproduce these high entropic contributions, as observed in experiments and those predicted by transition state theory modeled by higher levels of theory. We also show that infrequent metadynamics and DFTB are successful in describing the relationship between transition state ring size and kinetic coefficients (e.g., activation energies and the pre-exponential factors).

Theoretical study of metal noble-gas positive ions

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R.

1989-01-01

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors

NASA Astrophysics Data System (ADS)

Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2011-04-01

Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO2 could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO2 (10-5-10-6 S cm-1) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO2 have enhanced conductivity, resulting in a specific capacitance of the constituent MnO2 (~1,145 F g-1) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO2, and facilitates fast ion diffusion between the MnO2 and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery.

Nanoporous metal/oxide hybrid electrodes for electrochemical supercapacitors.

PubMed

Lang, Xingyou; Hirata, Akihiko; Fujita, Takeshi; Chen, Mingwei

2011-04-01

Electrochemical supercapacitors can deliver high levels of electrical power and offer long operating lifetimes, but their energy storage density is too low for many important applications. Pseudocapacitive transition-metal oxides such as MnO(2) could be used to make electrodes in such supercapacitors, because they are predicted to have a high capacitance for storing electrical charge while also being inexpensive and not harmful to the environment. However, the poor conductivity of MnO(2) (10(-5)-10(-6) S cm(-1)) limits the charge/discharge rate for high-power applications. Here, we show that hybrid structures made of nanoporous gold and nanocrystalline MnO(2) have enhanced conductivity, resulting in a specific capacitance of the constituent MnO(2) (~1,145 F g(-1)) that is close to the theoretical value. The nanoporous gold allows electron transport through the MnO(2), and facilitates fast ion diffusion between the MnO(2) and the electrolytes while also acting as a double-layer capacitor. The high specific capacitances and charge/discharge rates offered by such hybrid structures make them promising candidates as electrodes in supercapacitors, combining high-energy storage densities with high levels of power delivery.

Ultrafast Carrier dynamics of InxGa1-xN nanostructures grown directly on Si(111)

NASA Astrophysics Data System (ADS)

Kumar, Praveen; Devi, Pooja; Rodriguez⁠, P. E. D. S.; Kumar, Manish; Shivling, V. D.; Noetzel, Richard; Sharma, Chhavi; Sinha, R. K.; Kumar, Mahesh

2018-05-01

We show a flux dependence changes in structural, optical and electronic properties of InxGa1-xN nanostructures (NSs) namely nanocolumns (NCs), nanoflakes (NFs) and nanowall network (NWN) grown directly on Si(111) surface. Field emission scanning electron microscopy (FESEM) images were recorded to see morphological changes from NFs to NCs and NWNc etc, while high-resolution X-ray diffraction (HRXRD) ω-2θ scans were used to determine In incorporation. The maximum In incorporation was observed to be 20, 33 and 38% for the sharp transition from NFs to NCs and NWNs, respectively. The charge carrier dynamics of these grown NSs were probed using Ultrafast Femtosecond Transient Absorption Spectroscopy (UFTAS) with excitation at 350 nm pump wavelength. The UFTAS studies show the comparative charge carriers dynamics of the NWS, NCs and NFs. The charge carrier studies show a higher lifetime in NWNs as compare to NCs and NFs. Further, to examine electronic structure and level of degeneracy of these NSs, core-level and valence band spectra were analyzed by X-ray photoelectron spectroscopy (XPS), which manifest the upward band bending ranging from 0.2 eV to 0.4 eV.

Optical manifestation of the Stoner ferromagnetic transition in two-dimensional electron systems

NASA Astrophysics Data System (ADS)

Van'kov, A. B.; Kaysin, B. D.; Kukushkin, I. V.

2017-12-01

We perform a magneto-optical study of a two-dimensional electron systems in the regime of the Stoner ferromagnetic instability for even quantum Hall filling factors on MgxZn1 -xO /ZnO heterostructures. Under conditions of Landau-level crossing, caused by enhanced spin susceptibility in combination with the tilting of the magnetic field, the transition between two rivaling phases, paramagnetic and ferromagnetic, is traced in terms of optical spectra reconstruction. Synchronous sharp transformations are observed both in the photoluminescence structure and parameters of collective excitations upon transition from paramagnetic to ferromagnetic ordering. Based on these measurements, a phase diagram is constructed in terms of the two-dimensional electron density and tilt angle of the magnetic field. Apart from stable paramagnetic and ferromagnetic phases, an instability region is found at intermediate parameters with the Stoner transition occurring at ν ≈2 . The spin configuration in all cases is unambiguously determined by means of inelastic light scattering by spin-sensitive collective excitations. One indicator of the spin ordering is the intra-Landau-level spin exciton, which acquires a large spectral weight in the ferromagnetic phases. The other is an abrupt energy shift of the intersubband charge density excitation due to reconstruction of the many-particle energy contribution. From our analysis of photoluminescence and light scattering data, we estimate the ratio of surface areas occupied by the domains of the two phases in the vicinity of a transition point. In addition, the thermal smearing of a phase transition is characterized.

Recent progress in the transition radiation detector techniques

NASA Technical Reports Server (NTRS)

Yuan, L. C. L.

1973-01-01

A list of some of the major experimental achievements involving charged particles in the relativistic region are presented. With the emphasis mainly directed to the X-ray region, certain modes of application of the transition radiation for the identification and separation of relativistic charged particles are discussed. Some recent developments in detection techniques and improvements in detector performances are presented. Experiments were also carried out to detect the dynamic radiation, but no evidence of such an effect was observed.

Jahn-Teller effects in transition-metal compounds with small charge-transfer energy

NASA Astrophysics Data System (ADS)

Mizokawa, Takashi

2013-04-01

We have studied Jahn-Teller effects in Cs2Au2Br6, ACu3Co4O12(A=Ca or Y), and IrTe2 in which the ligand p-to-transition-metal d charge-transfer energy is small or negative. The Au+/Au3+ charge disproportionation of Cs2Au2Br6 manifests in Au 4f photoemission spectra. In Cs2Au2Br6 with negative Δ and intermediate U, the charge disproportionation can be described using effective d orbitals constructed from the Au 5d and Br 4p orbitals and is stabilized by the Jahn-Teller distortion of the Au3+ site with low-spin d8 configuration. In ACu3Co4O12, Δs for Cu3+ and Co4+ are negative and Us are very large. The Zhang-Rice picture is valid to describe the electronic state, and the valence change from Cu2+/Co4+ to Cu3+/Co3+ can be viewed as the O 2p hole transfer from Co to Cu or d9 + d6L → d9L + d6. In IrTe2, both Δ and U are small and the Ir 5d and Te 5p electrons are itinerant to form the multi-band Fermi surfaces. The ideas of band Jahn-Teller transition and Peierls transition are useful to describe the structural instabilities.

Critical phenomena and chemical potential of a charged AdS black hole

NASA Astrophysics Data System (ADS)

Wei, Shao-Wen; Liang, Bin; Liu, Yu-Xiao

2017-12-01

Inspired by the interpretation of the cosmological constant from the boundary gauge theory, we here treat it as the number of colors N and its conjugate quantity as the associated chemical potential μ in the black hole side. Then the thermodynamics and the chemical potential for a five-dimensional charged AdS black hole are studied. It is found that there exists a small-large black hole phase transition of van der Waals type. The critical phenomena are investigated in the N2-μ chart. The result implies that the phase transition can occur for large number of colors N , while is forbidden for small number. This to some extent implies that the interaction of the system increases with the number. In particular, in the reduced parameter space, all the thermodynamic quantities can be rescaled with the black hole charge such that these reduced quantities are charge-independent. Then we obtain the coexistence curve and the phase diagram. The latent heat is also numerically calculated. Moreover, the heat capacity and the thermodynamic scalar are studied. The result indicates that the information of the first-order black hole phase transition is encoded in the heat capacity and scalar. However, the phase transition point cannot be directly calculated with them. Nevertheless, the critical point linked to a second-order phase transition can be determined by either the heat capacity or the scalar. In addition, we calculate the critical exponents of the heat capacity and the scalar for the saturated small and large black holes near the critical point.

Electronic band structure and charge density wave transition in quasi-2D KMo6O17 purple bronze

NASA Astrophysics Data System (ADS)

Valbuena, M. A.; Avila, J.; Vyalikh, D. V.; Guyot, H.; Laubschat, C.; Molodtsov, S. L.; Asensio, M. C.

2008-03-01

High resolution angle-resolved photoemission of quasi-2D KMo6O17 purple bronze has been performed in the range from room temperature to 130 K, slightly above the charge density wave (CDW) transition (Tc = 110 K), and down to 35 K (well below Tc). In this paper we report a detailed study of how electronic band structure is affected by this transition driven by the hidden nesting scenario. The expected spectroscopic fingerprints of the CDW phase transition have been found and discussed according to the hidden one dimension and the development of a quasi-commensurate CDW. The excellent agreement between theory and our experimental results makes of potassium purple bronze a reference system for studying this type of instabilities.

Simulating Ru L3-edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

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

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-01

Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+,more » [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.« less

Analysis of spectra of 3s-3p and 3p-3d transitions of highly-charged copper ions

NASA Astrophysics Data System (ADS)

Su, M. G.; Min, Q.; He, S. Q.; Wu, L.; Sun, R.; Ding, X. B.; Sun, D. X.

2017-08-01

Beam-foil excited spectra in the range of 160-360 Å from highly charged copper ions were identified with the aid of the National Institute of Standards and Technology Atomic Spectra Database and theoretical calculations with Cowan and Flexible Atomic Code (FAC) calculations. Spectra arising from 3s-3p and 3p-3d transitions of Cu13+-Cu22+ ions were considered. The ion fraction at an ion beam energy of 110 MeV was estimated from the equilibrium charge distribution of the fast ion beams after passing through the solid. The corresponding simulated spectra were in good agreement with the experimental result. Our Cowan and FAC calculation results should be useful for further spectral identification and lifetime measurements of highly charged copper ions.

Stacked charge stripes in the quasi-2D trilayer nickelate La4Ni3O8

NASA Astrophysics Data System (ADS)

Zhang, Junjie; Chen, Yu-Sheng; Phelan, D.; Zheng, Hong; Norman, M. R.; Mitchell, J. F.

2016-08-01

The quasi-2D nickelate La4Ni3O8 (La-438), consisting of trilayer networks of square planar Ni ions, is a member of the so-called T' family, which is derived from the Ruddlesden-Popper (R-P) parent compound La4Ni3O10-x by removing two oxygen atoms and rearranging the rock salt layers to fluorite-type layers. Although previous studies on polycrystalline samples have identified a 105-K phase transition with a pronounced electronic and magnetic response but weak lattice character, no consensus on the origin of this transition has been reached. Here, we show using synchrotron X-ray diffraction on high-pO2 floating zone-grown single crystals that this transition is associated with a real space ordering of charge into a quasi-2D charge stripe ground state. The charge stripe superlattice propagation vector, q = (2/3, 0, 1), corresponds with that found in the related 1/3-hole doped single-layer R-P nickelate, La5/3Sr1/3NiO4 (LSNO-1/3; Ni2.33+), with orientation at 45° to the Ni-O bonds. The charge stripes in La-438 are weakly correlated along c to form a staggered ABAB stacking that reduces the Coulomb repulsion among the stripes. Surprisingly, however, we find that the charge stripes within each trilayer of La-438 are stacked in phase from one layer to the next, at odds with any simple Coulomb repulsion argument.

Cob(I)alamin: insight into the nature of electronically excited states elucidated via quantum chemical computations and analysis of absorption, CD and MCD data.

PubMed

Kornobis, Karina; Ruud, Kenneth; Kozlowski, Pawel M

2013-02-07

The nature of electronically excited states of the super-reduced form of vitamin B(12) (i.e., cob(I)alamin or B(12s)), a ubiquitous B(12) intermediate, was investigated by performing quantum-chemical calculations within the time-dependent density functional theory (TD-DFT) framework and by establishing their correspondence to experimental data. Using response theory, the electronic absorption (Abs), circular dichroism (CD) and magnetic CD (MCD) spectra of cob(I)alamin were simulated and directly compared with experiment. Several issues have been taken into considerations while performing the TD-DFT calculations, such as strong dependence on the applied exchange-correlation (XC) functional or structural simplification imposed on the cob(I)alamin. In addition, the low-lying transitions were also validated by performing CASSCF/MC-XQDPT2 calculations. By comparing computational results with existing experimental data a new level of understanding of electronic excitations has been established at the molecular level. The present study extends and confirms conclusions reached for other cobalamins. In particular, the better performance of the BP86 functional, rather than hybrid-type, was observed in terms of the excitations associated with both Co d and corrin π localized transitions. In addition, the lowest energy band was associated with multiple metal-to-ligand charge transfer excitations as opposed to the commonly assumed view of a single π → π* transition followed by vibrational progression. Finally, the use of the full cob(I)alamin structure, instead of simplified molecular models, shed new light on the spectral analyses of cobalamin systems and revealed new challenges of this approach related to long-range charge transfer excitations involving side chains.

Equilibrium charge fluctuations of a charge detector and its effect on a nearby quantum dot

NASA Astrophysics Data System (ADS)

Ruiz-Tijerina, David; Vernek, Edson; Ulloa, Sergio

2014-03-01

We study the Kondo state of a spin-1/2 quantum dot (QD), in close proximity to a quantum point contact (QPC) charge detector near the conductance regime of the 0.7 anomaly. The electrostatic coupling between the QD and QPC introduces a remote gate on the QD level, which varies with the QPC gate voltage. Furthermore, models for the 0.7 anomaly [Y. Meir et al., PRL 89,196802(2002)] suggest that the QPC lodges a Kondo-screened level with charge-correlated hybridization, which may be also affected by capacitive coupling to the QD, giving rise to a competition between the two Kondo ground states. We model the QD-QPC system as two capacitively-coupled Kondo impurities, and explore the zero-bias transport of both the QD and the QPC for different local gate voltages and coupling strengths, using the numerical renormalization group and variational methods. We find that the capacitive coupling produces a remote gating effect, non-monotonic in the gate voltages, which reduces the gate voltage window for Kondo screening in either impurity, and which can also drive a quantum phase transition out of the Kondo regime. Our study is carried out for intermediate coupling strengths, and as such is highly relevant to experiments; particularly, to recent studies of decoherence effects on QDs. Supported by MWN/CIAM and NSF PIRE.

18 CFR 11.2 - Use of government lands.

Code of Federal Regulations, 2012 CFR

2012-04-01

... bill (not including the installments described in paragraph (c)(1) of this section), whichever is less... Register. (c)(1) The annual land use charge payable for the nine month transition year of the... the land use charges bills for 1988, 1989, and 1990. (2) The charge for one year will equal an amount...

Multi-Skyrmions on AdS2 × S2, rational maps and popcorn transitions

NASA Astrophysics Data System (ADS)

Canfora, Fabrizio; Tallarita, Gianni

2017-08-01

By combining two different techniques to construct multi-soliton solutions of the (3 + 1)-dimensional Skyrme model, the generalized hedgehog and the rational map ansatz, we find multi-Skyrmion configurations in AdS2 ×S2. We construct Skyrmionic multi-layered configurations such that the total Baryon charge is the product of the number of kinks along the radial AdS2 direction and the degree of the rational map. We show that, for fixed total Baryon charge, as one increases the charge density on ∂ (AdS2 ×S2) , it becomes increasingly convenient energetically to have configurations with more peaks in the radial AdS2 direction but a lower degree of the rational map. This has a direct relation with the so-called holographic popcorn transitions in which, when the charge density is high, multi-layered configurations with low charge on each layer are favored over configurations with few layers but with higher charge on each layer. The case in which the geometry is M2 ×S2 can also be analyzed.

Assembly of luminescent ordered multilayer thin-films based on oppositely-charged MMT and magnetic NiFe-LDHs nanosheets with ultra-long lifetimes

PubMed Central

Liu, Meitang; Wang, Tianlei; Ma, Hongwen; Fu, Yu; Hu, Kunran; Guan, Chao

2014-01-01

In this present report, luminescent ordered multilayer thin films (OMFs) based on oppositely-charged inorganic nanosheets and the different oppositely-charged chromophores were fabricated via layer-by-layer assembly method. Exfoliated layered double hydroxides (LDHs) and montmorillonite (MMT) nanosheets with opposite charges can be expected to provide a pseudo electronic microenvironment (PEM) which has not been declared in previous literatures, and transition metal-bearing LDHs nanosheets can offer an additional ferromagnetic effect (FME) for the chromophores at the same time. Surprisingly, the luminescent lifetimes of those OMFs with PEM and FME are significantly prolonged compared with that of the pristine chromophores, even much longer than those of OMFs without oppositely-charged and ferromagnetic architecture. Therefore, it is highly expected that the PEM and FME formed by oppositely-charged and transition metal-bearing inorganic nanosheets have remarkable influence on obtaining better optical property, which suggests a new potential way to manipulate, control and develop the novel light-emitting materials and optical devices. PMID:25413710

Work Function of Oxide Ultrathin Films on the Ag(100) Surface.

PubMed

Sementa, Luca; Barcaro, Giovanni; Negreiros, Fabio R; Thomas, Iorwerth O; Netzer, Falko P; Ferrari, Anna Maria; Fortunelli, Alessandro

2012-02-14

Theoretical calculations of the work function of monolayer (ML) and bilayer (BL) oxide films on the Ag(100) surface are reported and analyzed as a function of the nature of the oxide for first-row transition metals. The contributions due to charge compression, charge transfer and rumpling are singled out. It is found that the presence of empty d-orbitals in the oxide metal can entail a charge flow from the Ag(100) surface to the oxide film which counteracts the decrease in the work function due to charge compression. This flow can also depend on the thickness of the film and be reduced in passing from ML to BL systems. A regular trend is observed along first-row transition metals, exhibiting a maximum for CuO, in which the charge flow to the oxide is so strong as to reverse the direction of rumpling. A simple protocol to estimate separately the contribution due to charge compression is discussed, and the difference between the work function of the bare metal surface and a Pauling-like electronegativity of the free oxide slabs is used as a descriptor quantity to predict the direction of charge transfer.

Two-dimensional vibrational-electronic spectroscopy

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

Courtney, Trevor L.; Fox, Zachary W.; Slenkamp, Karla M.

2015-10-21

Two-dimensional vibrational-electronic (2D VE) spectroscopy is a femtosecond Fourier transform (FT) third-order nonlinear technique that creates a link between existing 2D FT spectroscopies in the vibrational and electronic regions of the spectrum. 2D VE spectroscopy enables a direct measurement of infrared (IR) and electronic dipole moment cross terms by utilizing mid-IR pump and optical probe fields that are resonant with vibrational and electronic transitions, respectively, in a sample of interest. We detail this newly developed 2D VE spectroscopy experiment and outline the information contained in a 2D VE spectrum. We then use this technique and its single-pump counterpart (1D VE)more » to probe the vibrational-electronic couplings between high frequency cyanide stretching vibrations (ν{sub CN}) and either a ligand-to-metal charge transfer transition ([Fe{sup III}(CN){sub 6}]{sup 3−} dissolved in formamide) or a metal-to-metal charge transfer (MMCT) transition ([(CN){sub 5}Fe{sup II}CNRu{sup III}(NH{sub 3}){sub 5}]{sup −} dissolved in formamide). The 2D VE spectra of both molecules reveal peaks resulting from coupled high- and low-frequency vibrational modes to the charge transfer transition. The time-evolving amplitudes and positions of the peaks in the 2D VE spectra report on coherent and incoherent vibrational energy transfer dynamics among the coupled vibrational modes and the charge transfer transition. The selectivity of 2D VE spectroscopy to vibronic processes is evidenced from the selective coupling of specific ν{sub CN} modes to the MMCT transition in the mixed valence complex. The lineshapes in 2D VE spectra report on the correlation of the frequency fluctuations between the coupled vibrational and electronic frequencies in the mixed valence complex which has a time scale of 1 ps. The details and results of this study confirm the versatility of 2D VE spectroscopy and its applicability to probe how vibrations modulate charge and energy transfer in a wide range of complex molecular, material, and biological systems.« less

New Measurement of the 1S-3S Transition Frequency of Hydrogen: Contribution to the Proton Charge Radius Puzzle.

PubMed

Fleurbaey, Hélène; Galtier, Sandrine; Thomas, Simon; Bonnaud, Marie; Julien, Lucile; Biraben, François; Nez, François; Abgrall, Michel; Guéna, Jocelyne

2018-05-04

We present a new measurement of the 1S-3S two-photon transition frequency of hydrogen, realized with a continuous-wave excitation laser at 205 nm on a room-temperature atomic beam, with a relative uncertainty of 9×10^{-13}. The proton charge radius deduced from this measurement, r_{p}=0.877(13)  fm, is in very good agreement with the current CODATA-recommended value. This result contributes to the ongoing search to solve the proton charge radius puzzle, which arose from a discrepancy between the CODATA value and a more precise determination of r_{p} from muonic hydrogen spectroscopy.

Ab Initio Study of Aluminium Impurity and Interstitial-Substitutional Complexes in Ge Using a Hybrid Functional (HSE)

NASA Astrophysics Data System (ADS)

Igumbor, E.; Mapasha, R. E.; Meyer, W. E.

2017-07-01

The results of an ab initio modelling of aluminium substitutional impurity ({\\hbox {Al}}_Ge), aluminium interstitial in Ge [{\\hbox {I}}_Al for the tetrahedral (T) and hexagonal (H) configurations] and aluminium interstitial-substitutional pairs in Ge ({\\hbox {I}}_Al{\\hbox {Al}}_Ge) are presented. For all calculations, the hybrid functional of Heyd, Scuseria, and Ernzerhof in the framework of density functional theory was used. Defects formation energies, charge state transition levels and minimum energy configurations of the {\\hbox {Al}}_Ge, {\\hbox {I}}_Al and {\\hbox {I}}_Al{\\hbox {Al}}_Ge were obtained for -2, -1, 0, +1 and +2 charge states. The calculated formation energy shows that for the neutral charge state, the {\\hbox {I}}_Al is energetically more favourable in the T than the H configuration. The {\\hbox {I}}_Al{\\hbox {Al}}_Ge forms with formation energies of -2.37 eV and -2.32 eV, when the interstitial atom is at the T and H sites, respectively. The {\\hbox {I}}_Al{\\hbox {Al}}_Ge is energetically more favourable when the interstitial atom is at the T site with a binding energy of 0.8 eV. The {\\hbox {I}}_Al in the T configuration, induced a deep donor (+2/+1) level at EV+0.23 eV and the {\\hbox {Al}}_Ge induced a single acceptor level (0/-1) at EV+0.14 eV in the band gap of Ge. The {\\hbox {I}}_Al{\\hbox {Al}}_Ge induced double-donor levels are at E_V+0.06 and E_V+0.12 eV, when the interstitial atom is at the T and H sites, respectively. The {\\hbox {I}}_Al and {\\hbox {I}}_Al{\\hbox {Al}}_Ge exhibit properties of charge state-controlled metastability.

Topological phase transition and the effect of Hubbard interactions on the one-dimensional topological Kondo insulator

NASA Astrophysics Data System (ADS)

Pillay, Jason C.; McCulloch, Ian P.

2018-05-01

The effect of a local Kondo coupling and Hubbard interaction on the topological phase of the one-dimensional topological Kondo insulator (TKI) is numerically investigated using the infinite matrix-product state density-matrix renormalization group algorithm. The ground state of the TKI is a symmetry-protected topological (SPT) phase protected by inversion symmetry. It is found that on its own, the Hubbard interaction that tends to force fermions into a one-charge per site order is insufficient to destroy the SPT phase. However, when the local Kondo Hamiltonian term that favors a topologically trivial ground state with a one-charge per site order is introduced, the Hubbard interaction assists in the destruction of the SPT phase. This topological phase transition occurs in the charge sector where the correlation length of the charge excitation diverges while the correlation length of the spin excitation remains finite. The critical exponents, central charge, and the phase diagram separating the SPT phase from the topologically trivial phase are presented.

Role of cooperative structural distortions in the metal--insulator transitions of perovskite ferrates

NASA Astrophysics Data System (ADS)

Cammarata, Antonio; Rondinelli, James

2012-02-01

Transition-metal oxides within the perovskite crystal family exhibit strong electron--electron correlation effects that coexist with complex structural distortions, leading to metal-insulator (MI) transitions. Using first-principles density functional calculations, we investigate the effects of cooperative octahedral rotations and dilations/contractions on the charge-ordering MI-transition in CaFeO3. By calculating the evolution in the lattice phonons, which describe the different octahedral distortions present in the low-symmetry monoclinic phase of CaFeO3 with increasing electron correlation, we show that the MI-transition results from a complex interplay between these modes and correlation effects. We combine this study with group theoretical tools to disentangle the electron--lattice interactions by computing the evolution in the low-energy electronic band structure with the lattice phonons, demonstrating the MI-transition in CaFeO3 proceeds through a symmetry-lowering transition driven by a cooperative three-dimensional octahedral dilation/contraction pattern. Finally, we suggest a possible route by which to control the charge ordering by fine-tuning the electron--lattice coupling.

Molecular Origins of Thermal Transitions in Polyelectrolyte Assemblies

NASA Astrophysics Data System (ADS)

Yildirim, Erol; Zhang, Yanpu; Antila, Hanne S.; Lutkenhaus, Jodie L.; Sammalkorpi, Maria; Aalto Team; Texas A&M Team

2015-03-01

Polyelectrolyte (PE) multilayers and complexes formed from oppositely charged polymers can exhibit extraordinary superhydrophobicity, mechanical strength and responsiveness resulting in applications ranging functional membranes, optics, sensors and drug delivery. Depending on the assembly conditions, PE assemblies may undergo a thermal transition from glassy to soft behavior under heating. Our earlier work using thermal analysis measurements shows a distinct thermal transition for PE layer-by-layer (LbL) systems assembled with added salt but no analogous transition in films assembled without added salt or dry systems. These findings raise interesting questions on the nature of the thermal transition; here, we explore its molecular origins through characterization of the PE aggregates by temperature-controlled all-atom molecular dynamics simulations. We show via molecular simulations the thermal transition results from the existence of an LCST (lower critical solution temperature) in the PE systems: the diffusion behavior, hydrogen bond formation, and bridging capacity of water molecules plasticizing the complex changes at the transition temperature. We quantify the behavior, map its chemistry specificity through comparison of strongly and weakly charged PE complexes, and connect the findings to our interrelated QCM-D experiments.

Scaling of terahertz conductivity at the metal-insulator transition in doped manganites

NASA Astrophysics Data System (ADS)

Pimenov, A.; Biberacher, M.; Ivannikov, D.; Loidl, A.; Mukhin, A. A.; Goncharov, Yu. G.; Balbashov, A. M.

2006-06-01

Magnetic field and temperature dependence of the terahertz conductivity and permittivity of the colossal magnetoresistance manganite Pr0.65Ca0.28Sr0.07MnO3 (PCSMO) is investigated approaching the metal-to-insulator transition (MIT) from the insulating side. In the charge-ordered state of PCSMO both conductivity and dielectric permittivity increase as a function of magnetic field and temperature. Universal scaling relationships Δɛ∝Δσ are observed in a broad range of temperatures and magnetic fields. Similar scaling is also seen in La1-xSrxMnO3 for different doping levels. The observed proportionality points towards the importance of pure ac-conductivity and phononic energy scale at MIT in manganites.

Nuclear magnetic resonance in high magnetic field: Application to condensed matter physics

NASA Astrophysics Data System (ADS)

Berthier, Claude; Horvatić, Mladen; Julien, Marc-Henri; Mayaffre, Hadrien; Krämer, Steffen

2017-05-01

In this review, we describe the potentialities offered by the nuclear magnetic resonance (NMR) technique to explore at a microscopic level new quantum states of condensed matter induced by high magnetic fields. We focus on experiments realised in resistive (up to 34 T) or hybrid (up to 45 T) magnets, which open a large access to these quantum phase transitions. After an introduction on NMR observables, we consider several topics: quantum spin systems (spin-Peierls transition, spin ladders, spin nematic phases, magnetisation plateaus, and Bose-Einstein condensation of triplet excitations), the field-induced charge density wave (CDW) in high-Tc superconductors, and exotic superconductivity including the Fulde-Ferrel-Larkin-Ovchinnikov superconducting state and the field-induced superconductivity due to the Jaccarino-Peter mechanism.

Two superconducting transitions in single-crystal La 2 - x Ba x CuO 4

DOE PAGES

Tee, X. Y.; Ito, T.; Ushiyama, T.; ...

2017-02-27

Here, we use spatially-resolved transport techniques to investigate the superconducting properties of single crystals La 2-xBa xCuO 4. We also found a superconducting transition temperature T cs associated with the ab-plane surface region which is considerably higher than the bulk T c. This effect is pronounced in the region of charge carrier doping x with strong spin-charge stripe correlations, reaching T cs = 36 K or 1.64T c.

Nanoscale measurement of Nernst effect in two-dimensional charge density wave material 1T-TaS 2

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

Wu, Stephen M.; Luican-Mayer, Adina; Bhattacharya, Anand

Advances in nanoscale material characterization on two-dimensional van der Waals layered materials primarily involve their optical and electronic properties. The thermal properties of these materials are harder to access due to the difficulty of thermal measurements at the nanoscale. In this work, we create a nanoscale magnetothermal device platform to access the basic out-of-plane magnetothermal transport properties of ultrathin van der Waals materials. Specifically, the Nernst effect in the charge density wave transition metal dichalcogenide 1T-TaS 2 is examined on nano-thin flakes in a patterned device structure. It is revealed that near the commensurate charge density wave (CCDW) to nearlymore » commensurate charge density wave (NCCDW) phase transition, the polarity of the Nernst effect changes. Since the Nernst effect is especially sensitive to changes in the Fermi surface, this suggests that large changes are occurring in the out-of-plane electronic structure of 1T-TaS 2, which are otherwise unresolved in just in-plane electronic transport measurements. This may signal a coherent evolution of out-of-plane stacking in the CCDW! NCCDW transition.« less

Near ultraviolet spectroscopic studies of 2,4-diamino-6-piperidinopyrimidine-3-oxide (minoxidil) and 2,4-diamino-6-piperidinopyrimidine (desoxyminoxidil)

NASA Astrophysics Data System (ADS)

Thamann, Thomas J.

The near u.v. spectra of 2,4-diamino-6-piperidinopyrimidine (desoxyminoxidil) and 2,4-diamino-6-piperidinopyrimidine-3-oxide (minoxidil) can be viewed as perturbed pyrimidine spectra. The u.v. properties of pyrimidine and a series of aminopyrimidines, specifically 2,4,6-triaminopyrimidine, are examined to obtain u.v. spectral assignments for desoxyminoxidil and minoxidil. Minoxidil and its desoxy counterpart have C s symmetry, and all π → π* absorptions are allowed 1A' ← 1A' transitions. The two lowest energy π →- π* absorptions observed in minoxidil (262 nm, 292 nm) are tentatively assigned as very mild oxygen → pyrimidine ring charge-transfer transitions. Intensity decreases in protic solvents, and the results of simple Hückel molecular orbital calculations indicate that the 292 nm transition has more charge-transfer character than the 262 nm absorption. The protonated species of desoxyminoxidil and minoxidil have very similar u.v. spectra. This is due to the lack of oxygen-related charge transfer in protonated minoxidil, and the high probability that the positive charge resides in similar environments in the minoxidil and desoxyminoxidil molecular frameworks.

Mass and charge transport relevant to the formation of toroidal lithium peroxide nanoparticles in an aprotic lithium-oxygen battery: An experimental and theoretical modeling study

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

Luo, Xiangyi; Amine, Rachid; Lau, Kah Chun

2017-05-26

The discharge and charge mechanisms of rechargeable Li-O-2 batteries have been the subject of extensive investigation recently. However, they are not fully understood yet. Here we report a systematic study of the morphological transition of Li2O2 from a single crystalline structure to a toroid like particle during the discharge-charge cycle, with the help of a theoretical model to explain the evolution of the Li2O2 at different stages of this process. The model suggests that the transition starts in the first monolayer of Li2O2, and is subsequently followed by a transition from particle growth to film growth if the applied currentmore » exceeds the exchange current for the oxygen reduction reaction in a Li-O-2 cell. Furthermore, a sustainable mass transport of the diffusive active species (e.g., O-2 and Li+) and evolution of the underlying interfaces are critical to dictate desirable oxygen reduction (discharge) and evolution (charge) reactions in the porous carbon electrode of a Li-O-2 cell.« less

Giant Gating Tunability of Optical Refractive Index in Transition Metal Dichalcogenide Monolayers.

PubMed

Yu, Yiling; Yu, Yifei; Huang, Lujun; Peng, Haowei; Xiong, Liwei; Cao, Linyou

2017-06-14

We report that the refractive index of transition metal dichacolgenide (TMDC) monolayers, such as MoS 2 , WS 2 , and WSe 2 , can be substantially tuned by >60% in the imaginary part and >20% in the real part around exciton resonances using complementary metal-oxide-semiconductor (CMOS) compatible electrical gating. This giant tunablility is rooted in the dominance of excitonic effects in the refractive index of the monolayers and the strong susceptibility of the excitons to the influence of injected charge carriers. The tunability mainly results from the effects of injected charge carriers to broaden the spectral width of excitonic interband transitions and to facilitate the interconversion of neutral and charged excitons. The other effects of the injected charge carriers, such as renormalizing bandgap and changing exciton binding energy, only play negligible roles. We also demonstrate that the atomically thin monolayers, when combined with photonic structures, can enable the efficiencies of optical absorption (reflection) tuned from 40% (60%) to 80% (20%) due to the giant tunability of the refractive index. This work may pave the way toward the development of field-effect photonics in which the optical functionality can be controlled with CMOS circuits.

X-ray photoemission spectroscopy investigation of CaTiO{sub 3}:Eu for luminescence property: effect of Eu{sup 3+} ion

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

Wang, Kaichen; Zhao, Baijun; Gao, Lu, E-mail: gaolu@jlu.edu.cn

2016-06-15

Graphical abstract: The influence on the photoluminescent performance due to the electronic structure change in Eu-doped CaTiO{sub 3} of the specific core-level and valence band spectrum via X-ray photoemission spectroscopy were characterized. - Highlights: • Single phase CaTiO{sub 3} and CaTiO{sub 3}: Eu crystals were prepared under mild hydrothermal method. • Crystal structure, doping level and the relations to their luminescent property were discussed. • Charge compensation mechanism was discussed via valance band spectrum by XPS. - Abstract: Charge compensation of on-site Eu 4f–5d transition that determines the luminescent performance was confirmed with valance band spectrum. Influence of photoelectrons frommore » CaTiO{sub 3}: Eu to the corresponding luminescent performance was discussed based on the crystal structure, doping level and the relations to their luminescent property. This paper is important to further optimize the luminescent performance for improving the efficiency and reducing the cost in light emitting diode industry.« less

Charge transfer photodissociation of phenol on Ag(111)

NASA Astrophysics Data System (ADS)

Lee, Junseok; Ryu, Sunmin; Ku, Jong Seok; Kim, Seong Keun

2001-12-01

The photochemistry of phenol on Ag(111) has been investigated by post-irradiation temperature programmed desorption (TPD). Ultraviolet (UV) irradiation at 355 and 266 nm was found to affect only the chemisorption layer in direct contact with the metal surface, while leaving the multilayer virtually intact. The main photoinduced reaction was found to be photodissociation of the O-H bond of phenol. Two new peaks were observed at the mass of phenol in the post-irradiation TPD spectrum at 335 K and 455 K. These peaks were assigned to the recombinative desorption of phenoxy with the hydrogen from O-H bond photodissociation and from thermal C-H bond fission, respectively. The photodissociation cross section was measured at different wavelengths and coverages. A charge transfer type photodissociation mechanism was proposed, where hot electrons generated in the substrate by UV photons attach to the affinity level of the adsorbed phenol. The transition to the transient anionic potential then leads to facile dissociation of O-H bond. The affinity level of phenol has been estimated to lie at 3.2-3.5 eV above the Fermi level for the 1 ML case.

FT-Raman, FT-IR spectra and total energy distribution of 3-pentyl-2,6-diphenylpiperidin-4-one: DFT method.

PubMed

Subashchandrabose, S; Saleem, H; Erdogdu, Y; Rajarajan, G; Thanikachalam, V

2011-11-01

FT-Raman and FT-IR spectra were recorded for 3-pentyl-2,6-diphenylpiperidin-4-one (PDPO) sample in solid state. The equilibrium geometries, harmonic vibrational frequencies, infrared and the Raman scattering intensities were computed using DFT/6-31G(d,p) level. Results obtained at this level of theory were used for a detailed interpretation of the infrared and Raman spectra, based on the total energy distribution (TED) of the normal modes. Molecular parameters such as bond lengths, bond angles and dihedral angles were calculated and compared with X-ray diffraction data. This comparison was good agreement. The intra-molecular charge transfer was calculated by means of natural bond orbital analysis (NBO). Hyperconjugative interaction energy was more during the π-π* transition. Energy gap of the molecule was found using HOMO and LUMO calculation, hence the less band gap, which seems to be more stable. Atomic charges of the carbon, nitrogen and oxygen were calculated using same level of calculation. Copyright © 2011 Elsevier B.V. All rights reserved.

Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers.

PubMed

Heera, Thekinneydath Rajan; Cindrella, Louis

2010-03-01

The relationship between structure and photo electrochemical property of ten natural pigments from plants, insects and microbes has been analyzed using density functional theory (DFT) at the B3LYP/6-31G(d) level. The essential parameters for their photoelectrochemical behaviour such as ground state geometries, electronic transition energies and oxidation potentials are computed. The attachment tendency of the anchoring groups, expressed as the deprotonation order, is determined by calculating the proton affinities at different sites of the molecules. A thorough analysis of the charge flow dynamics in the molecular orbitals (HOMO and LUMO) of these molecules has been carried out and presented to emphasize the role of these orbitals in effective charge separation, the important feature of photosensitizers for DSSC. This study highlights that the flexible spatial orientation provided by the bridging aliphatic unsaturation favours the oscillator strength and the hydroxyl anchor group attached to the ring of delocalized pi electron cloud acts as the effective anchor.

Radiative loss and charge exchange in low energy Na - Ca+ collisions

NASA Astrophysics Data System (ADS)

McLaughlin, B. M.; McAlpine, K.; McCann, J. F.; Pattillo, R.; Stancil, P. C.; Forrey, R. C.; Babb, J. F.

2016-05-01

Experiments on radiative loss and capture are currently being performed at the University of Connecticut. In response to this experimental effort we have performed detailed calculations for a variety of loss and capture processes. Several low lying states of the NaCa+ cation are used with the accurate potentials energy curves, transition dipole moments and non-adiabatic coupling matrix elements between the states, obtained at the MRCI+Q level of approximation with the MOLPRO suite of quantum chemistry codes. Cross sections and rate coefficients are calculated for radiative charge transfer (RCX), radiative association (RA) and charge exchange in a fully quantum molecular close-coupling (MOCC) approximation at the higher energies. We use a variety of approaches, the optical potential method, semi-classical and MOCC methods to compare and contrast approximations. In addition a kinetic theory recently applied to SiO is utilized which illustrates the dramatic impact resonances have on the radiative association rates. Supported by NASA and HLRS at Stuttgart University.

Interfacial charge-transfer transitions in a TiO2-benzenedithiol complex with Ti-S-C linkages.

PubMed

Fujisawa, Jun-ichi; Muroga, Ryuki; Hanaya, Minoru

2015-11-28

Interfacial charge-transfer (ICT) transitions between organic materials and inorganic semiconductors are a new mechanism for light absorption at organic-semiconductor interfaces. ICT transitions cause one-step interfacial charge separation without loss of energy. This feature is potentially useful to realize efficient organic-inorganic hybrid solar cells. ICT transitions have been examined by employing titanium dioxide (TiO2) nanoparticles chemisorbed with π-conjugated molecules via Ti-O-C linkages. Here, we report ICT transitions in a TiO2 and 1,2-benzenedithiol (BDT) complex with Ti-S-C linkages. BDT adsorbs on TiO2 by the bridging bidentate coordination of the sulfur atoms to surface titanium atoms. The TiO2-BDT complex shows ICT transitions from the BDT moiety to the conduction band of TiO2 in the visible region. The ICT transitions occur by orbital overlaps between the d orbitals of the surface titanium atoms and the π orbitals of the benzene ring. Our density-functional-theory (DFT) analysis reveals that the 3p valence orbitals of the sulfur bridging atoms contribute to more than 50% of the highest occupied molecular orbital (HOMO) and the 3d-3p(sulfur)-π interaction via the Ti-S-C linkage enhances the electronic mixing between the titanium atoms and the benzene moiety as compared to the 3d-2p(oxygen)-πvia the Ti-O-C linkage. This result indicates the important role of the heavier-atom linkers for strong organic-inorganic electronic couplings.

Structural Variations in β-(BDA-TTP)2FeCl4 at Low Temperature and under Pressure: Charge-Ordered State with a Two-Fold Crystal Structure

NASA Astrophysics Data System (ADS)

Sasamori, Kota; Takahashi, Kazuyuki; Kodama, Takeshi; Fujita, Wataru; Kikuchi, Koichi; Yamada, Jun-ichi

2013-05-01

The pressure-induced organic superconductor β-(BDA-TTP)2FeCl4 [BDA-TTP = 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene], which shows a metal--insulator (MI) transition at TMI = 113 K under ambient pressure, has been found by X-ray study to have a two-fold crystal structure along the c-axis in the insulating state at 10 K. In the donor layer, there are four independent BDA-TTP molecules, which are divided into two charge-poor ones and two charge-rich ones on the basis of the folding dihedral angles around the intramolecular sulfur-to-sulfur axes of two outer dithiane rings in BDA-TTP. The charge separation leads to the formation of two types of dimers: a dimer consisting of two charge-poor donors and a dimer consisting of two charge-rich ones. The tight-binding band calculation revealed a band gap of 5.3 meV in the energy dispersion. The MI transition can be therefore accounted for by the charge separation. In addition, we investigated the crystal and electronic structures of β-(BDA-TTP)2FeCl4 at different pressures up to 21 kbar, and found that the application of pressures causes variations in both the conformation of donor molecule and the donor arrangement, which are responsible for almost uniform interaction in the donor stacking and for an increase in bandwidth (W). As a result, the suppression of MI transition and subsequent occurrence of superconductivity in β-(BDA-TTP)2FeCl4 would be observed with increasing pressure.

Enhancement of IR and VCD intensities due to charge transfer.

PubMed

Nicu, Valentin Paul; Autschbach, Jochen; Baerends, Evert Jan

2009-03-14

Donor-acceptor interactions such as the one between the Cl(-) base and the N-H sigma* acceptor orbitals encountered in the complexation of Cl(-) counterions to the [Co(en)(3)](3+) transition metal complex, have been shown to cause huge enhancement (between 1 and 2 orders of magnitude) of the VCD intensities of N-H stretching modes. This effect has been fully analyzed, and could be attributed to increased charge flow from the Cl(-) donors when the N-H bonds become stretched. The transfer of charge counteracts the movement of negative electronic charge that happens along with the motion of the H nuclei, effectively reversing the electronic part of the electric dipole transition moment (EDTM) in the direction of the charge flow (z, say), and of the magnetic transition dipole moment (MDTM) in the perpendicular direction. The consequences for the IR and VCD intensity follow: IR intensity is strongly increased if the EDTM is polarized in the z direction, e.g. in A(2) modes, but not so much if it is polarized in the xy plane (E modes), the VCD is strongly enhanced if the EDTM and MTDM are polarized in the xy plane (in E modes), but less so when they are polarized in the z direction (in A(2) modes). The explanation holds generally for complexation phenomena of this sort, including the donor-acceptor part of hydrogen bonding interactions, e.g. with solvent molecules.

Effect of Low Temperature on Charge Transport in Operational Planar and Mesoporous Perovskite Solar Cells.

PubMed

Petrović, Miloš; Ye, Tao; Chellappan, Vijila; Ramakrishna, Seeram

2017-12-13

Low-temperature optoelectrical studies of perovskite solar cells using MAPbI 3 and mixed-perovskite absorbers implemented into planar and mesoporous architectures reveal fundamental charge transporting properties in fully assembled devices operating under light bias. Both types of devices exhibit inverse correlation of charge carrier lifetime as a function of temperature, extending carrier lifetimes upon temperature reduction, especially after exposure to high optical biases. Contribution of bimolecular channels to the overall recombination process should not be overlooked because the density of generated charge surpasses trap-filling concentration requirements. Bimolecular charge recombination coefficient in both device types is smaller than Langevin theory prediction, and its mean value is independent of the applied illumination intensity. In planar devices, charge extraction declines upon MAPbI 3 transition from a tetragonal to an orthorhombic phase, indicating a connection between the trapping/detrapping mechanism and temperature. Studies on charge extraction by linearly increasing voltage further support this assertion, as charge carrier mobility dependence on temperature follows multiple-trapping predictions for both device structures. The monotonously increasing trend following the rise in temperature opposes the behavior observed in neat perovskite films and indicates the importance of transporting layers and the effect they have on charge transport in fully assembled solar cells. Low-temperature phase transition shows no pattern of influence on thermally activated electron/hole transport.

76 FR 57044 - Announcement of Requirements and Registration for “Ensuring Safe Transitions From Hospital to Home”

Federal Register 2010, 2011, 2012, 2013, 2014

2011-09-15

... DEPARTMENT OF HEALTH AND HUMAN SERVICES Announcement of Requirements and Registration for... Coordinator for Health Information Technology, HHS. ACTION: Notice. SUMMARY: The ``Ensuring Safe Transitions... discharged patients to take charge of their health care during transitions of places of care. Innovative...

47 CFR 51.907 - Transition of price cap carrier access charges.

Code of Federal Regulations, 2013 CFR

2013-10-01

... carrier shall, in accordance with bill-and-keep, as defined in § 51.713, revise and refile its interstate.... 51.907 Section 51.907 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.907 Transition of price cap...

47 CFR 51.907 - Transition of price cap carrier access charges.

Code of Federal Regulations, 2014 CFR

2014-10-01

..., each Price Cap carrier shall, in accordance with bill-and-keep, as defined in § 51.713, revise and.... 51.907 Section 51.907 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.907 Transition of price cap...

47 CFR 51.907 - Transition of price cap carrier access charges.

Code of Federal Regulations, 2012 CFR

2012-10-01

... carrier shall, in accordance with bill-and-keep, as defined in § 51.713, revise and refile its interstate.... 51.907 Section 51.907 Telecommunication FEDERAL COMMUNICATIONS COMMISSION (CONTINUED) COMMON CARRIER SERVICES (CONTINUED) INTERCONNECTION Transitional Access Service Pricing § 51.907 Transition of price cap...

Closed-form expressions for state-to-state charge-transfer differential cross sections in a modified Faddeev three-body approach

NASA Astrophysics Data System (ADS)

Adivi, E. Ghanbari; Brunger, M. J.; Bolorizadeh, M. A.; Campbell, L.

2007-02-01

The second-order Faddeev-Watson-Lovelace approximation in a modified form is applied to charge transfer from hydrogenlike target atoms by a fully stripped energetic projectile ion. The state-to-state, nlm→n'l'm' , partial transition amplitudes are calculated analytically. The method is specifically applied to the collision of protons with hydrogen atoms, where differential cross sections of different transitions are calculated for incident energies of 2.8 and 5.0MeV . It is shown that the Thomas peak is present in all transition cross sections. The partial cross sections are then summed and compared with the available forward-angle experimental data, showing good agreement.

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

NASA Astrophysics Data System (ADS)

Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth

2017-03-01

Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

Pattern formation in triboelectrically charged binary packings

NASA Astrophysics Data System (ADS)

Schella, Andre; Vincent, Thomas; Herminghaus, Stephan; Schröter, Matthias

2015-11-01

Electrostatic self-assembly is an interesting route to aim at creating well-defined microstructures. In this spirit, we study the process of self-assembling for vertically shaken granular materials. Our system consists from 1 to 400 plastic beads of 3mm size made from Teflon and Nylon in 2D and 3D geometries. We find self-organization in four, five and sixfold order which is due to charging of the system via triboelectric effects between the grains. We observe that the binary system solidifies on a time scale of a few minutes. Image processing is used to extract the structural and dynamical properties of the assemblies. The mixture ratio is tuned from 1:5 to 5:1 and the humidity level is varied between 10% and 90% leading to various transitions between the morphologies.

Li-Like CX

NASA Astrophysics Data System (ADS)

Dorsey, Zachary

2018-06-01

A fantastic discovery in 1996 caused an epiphany when it was realized that the charge exchange (CX) process was an important source of X-ray emission from comets. Over the last two decades, CX induced X-ray emission has been detected in a wide variety of solar and extra-solar sources. Recently, our group developed the Kronos database which contains CX cross sections and emission spectra for all H-like and most He-Like ions up to iron, based primarily on multichannel Landau-Zener calculations. Here we present preliminary results for extending Kronos to Li-like ions. Due to the incompleteness of highly-charged Li-like atomic structure data, we estimate missing energy levels and transition probabilities with a quantum defect approach and the package Autostructure.This work was support by NASA grants NNX13AF31G.

Features of Stationary Photoconductivity of High-Ohmic Semiconductors Under Local Illumination

NASA Astrophysics Data System (ADS)

Lysenko, A. P.; Belov, A. G.; Kanevskii, V. E.; Odintsova, E. A.

2018-04-01

Photoconductivity has been thoroughly studied for a long time. However, most researchers have examined photoconductivity of semiconductors while illuminating the entire surface of samples. The present paper examines the effect of local exposure that ensures a high level of injection of free charge carriers upon the conductivity of high-ohmic cadmium telluride and semi-insulating gallium arsenide samples and upon the properties of ohmic contacts to samples. The authors found that regardless of the exposure area the value of transition resistance of ohmic contacts decreases and the concentration of the main charge carriers increases in the sample in proportion to radiation intensity. This research uncovered a number of previously unknown effects that are interesting from the physical point of view. This paper focuses on discussing these effects.

Microscopic interpretation of inelastic electron scattering from even Ni isotopes

NASA Astrophysics Data System (ADS)

Yokoyama, Atsushi; Ogawa, Kengo

1990-10-01

Transition charge densities of inelastic electron scattering for the excitation of 2+ and 4+ states in even-mass Ni isotopes are investigated in terms of the standard shell model of the (p3/2,p1/2,f5/2)n configurations. Effective transition operators pertinent to the model space are derived by considering particle-hole excitations up to 12ħω for C2 and 14ħω for C4 transitions within the framework of a first-order perturbation theory. It is shown that surface-peaked transition charge densities can be obtained for the first excited 2+ and 4+ states, being in agreement with experiment. Particle-hole excitations up to λħω, e.g., λ=2 for C2 transition, are most responsible for that feature. Higher ħω excitations appear relatively significant in the interior region of the nucleus: They enhance the peak around the surface, improving further agreement with experiment, but for C2 transition they tend to generate another peak inside the nucleus and thus seem to deteriorate agreement with experiment. Transition densities for the 0+g.s.-->2+2,3 and 0+g.s.-->4+2 transitions are also discussed.

On the nature of the Mott transition in multiorbital systems

NASA Astrophysics Data System (ADS)

Facio, Jorge I.; Vildosola, V.; García, D. J.; Cornaglia, Pablo S.

2017-02-01

We analyze the nature of a Mott metal-insulator transition in multiorbital systems using dynamical mean-field theory. The auxiliary multiorbital quantum impurity problem is solved using continuous-time quantum Monte Carlo and the rotationally invariant slave-boson (RISB) mean-field approximation. We focus our analysis on the Kanamori Hamiltonian and find that there are two markedly different regimes determined by the nature of the lowest-energy excitations of the atomic Hamiltonian. The RISB results at T →0 suggest the following rule of thumb for the order of the transition at zero temperature: a second-order transition is to be expected if the lowest-lying excitations of the atomic Hamiltonian are charge excitations, while the transition tends to be first order if the lowest-lying excitations are in the same charge sector as the atomic ground state. At finite temperatures, the transition is first order and its strength, as measured, e.g., by the jump in the quasiparticle weight at the transition, is stronger in the parameter regime where the RISB method predicts a first-order transition at zero temperature. Interestingly, these results seem to apply to a wide variety of models and parameter regimes.

Relativistic DFT investigation of electronic structure effects arising from doping the Au25 nanocluster with transition metals.

PubMed

Alkan, Fahri; Muñoz-Castro, Alvaro; Aikens, Christine M

2017-10-26

We perform a theoretical investigation using density functional theory (DFT) and time-dependent DFT (TDDFT) on the doping of the Au 25 (SR) 18 -1 nanocluster with group IX transition metals (M = cobalt, rhodium and iridium). Different doping motifs, charge states and spin multiplicities were considered for the single-atom doped nanoclusters. Our results show that the interaction (or the lack of interaction) between the d-type energy levels that mainly originate from the dopant atom and the super-atomic levels plays an important role in the energetics, the electronic structure and the optical properties of the doped systems. The evaluated MAu 24 (SR) 18 q (q = -1, -3) systems favor an endohedral disposition of the doping atom typically in a singlet ground state, with either a 6- or 8-valence electron icosahedral core. For the sake of comparison, the role of the d energy levels in the electronic structure of a variety of doped Au 25 (SR) 18 -1 nanoclusters was investigated for dopant atoms from other families such as Cd, Ag and Pd. Finally, the effect of spin-orbit coupling (SOC) on the electronic structure and absorption spectra was determined. The information in this study regarding the relative energetics of the d-based and super-atom energy levels can be useful to extend our understanding of the preferred doping modes of different transition metals in protected gold nanoclusters.

Symmetry-Breaking Phase Transition without a Peierls Instability in Conducting Monoatomic Chains

NASA Astrophysics Data System (ADS)

Blumenstein, C.; Schäfer, J.; Morresi, M.; Mietke, S.; Matzdorf, R.; Claessen, R.

2011-10-01

The one-dimensional (1D) model system Au/Ge(001), consisting of linear chains of single atoms on a surface, is scrutinized for lattice instabilities predicted in the Peierls paradigm. By scanning tunneling microscopy and electron diffraction we reveal a second-order phase transition at 585 K. It leads to charge ordering with transversal and vertical displacements and complex interchain correlations. However, the structural phase transition is not accompanied by the electronic signatures of a charge density wave, thus precluding a Peierls instability as origin. Instead, this symmetry-breaking transition exhibits three-dimensional critical behavior. This reflects a dichotomy between the decoupled 1D electron system and the structural elements that interact via the substrate. Such substrate-mediated coupling between the wires thus appears to have been underestimated also in related chain systems.

A charge-density-wave oscillator based on an integrated tantalum disulfide-boron nitride-graphene device operating at room temperature.

PubMed

Liu, Guanxiong; Debnath, Bishwajit; Pope, Timothy R; Salguero, Tina T; Lake, Roger K; Balandin, Alexander A

2016-10-01

The charge-density-wave (CDW) phase is a macroscopic quantum state consisting of a periodic modulation of the electronic charge density accompanied by a periodic distortion of the atomic lattice in quasi-1D or layered 2D metallic crystals. Several layered transition metal dichalcogenides, including 1T-TaSe 2 , 1T-TaS 2 and 1T-TiSe 2 exhibit unusually high transition temperatures to different CDW symmetry-reducing phases. These transitions can be affected by the environmental conditions, film thickness and applied electric bias. However, device applications of these intriguing systems at room temperature or their integration with other 2D materials have not been explored. Here, we demonstrate room-temperature current switching driven by a voltage-controlled phase transition between CDW states in films of 1T-TaS 2 less than 10 nm thick. We exploit the transition between the nearly commensurate and the incommensurate CDW phases, which has a transition temperature of 350 K and gives an abrupt change in current accompanied by hysteresis. An integrated graphene transistor provides a voltage-tunable, matched, low-resistance load enabling precise voltage control of the circuit. The 1T-TaS 2 film is capped with hexagonal boron nitride to provide protection from oxidation. The integration of these three disparate 2D materials in a way that exploits the unique properties of each yields a simple, miniaturized, voltage-controlled oscillator suitable for a variety of practical applications.

Apparatus and method of determining molecular weight of large molecules

DOEpatents

Fuerstenau, S.; Benner, W.H.; Madden, N.M.; Searles, W.

1998-06-23

A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e{sup {minus}} are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation. 14 figs.

Apparatus and method of determining molecular weight of large molecules

DOEpatents

Fuerstenau, Stephen; Benner, W. Henry; Madden, Norman; Searles, William

1998-01-01

A mass spectrometer determines the mass of multiply charged high molecular weight molecules. This spectrometer utilizes an ion detector which is capable of simultaneously measuring the charge z and transit time of a single ion as it passes through the detector. From this transit time, the velocity of the single ion may then be derived, thus providing the mass-to-charge ratio m/z for a single ion which has been accelerated through a known potential. Given z and m/z, the mass m of the single ion can then be calculated. Electrospray ions with masses in excess of 1 MDa and charge numbers greater than 425 e.sup.- are readily detected. The on-axis single ion detection configuration enables a duty cycle of nearly 100% and extends the practical application of electrospray mass spectrometry to the analysis of very large molecules with relatively inexpensive instrumentation.

Transition from direct to inverted charge transport Marcus regions in molecular junctions via molecular orbital gating

NASA Astrophysics Data System (ADS)

Yuan, Li; Wang, Lejia; Garrigues, Alvar R.; Jiang, Li; Annadata, Harshini Venkata; Anguera Antonana, Marta; Barco, Enrique; Nijhuis, Christian A.

2018-04-01

Solid-state molecular tunnel junctions are often assumed to operate in the Landauer regime, which describes essentially activationless coherent tunnelling processes. In solution, on the other hand, charge transfer is described by Marcus theory, which accounts for thermally activated processes. In practice, however, thermally activated transport phenomena are frequently observed also in solid-state molecular junctions but remain poorly understood. Here, we show experimentally the transition from the Marcus to the inverted Marcus region in a solid-state molecular tunnel junction by means of intra-molecular orbital gating that can be tuned via the chemical structure of the molecule and applied bias. In the inverted Marcus region, charge transport is incoherent, yet virtually independent of temperature. Our experimental results fit well to a theoretical model that combines Landauer and Marcus theories and may have implications for the interpretation of temperature-dependent charge transport measurements in molecular junctions.

Ising tricriticality in the extended Hubbard model with bond dimerization

NASA Astrophysics Data System (ADS)

Fehske, Holger; Ejima, Satoshi; Lange, Florian; Essler, Fabian H. L.

We explore the quantum phase transition between Peierls and charge-density-wave insulating states in the one-dimensional, half-filled, extended Hubbard model with explicit bond dimerization. We show that the critical line of the continuous Ising transition terminates at a tricritical point, belonging to the universality class of the tricritical Ising model with central charge c=7/10. Above this point, the quantum phase transition becomes first order. Employing a numerical matrix-product-state based (infinite) density-matrix renormalization group method we determine the ground-state phase diagram, the spin and two-particle charge excitations gaps, and the entanglement properties of the model with high precision. Performing a bosonization analysis we can derive a field description of the transition region in terms of a triple sine-Gordon model. This allows us to derive field theory predictions for the power-law (exponential) decay of the density-density (spin-spin) and bond-order-wave correlation functions, which are found to be in excellent agreement with our numerical results. This work was supported by Deutsche Forschungsgemeinschaft (Germany), SFB 652, project B5, and by the EPSRC under Grant No. EP/N01930X/1 (FHLE).

X-ray and gamma-ray line production by nonthermal ions

NASA Technical Reports Server (NTRS)

Bussard, R. W.; Omidvar, K.; Ramaty, R.

1977-01-01

X-ray production was calculated at approximately 6.8 keV by the 2p to 1s transition in fast hydrogen- and helium-like iron ions, following both electron capture to excited levels and collisional excitation. A refinement of the OBK approximation was used to obtain an improved charge exchange cross section. This, and the corresponding ionization cross section were used to determine equilibrium charge fractions for iron ions as functions of their energy. The effective X-ray line production cross section was found to be sharply peaked in energy at about 8 to 12 MeV/amu. Because fast ions of similar energies can also excite nuclear levels, the ratio of selected strong gamma ray line emissivities to the X-ray line emissivity was also calculated. Limits set by this method on the intensity of gamma ray line emission from the galactic center and the radio galaxy Centaurus A are generally lower than those reported in the literature.

Plentiful magnetic moments in oxygen deficient SrTiO 3

DOE PAGES

Ganesh, Panchapakesan; Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

2015-10-06

In this research, correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO 3. Hole and electron doping of oxygen deficient SrTiO 3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO 3–δ is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments inmore » the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.« less

Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

PubMed Central

Bisogni, Valentina; Catalano, Sara; Green, Robert J.; Gibert, Marta; Scherwitzl, Raoul; Huang, Yaobo; Strocov, Vladimir N.; Zubko, Pavlo; Balandeh, Shadi; Triscone, Jean-Marc; Sawatzky, George; Schmitt, Thorsten

2016-01-01

The metal–insulator transition and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. Nonetheless, a complete understanding of these materials remains elusive. Here we combine X-ray absorption and resonant inelastic X-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of rare-earth nickelates, taking NdNiO3 thin film as representative example. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for abundant oxygen holes in the ground state of these materials. Using cluster calculations and Anderson impurity model interpretation, we show that distinct spectral signatures arise from a Ni 3d8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a conventional positive charge-transfer picture, but instead exhibit a negative charge-transfer energy in line with recent models interpreting the metal–insulator transition in terms of bond disproportionation. PMID:27725665

Structure and properties of composite films formed by cellulose nanocrystals and charged latex nanoparticles

NASA Astrophysics Data System (ADS)

Thérien-Aubin, Héloïse; Lukach, Ariella; Pitch, Natalie; Kumacheva, Eugenia

2015-04-01

We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase.We report the structural and optical properties of composite films formed from mixed suspensions of cellulose nanocrystals (CNCs) and fluorescent latex nanoparticles (NPs). We explored the effect of NP concentration, size, surface charge, glass transition temperature and film processing conditions on film structure and properties. The chiral nematic order, typical of CNC films, was preserved in films with up to 50 wt% of negatively-charged latex NPs. Composite films were characterized by macroscopically close-to-uniform fluorescence, birefringence, and circular dichroism properties. In contrast, addition of positively charged latex NPs led to gelation of CNC-latex suspensions and disruption of the chiral nematic order in the composite films. Large latex NPs disrupted the chiral nematic order to a larger extend than small NPs. Furthermore, the glass transition of latex NPs had a dramatic effect on the structure of CNC-latex films. Latex particles in the rubbery state were easily incorporated in the ordered CNC matrix and improved the structural integrity of its chiral nematic phase. Electronic supplementary information (ESI) available: Detailed latex synthesis. Additional characterization of the nanoparticles and films. See DOI: 10.1039/c5nr00660k

Detonation propagation in annular arcs of condensed phase explosives

NASA Astrophysics Data System (ADS)

Ioannou, Eleftherios; Schoch, Stefan; Nikiforakis, Nikolaos; Michael, Louisa

2017-11-01

We present a numerical study of detonation propagation in unconfined explosive charges shaped as an annular arc (rib). Steady detonation in a straight charge propagates at constant speed, but when it enters an annular section, it goes through a transition phase and eventually reaches a new steady state of constant angular velocity. This study examines the speed of the detonation wave along the annular charge during the transition phase and at steady state, as well as its dependence on the dimensions of the annulus. The system is modeled using a recently proposed diffuse-interface formulation which allows for the representation of a two-phase explosive and of an additional inert material. The explosive considered is the polymer-bonded TATB-based LX-17 and is modeled using two Jones-Wilkins-Lee (JWL) equations of state and the ignition and growth reaction rate law. Results show that steady state speeds are in good agreement with experiment. In the transition phase, the evolution of outer detonation speed deviates from the exponential bounded growth function suggested by previous studies. We propose a new description of the transition phase which consists of two regimes. The first regime is caused by local effects at the outer edge of the annulus and leads to a dependence of the outer detonation speed on the angular position along the arc. The second regime is induced by effects originating from the inner edge of the annular charge and leads to the deceleration of the outer detonation until steady state is reached. The study concludes with a parametric study where the dependence of the steady state and the transition phase on the dimensions of the annulus is investigated.

Charge-Transfer-Induced p-Type Channel in MoS2 Flake Field Effect Transistors.

PubMed

Min, Sung-Wook; Yoon, Minho; Yang, Sung Jin; Ko, Kyeong Rok; Im, Seongil

2018-01-31

The two-dimensional transition-metal dichalcogenide semiconductor MoS 2 has received extensive attention for decades because of its outstanding electrical and mechanical properties for next-generation devices. One weakness of MoS 2 , however, is that it shows only n-type conduction, revealing its limitations for homogeneous PN diodes and complementary inverters. Here, we introduce a charge-transfer method to modify the conduction property of MoS 2 from n- to p-type. We initially deposited an n-type InGaZnO (IGZO) film on top of the MoS 2 flake so that electron charges might be transferred from MoS 2 to IGZO during air ambient annealing. As a result, electron charges were depleted in MoS 2 . Such charge depletion lowered the MoS 2 Fermi level, which makes hole conduction favorable in MoS 2 when optimum source/drain electrodes with a high work function are selected. Our IGZO-supported MoS 2 flake field effect transistors (FETs) clearly display channel-type conversion from n- to p-channel in this way. Under short- and long-annealing conditions, n- and p-channel MoS 2 FETs are achieved, respectively, and a low-voltage complementary inverter is demonstrated using both channels in a single MoS 2 flake.

The Lamb shift in muonic hydrogen and the proton radius

NASA Astrophysics Data System (ADS)

Antognini, A.; Pohl, R.; Amaro, F. D.; Biraben, F.; Cardoso, J. M. R.; Covita, D. S.; Dax, A.; Dhawan, S.; Fernandes, L. M. P.; Giesen, A.; Gouvea, A. L.; Graf, T.; Ḧansch, T. W.; Hildebrandt, M.; Indelicato, P.; Julien, L.; Kao, C.-Y.; Kirch, K.; Knowles, P.; Le Bigot, E.-O.; Liu, Y.-W.; Lopes, J. A. M.; Ludhova, L.; Monteiro, C. M. B.; Mulhauser, F.; Nebel, T.; Nez, F.; Rabinowitz, P.; dos Santos, J. M. F.; Schaller, L. A.; Schuhmann, K.; Schwob, C.; Taqqu, D.; Veloso, J. F. C. A.; Voss, A.; Kottmann, F.

By means of pulsed laser spectroscopy applied to muonic hydrogen (μ- p) we have measured the 2S F = 1 1/2 - 2PF = 2 3/2 transition frequency to be 49881.88(76) GHz. By comparing this measurement with its theoretical prediction based on bound-state QED we have determined a proton radius value of rp = 0.84184 (67) fm. This new value is an order of magnitude preciser than previous results but disagrees by 5 standard deviations from the CODATA and the electronproton scattering values. An overview of the present effort attempting to solve the observed discrepancy is given. Using the measured isotope shift of the 1S-2S transition in regular hydrogen and deuterium also the rms charge radius of the deuteron rd = 2.12809 (31) fm has been determined. Moreover we present here the motivations for the measurements of the μ 4He + and μ 3He + 2S-2P splittings. The alpha and triton charge radii are extracted from these measurements with relative accuracies of few 10 - 4. Measurements could help to solve the observed discrepancy, lead to the best test of hydrogen-like energy levels and provide crucial tests for few-nucleon ab-initio theories and potentials.

Hydrogel, aerogel and film of cellulose nanofibrils functionalized with silver nanoparticles.

PubMed

Dong, Hong; Snyder, James F; Tran, Dat T; Leadore, Julia L

2013-06-20

In this work, we describe hydrogels, aerogels and films of nanofibrillated cellulose (NFC) functionalized with metal nanoparticles using silver as an example. The TEMPO process used to produce NFC generates negatively charged surface carboxylate groups that provide high binding capability to transition metal species such as Ag(+). The gelation of NFC triggered by transition monovalent metal ions was revealed for the first time. The interaction was utilized to bind Ag(+) on the NFC surface and simultaneously induce formation of NFC-Ag(+) hydrogels, where Ag(+) was slowly reduced to Ag nanoparticles by hydroxyl groups on NFC without additional reducing agent. The NFC-Ag(+) hydrogel was initiated by strong association of carboxylate groups on NFC with Ag(+) and sufficient NFC surface charge reduction. The stiff hydrogel has a storage modulus leveled off at a plateau value of ~6800Pa. Porous aerogels and flat thin films comprising a continuous matrix of NFC were decorated with Ag nanoparticles through freeze-drying or solution-casting of NFC-Ag(+) dispersions with low contents of Ag(+), respectively, followed by UV reduction. The presence of Ag species on NFC reduced coalescence of nanofibrils in the film formation as revealed from AFM phase images. Copyright © 2013 Elsevier Ltd. All rights reserved.

Oxidative stability of soybean oil in oleosomes as affected by pH and iron.

PubMed

Kapchie, Virginie N; Yao, Linxing; Hauck, Catherine C; Wang, Tong; Murphy, Patricia A

2013-12-01

The oxidative stability of oil in soybean oleosomes, isolated using the Enzyme-Assisted Aqueous Extraction Process (EAEP), was evaluated. The effects of ferric chloride, at two concentration levels (100 and 500 μM), on lipid oxidation, was examined under pH 2 and 7. The peroxide value (PV) and thiobarbituric acid-reactive substance (TBARS) value of oil, in oleosome suspensions stored at 60 °C, were measured over a 12 day period. The presence of ferric chloride significantly (P<0.05) affected the oxidative stability of oil in the isolated oleosome, as measured by the PV and TBARS. Greater lipid oxidation occurred under an acidic pH. In the pH 7 samples, the positively charged transition metals were strongly attracted to the negatively charged droplets. However, the low ζ-potential and the high creaming rate at this pH, may have limited the oxidation. Freezing, freeze-drying or heating of oleosomes have an insignificant impact on the oxidative stability of oil in isolated soybean oleosomes. Manufacturers should be cautious when adding oleosomes as ingredients in food systems containing transition metal ions. Published by Elsevier Ltd.

Stacked charge stripes in the quasi-2D trilayer nickelate La 4 Ni 3 O 8

DOE PAGES

Zhang, Junjie; Chen, Yu-Sheng; Phelan, D.; ...

2016-07-26

The quasi-2D nickelate La 4Ni 3O 8 (La-438), consisting of trilayer networks of square planar Ni ions, is a member of the so-called T' family, which is derived from the Ruddlesden-Popper (R-P) parent compound La 4Ni 3O 10-x by removing two oxygen atoms and rearranging the rock salt layers to fluorite-type layers. Although previous studies on polycrystalline samples have identified a 105-K phase transition with a pronounced electronic and magnetic response but weak lattice character, no consensus on the origin of this transition has been reached. We show using synchrotron X-ray diffraction on high-pO(2) floating zone-grown single crystals that thismore » transition is associated with a real space ordering of charge into a quasi-2D charge stripe ground state. We found that the charge stripe superlattice propagation vector, q = (2/3, 0, 1), corresponds with that those in the related 1/3-hole doped single- layer R-P nickelate, La 5/3Sr 1/3NiO 4 (LSNO-1/3; Ni 2.33+), with orientation at 45 degrees to the Ni-O bonds. Furthermore, the charge stripes in La-438 are weakly correlated along c to form a staggered ABAB stacking that reduces the Coulomb repulsion among the stripes. Surprisingly, however, we find that the charge stripes within each trilayer of La-438 are stacked in phase from one layer to the next, at odds with any simple Coulomb repulsion argument.« less

Stacked charge stripes in the quasi-2D trilayer nickelate La 4 Ni 3 O 8

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

Zhang, Junjie; Chen, Yu-Sheng; Phelan, D.

The quasi-2D nickelate La 4Ni 3O 8 (La-438), consisting of trilayer networks of square planar Ni ions, is a member of the so-called T' family, which is derived from the Ruddlesden-Popper (R-P) parent compound La 4Ni 3O 10-x by removing two oxygen atoms and rearranging the rock salt layers to fluorite-type layers. Although previous studies on polycrystalline samples have identified a 105-K phase transition with a pronounced electronic and magnetic response but weak lattice character, no consensus on the origin of this transition has been reached. We show using synchrotron X-ray diffraction on high-pO(2) floating zone-grown single crystals that thismore » transition is associated with a real space ordering of charge into a quasi-2D charge stripe ground state. We found that the charge stripe superlattice propagation vector, q = (2/3, 0, 1), corresponds with that those in the related 1/3-hole doped single- layer R-P nickelate, La 5/3Sr 1/3NiO 4 (LSNO-1/3; Ni 2.33+), with orientation at 45 degrees to the Ni-O bonds. Furthermore, the charge stripes in La-438 are weakly correlated along c to form a staggered ABAB stacking that reduces the Coulomb repulsion among the stripes. Surprisingly, however, we find that the charge stripes within each trilayer of La-438 are stacked in phase from one layer to the next, at odds with any simple Coulomb repulsion argument.« less

Low-frequency noise in charge ordered system Pr0.63Ca0.37MnO3 near the charge-ordering transition and in the current induced destabilized state

NASA Astrophysics Data System (ADS)

Bid, Aveek; Raychaudhuri, Arup K.

2003-05-01

We have investigated the dynamics of co-existing phases in the Charge Ordered (CO) manganite Pr0.63Ca0.37MnO3 using the technique of conductance noise spectroscopy. We note that close to the CO transition temperature Tco the spectral power of Sv(f)/V2 deviates significantly from the 1/f frequency dependence for f<=0.12Hz. Our analysis shows that this deviation can be described by a single frequency Lorentzian with corner frequency fc in addition to the usual broadband 1/f noise. Such a Lorentzian contribution to Sv(f)/V2 can come from a two level system (TLS). In the time serioues this shows up as RTN. For T<=Tco the system shows the onset of a non-linear conduction close to a threshold value Jdc = Jth the noise spectra is mainly 1/f in nature. For J > Jth a large low frequency component of noise (characterized again by a frequency fc) appears. We associate fc with the relaxation time tc of the TLS fluctuator so the tc = 1/fc. For thermal activation of the TLS the temperature dependence of fc will follow fc=foexp(-Ea/kBT) where Ea is an energy barrier. The value of fc shows an increase with Jdc showing that the value of the activation energy Ea is being lowered by the applied bias.

Enhancement of Catalytic Activity of Reduced Graphene Oxide Via Transition Metal Doping Strategy

NASA Astrophysics Data System (ADS)

Lee, Hangil; Hong, Jung A.

2017-06-01

To compare the catalytic oxidation activities of reduced graphene oxide (rGO) and rGO samples doped with five different transition metals (TM-rGO), we determine their effects on the oxidation of L-cysteine (Cys) in aqueous solution by performing electrochemistry (EC) measurements and on the photocatalytic oxidation of Cys by using high-resolution photoemission spectroscopy (HRPES) under UV illumination. Our results show that Cr-, Fe-, and Co-doped rGO with 3+ charge states (stable oxide forms: Cr3+, Fe3+, and Co3+) exhibit enhanced catalytic activities that are due to the charge states of the doped metal ions as we compare them with Cr-, Fe-, and Co-doped rGO with 2+ charge states.

AOARD Overview Power and Energy Emphasis

DTIC Science & Technology

2010-09-01

Evolutionary Research (Incremental Advances) P&E Materials Including Fluids: - Tunable thermal conductivity - Large CTE material matching - Nanofluids ...Charge Rate Objective: • Investigate 10-20x smaller nano-powder particle sizes to shorten charging rate • Study doping transition metals into the

47 CFR 61.48 - Transition rules for price cap formula calculations.

Code of Federal Regulations, 2011 CFR

2011-10-01

... charges due to GDP-PI—X targeting for $0.0095 filing entities. (ii) Reductions in Average Traffic Sensitive charges resulting from: (A) Targeting of the application of the (GDP-PI—X) portion of the formula...

Effects of non-Hermitian perturbations on Weyl Hamiltonians with arbitrary topological charges

NASA Astrophysics Data System (ADS)

Cerjan, Alexander; Xiao, Meng; Yuan, Luqi; Fan, Shanhui

2018-02-01

We provide a systematic study of non-Hermitian topologically charged systems. Starting from a Hermitian Hamiltonian supporting Weyl points with arbitrary topological charge, adding a non-Hermitian perturbation transforms the Weyl points to one-dimensional exceptional contours. We analytically prove that the topological charge is preserved on the exceptional contours. In contrast to Hermitian systems, the addition of gain and loss allows for a new class of topological phase transition: when two oppositely charged exceptional contours touch, the topological charge can dissipate without opening a gap. These effects can be demonstrated in realistic photonics and acoustics systems.

Redox levels in aqueous solution: Effect of van der Waals interactions and hybrid functionals

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

Ambrosio, Francesco, E-mail: Francesco.Ambrosio@epfl.ch; Miceli, Giacomo; Pasquarello, Alfredo

2015-12-28

We investigate redox levels in aqueous solution using a combination of ab initio molecular dynamics (MD) simulations and thermodynamic integration methods. The molecular dynamics are performed with both the semilocal Perdew-Burke-Ernzerhof functional and a nonlocal functional (rVV10) accounting for van der Waals (vdW) interactions. The band edges are determined through three different schemes, namely, from the energy of the highest occupied and of the lowest unoccupied Kohn-Sham states, from total-energy differences, and from a linear extrapolation of the density of states. It is shown that the latter does not depend on the system size while the former two are subjectmore » to significant finite-size effects. For the redox levels, we provide a formulation in analogy to the definition of charge transition levels for defects in crystalline materials. We consider the H{sup +}/H{sub 2} level defining the standard hydrogen electrode, the OH{sup −}/OH{sup ∗} level corresponding to the oxidation of the hydroxyl ion, and the H{sub 2}O/OH{sup ∗} level for the dehydrogenation of water. In spite of the large structural modifications induced in liquid water, vdW interactions do not lead to any significant structural effect on the calculated band gap and band edges. The effect on the redox levels is also small since the solvation properties of ionic species are little affected by vdW interactions. Since the electronic properties are not significantly affected by the underlying structural properties, it is justified to perform hybrid functional calculations on the configurations of our MD simulations. The redox levels calculated as a function of the fraction α of Fock exchange are found to remain constant, reproducing a general behavior previously observed for charge transition levels of defects. Comparison with experimental values shows very good agreement. At variance, the band edges and the band gap evolve linearly with α. For α ≃ 0.40, we achieve a band gap, band-edge positions, and redox levels in overall good agreement with experiment.« less

Effect of strain on structure and charge order transitions in epitaxial Bi0.4Ca0.6MnO3 films on perovskite (001) and (011) substrates

NASA Astrophysics Data System (ADS)

Kim, Dae Ho; Christen, Hans M.; Varela, Maria; Lee, Ho Nyung; Lowndes, Douglas H.

2006-05-01

The effect of epitaxial strain on the charge order (CO) transition in Bi0.4Ca0.6MnO3 films was studied by varying the strain's strength and symmetry via the use of SrTiO3 and LaAlO3 substrates having different crystallographic orientations. The film on pseudocubic (001) LaAlO3, under symmetric compressive strain, exhibits a clear CO transition. In the film on a (001) SrTiO3 substrate, under symmetric tensile strain, highly segregated line-shaped features in the Bi distribution are seen in Z-contrast scanning transmission microscopy, accompanied by a strongly broadened CO transition. The asymmetric tensile stress on (011) SrTiO3 results in an apparent compressive strain state with a deviation from tetragonality (i.e., γ ≠90°), accompanied by the sharpest CO transition. These comparisons illustrate the importance of considering both the strength and symmetry of epitaxial strain.

Photoabsorption of green and red fluorescent protein chromophore anions in vacuo.

PubMed

Wan, Songbo; Liu, Shasha; Zhao, Guangjiu; Chen, Maodu; Han, Keli; Sun, Mengtao

2007-09-01

Photoabsorption properties of green and red fluorescent protein chromophore anions in vacuo were investigated theoretically, based on the experimental results in gas phase [Phys. Rev. Lett. 2001, 87, 228102; Phys. Rev. Lett. 2003, 90, 118103]. Their calculated transition energies in absorption with TD-DFT and ZINDO methods are directly compared to the experimental reports in gas phase, and the calculations with ZINDO method can correctly reproduce the absorption spectra. The orientation and strength of their transition dipole moments were revealed with transition density. We also showed the orientation and result of their intramolecular charge transfer with transition difference density. The calculated results show that with the increase of the extended conjugated system, the orientation of transition dipole moments and the orientation of charge transfer can be reversed. They are the linear responds with the external electric fields. These theoretical results reveal the insight understanding of the photoinduced dynamics of green and red fluorescent protein chromophore anions and cations in vacuo.

Measurements of Metastable Lifetimes of Highly-Charged Ions

NASA Astrophysics Data System (ADS)

Smith, Steven J.; Chutjian, A.; Lozano, J.

2002-11-01

Measurements have been made of the lifetimes and f -values of metastable levels of singly- and highly-charged positive ions (HCI). These contribute to the optical absorption, emission and energy balance in the ISM, stellar and solar atmospheres, etc. These ions and charge states are important for interpretations of data obtained from HST, EUVE, FUSE, Chandra and Newton missions. The vast majority of the millions of transition probabilities are presently being calculated by theory. However, the use of theory alone, unchecked by experimental verification, can lead to orders of magnitude error in the calculated electron densities and temperatures determined from diagnostic line ratios. The experimental lifetime measurements are carried out using the 14.0 GHz electron cyclotron ion source at the JPL facility. [1,2] The ECR ion source provides microampere current of ions such as O(1-6)+ and Mg(1-6)+. Ions are injected into a Kingdon ion trap and stored for times longer than the metastable lifetimes. Decay channels include intercombination, E2, M1 and 2E transitions. The UV photons are filtered by an interference filter and detected by a UV grade photomultiplier tube using a UV grade optical system. For wavelengths less than 180 nm, a cesium-iodide coated microchannel plate enhanced for UV performance is used. The Kingdon trap was constructed in collaboration with Texas A & M University. [3] Base vacuum is 4 x 10-10 Torr, hence quenching corrections are negligible. We have previously reported [1] lifetimes for the 2Po-4P intercombination transitions of C+ and have recently presented lifetime measurements of the 1S0 M1 transition of O2+ at 232 nm. [4] The measured lifetime of 541 ± 40 ms is in good agreement with previous measurements and a number of theoretical calculations. Additional metastable lifetimes have been measured and will be presented for Mg+6 , Fe9+, Fe10+ and Fe13+ metastable states. Additional lifetime measurements are planned for SIII, Ne V, Fe II and Fe XIII This work was carried out at the Jet Propulsion Laboratory, California Institute of Technology, and was supported by the National Aeronautics and Space Administration.

Surface Dangling-Bond States and Band Lineups in Hydrogen-Terminated Si, Ge, and Ge/Si Nanowires

NASA Astrophysics Data System (ADS)

Kagimura, R.; Nunes, R. W.; Chacham, H.

2007-01-01

We report an ab initio study of the electronic properties of surface dangling-bond (SDB) states in hydrogen-terminated Si and Ge nanowires with diameters between 1 and 2 nm, Ge/Si nanowire heterostructures, and Si and Ge (111) surfaces. We find that the charge transition levels ɛ(+/-) of SDB states behave as a common energy reference among Si and Ge wires and Si/Ge heterostructures, at 4.3±0.1eV below the vacuum level. Calculations of ɛ(+/-) for isolated atoms indicate that this nearly constant value is a periodic-table atomic property.

Charge transfer transitions in the photoluminescence spectra of Zn1-xMexO (Me = Mn, Ni, Co) oxide compounds

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Gruzdev, N. B.; Pustovarov, V. A.; Churmanov, V. N.

2013-01-01

Crystals of Zn1-xCoxO and Zn1-xNixO are studied by photoluminescence at temperatures of 8 and 90 K. By resolving the spectra into sums of gaussian distributions and using the known positions of donor and acceptor levels of 3d-impurities relative to the edges of the allowed bands, the observed peaks in the photoluminescence spectra are interpreted in terms of radiative recombination through donor and acceptor levels of nickel and cobalt ions. These results are compared with previously observed features of the photoluminescence spectra of Zn1-xMnxO crystals.

Identification of neutron deficient niobium, molybdenum and technetium isotopes

NASA Astrophysics Data System (ADS)

Gross, C. J.

We report on the in-beam identification of fourteen new isotopes in the A=80-90 region. Heavy-ion reactions with a recoil separator or charged particle and neutron detectors provided identification of γ-rays from these new niobium, molybdenum, and technetium isotopes. The procedures used are described and energy level systematics are discussed. The energy levels appear to be organized into rotational bands in nuclei with N≤44 while those with N ≥ 46 have more single-particle-like transitions. Lifetime measurements in 87Mo and 87Nb indicate that g {9}/{2} particle alignment strongly influences the collectivity of these nuclei.

139La and 63Cu NMR investigation of charge order in La2CuO4 +y (Tc=42 K)

NASA Astrophysics Data System (ADS)

Imai, T.; Lee, Y. S.

2018-03-01

We report 139La and 63Cu NMR investigation of the successive charge order, spin order, and superconducting transitions in superoxygenated La2CuO4 +y single crystal with stage-4 excess oxygen order at Tstage≃290 K. We show that the stage-4 order induces tilting of CuO6 octahedra below Tstage, which in turn causes 139La NMR line broadening. The structural distortion continues to develop far below Tstage, and completes at Tcharge≃60 K, where charge order sets in. This sequence is reminiscent of the the charge-order transition in Nd codoped La1.88Sr0.12CuO4 that sets in once the low-temperature tetragonal phase is established. We also show that the paramagnetic 63Cu NMR signals are progressively wiped out below Tcharge due to enhanced low-frequency spin fluctuations in charge-ordered domains, but the residual 63Cu NMR signals continue to exhibit the characteristics expected for optimally doped superconducting CuO2 planes. This indicates that charge order in La2CuO4 +y does not take place uniformly in space. In addition, unlike the typical second-order magnetic phase transitions, low-frequency Cu spin fluctuations as probed by 139La nuclear spin-lattice relaxation rate do not exhibit critical divergence at Tspin(≃Tc ) =42 K. These findings, including the spatially inhomogeneous nature of the charge-ordered state, are qualitatively similar to the case of La1.885Sr0.115CuO4 [Imai et al., Phys. Rev. B 96, 224508 (2017), 10.1103/PhysRevB.96.224508 and Arsenault et al., Phys. Rev. B 97, 064511 (2018), 10.1103/PhysRevB.97.064511], but both charge and spin order take place more sharply in the present case.

The Variable Transition State in Polar Additions to Pi Bonds

ERIC Educational Resources Information Center

Weiss, Hilton M.

2010-01-01

A vast majority of polar additions of Bronsted acids to alkynes involve a termolecular transition state. With strong acids, considerable positive charge is developed on carbon and Markovnikov addition predominates. In less acidic solutions, however, the reaction is much slower and the transition state more closely resembles the olefinic product.…

Single crystal growth and structural evolution across the 1st order valence transition in (Pr1-yYy)1-xCaxCoO3-δ

NASA Astrophysics Data System (ADS)

Schreiber, N. J.; Zhang, Junjie; Zheng, Hong; Freeland, J. W.; Chen, Yu-Sheng; Mitchell, J. F.; Phelan, D.

2017-10-01

Praseodymium-containing cobalt perovskites, such as (Pr1-yYy)1-xCaxCoO3-δ, have been argued to undergo a first-order charge shift between Pr and hybridized Co-O orbitals that leads to a metal-insulator transition at a temperature, TVT. Magnetization and x-ray absorption spectroscopy measurements on single crystals of (Pr0.85Y0.15)0.7Ca0.3CoO3-δ grown in an IR image furnace under 40-60 bar of oxygen confirm the presence of this valence transition. Single crystal x-ray synchrotron diffraction measurements are consistent with an isomorphic phase transition at TVT. No evidence of charge ordering was revealed by the single crystal diffraction. Dissimilar to analytical transmission electron microscopy measurements performed on a grain from a polycrystalline sample that revealed an oxygen vacancy order-disorder transition at TVT, the present single-crystal measurements did not evidence such a transition, likely reflecting a lower density of oxygen vacancies in the high-pO2 grown single crystals.

Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

NASA Astrophysics Data System (ADS)

Shukla, P. K.; Mishra, P. C.; Suhai, S.

Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the other strongly carcinogenic methylating agents.

Contact and Length Dependent Effects in Single-Molecule Electronics

NASA Astrophysics Data System (ADS)

Hines, Thomas

Understanding charge transport in single molecules covalently bonded to electrodes is a fundamental goal in the field of molecular electronics. In the past decade, it has become possible to measure charge transport on the single-molecule level using the STM break junction method. Measurements on the single-molecule level shed light on charge transport phenomena which would otherwise be obfuscated by ensemble measurements of groups of molecules. This thesis will discuss three projects carried out using STM break junction. In the first project, the transition between two different charge transport mechanisms is reported in a set of molecular wires. The shortest wires show highly length dependent and temperature invariant conductance behavior, whereas the longer wires show weakly length dependent and temperature dependent behavior. This trend is consistent with a model whereby conduction occurs by coherent tunneling in the shortest wires and by incoherent hopping in the longer wires. Measurements are supported with calculations and the evolution of the molecular junction during the pulling process is investigated. The second project reports controlling the formation of single-molecule junctions by means of electrochemically reducing two axial-diazonium terminal groups on a molecule, thereby producing direct Au-C covalent bonds in-situ between the molecule and gold electrodes. Step length analysis shows that the molecular junction is significantly more stable, and can be pulled over a longer distance than a comparable junction created with amine anchoring bonds. The stability of the junction is explained by the calculated lower binding energy associated with the direct Au-C bond compared with the Au-N bond. Finally, the third project investigates the role that molecular conformation plays in the conductance of oligothiophene single-molecule junctions. Ethyl substituted oligothiophenes were measured and found to exhibit temperature dependent conductance and transition voltage for molecules with between two and six repeat units. While the molecule with only one repeat unit shows temperature invariant behavior. Density functional theory calculations show that at higher temperatures the oligomers with multiple repeat units assume a more planar conformation, which increases the conjugation length and decreases the effective energy barrier of the junction.

Photoinduced transition to charge-ordered phases from dynamical localization in the metallic phase of α -(BEDT-TTF)2I3

NASA Astrophysics Data System (ADS)

Oya, Koudai; Takahashi, Akira

2018-03-01

From theory, we investigate charge localization induced by higher-frequency off-resonance light-pulse excitation in the metallic phase of α -(BEDT-TTF) 2I3 by numerically solving the time-dependent Schrödinger equation in the quarter-filled extended Hubbard model for the material. Around e a A(max )=1 , where e a A(max ) is the maximum amplitude of the dimensionless vector potential of the pump pulse, the charge distribution is significantly changed by photoexcitation, and the light-pulse-induced collective charge oscillations continue after photoexcitation. Furthermore, the charge dynamics depend strongly on the polarization direction of the pump pulse. These results are consistent with experiment. The magnitudes of the effective transfer integrals are reduced by strong photoexcitation, and this precursory phenomenon for dynamical localization is mainly driven by a photoinduced change in the ratio of the effective transfer integrals between the two strongest bonds. For e a A(max )≳2 , the photoinduced transition to the charge-ordered state, which can be regarded as a light-dressed state, occurs because of dynamical localization. Furthermore, the type of photogenerated charge-ordered state can be controlled by choosing e a A(max ) and the polarization direction.

Charge Separation and Exciton Dynamics at Polymer/ZnO Interface from First-Principles Simulations.

PubMed

Wu, Guangfen; Li, Zi; Zhang, Xu; Lu, Gang

2014-08-07

Charge separation and exciton dynamics play a crucial role in determining the performance of excitonic photovoltaics. Using time-dependent density functional theory with a range-separated exchange-correlation functional as well as nonadiabatic ab initio molecular dynamics, we have studied the formation and dynamics of charge-transfer (CT) excitons at polymer/ZnO interface. The interfacial atomic structure, exciton density of states and conversions between exciton species are examined from first-principles. The exciton dynamics exhibits both adiabatic and nonadiabatic characters. While the adiabatic transitions are facilitated by C═C vibrations along the polymer (P3HT) backbone, the nonadiabatic transitions are realized by exciton hopping between the excited states. We find that the localized ZnO surface states lead to localized low-energy CT states and poor charge separation. In contrast, the surface states of crystalline C60 are indistinguishable from the bulk states, resulting in delocalized CT states and efficient charge separation in polymer/fullerene (P3HT/PCBM) heterojunctions. The hot CT states are found to cool down in an ultrafast time scale and may not play a major role in charge separation of P3HT/ZnO. Finally we suggest that the dimensions of nanostructured acceptors can be tuned to obtain both efficient charge separation and high open circuit voltages.

Structural instability and electronic localization in the 2:1 salts: The case of the Fabre and the (DMtTTF){2}CIO{4}salts

NASA Astrophysics Data System (ADS)

Ravy, S.; Foury-Leylekian, P.; Le Bolloc'h, D.; Pouget, J.-P.; Fabre, J. M.; Prado, R. J.; Lagarde, P.

2004-04-01

The charge ordering observed in the (TMTTF){2}X family has been studied by X-ray absorption spectroscopy. XANES measurements at the Sulfur K-edge show no evidence of charge disproportionation larger than 0.5 e, and EXAFS at the Phosphorus K-edge indicate no displacements of the PF{6} anion larger than 0.05 Å. The difficulty to observe a structural signature of this charge ordering is due to the triclinic symmetry of these salts. By contrast, in the monoclinic charge transfer salt (DMtTTF){2}ClO{4}, a screw axis symmetry constrains the molecular stacks to be uniform. In this real 1/4-filled system, charge localization is observed at about 150 K. We show that around this temperature an incommensurate modulation of reduced wave vector (0.58,0,-0.275) is stabilized. The transition is strongly hysteretic, but no long range order is established. We suggest that this modulation, which has the 4k{F} periodicity in the chain direction, stabilizes a local antiferroelectric state similar to the one previously observed in (TMTTF){2}SCN. Key words. Charge ordering, Structural phase transition.

Assessment of the amide-I local modes in gamma- and beta-turns of peptides.

PubMed

Wang, Jianping

2009-07-14

The amide-I local modes, mainly the C[double bond, length as m-dash]O stretching vibrations, form the structural basis of femtosecond 2D IR spectroscopy in characterizing backbone structures and dynamics of peptides and proteins. In this work, a density functional theory (DFT) level of computational assessment of the amide-I local modes in oligomers mostly in the turn conformations was carried out. It is shown that local mode properties, including transition frequencies and transition dipole magnitudes and orientations, are slightly conformational dependent. However, the distributions of these properties in the peptide oligomers are narrow and have mean values almost identical to those from an isolated peptide monomer, justifying the prevalent use of a uniform local mode in modeling the 1D and 2D IR spectra. In addition, it is shown that the transition dipole magnitude and orientation of the peptide monomer predicted by the DFT calculations can be well approximated by electrostatic potential-based transition charge schemes, e.g. Merz-Singh-Kollman, CHELP, as well as CHELPG.

Progress towards measuring the Rydberg Constant Using Circular Rydberg Atoms in an Intensity-Modulated Optical Lattice

NASA Astrophysics Data System (ADS)

Ramos, Andira; Moore, Kaitlin; Raithel, Georg

2015-05-01

Recent significant disagreement with the previously established size of the proton demonstrates a need to reconsider the current value of the Rydberg constant, the effects of the nuclear charge distribution and QED in hydrogen-like atoms. An experiment is in progress to obtain a measurement of the Rydberg constant by studying circular Rydberg atoms, which exhibit very small QED shifts and electron wavefunctions which do not overlap with the nucleus. Cold Rydberg atoms are trapped using a ponderomotive potential. To drive the transitions, a novel type of spectroscopy is used which utilizes an optical-lattice field that is intensity-modulated at the frequencies of atomic transitions. The method is free of typical spectroscopic selection rules and has been shown to drive transitions up to fifth order. Combined with optical Rydberg-atom trapping, the method enables the measurement of narrow, sub-THz transitions between long-lived circular Rydberg levels. Energy shifts affecting this precision measurement will also be discussed. This work is suported by NSF, NIST and NASA grants.

Study of dipion transitions among Υ(3S), Υ(2S), and Υ(1S) states

NASA Astrophysics Data System (ADS)

Cronin-Hennessy, D.; Gao, K. Y.; Hietala, J.; Kubota, Y.; Klein, T.; Lang, B. W.; Poling, R.; Scott, A. W.; Smith, A.; Zweber, P.; Dobbs, S.; Metreveli, Z.; Seth, K. K.; Tomaradze, A.; Ernst, J.; Ecklund, K. M.; Severini, H.; Love, W.; Savinov, V.; Lopez, A.; Mehrabyan, S.; Mendez, H.; Ramirez, J.; Huang, G. S.; Miller, D. H.; Pavlunin, V.; Sanghi, B.; Shipsey, I. P. J.; Xin, B.; Adams, G. S.; Anderson, M.; Cummings, J. P.; Danko, I.; Hu, D.; Moziak, B.; Napolitano, J.; He, Q.; Insler, J.; Muramatsu, H.; Park, C. S.; Thorndike, E. H.; Yang, F.; Artuso, M.; Blusk, S.; Khalil, S.; Li, J.; Menaa, N.; Mountain, R.; Nisar, S.; Randrianarivony, K.; Sia, R.; Skwarnicki, T.; Stone, S.; Wang, J. C.; Bonvicini, G.; Cinabro, D.; Dubrovin, M.; Lincoln, A.; Pappas, S. P.; Weinstein, A. J.; Asner, D. M.; Edwards, K. W.; Naik, P.; Briere, R. A.; Ferguson, T.; Tatishvili, G.; Vogel, H.; Watkins, M. E.; Rosner, J. L.; Adam, N. E.; Alexander, J. P.; Cassel, D. G.; Duboscq, J. E.; Ehrlich, R.; Fields, L.; Galik, R. S.; Gibbons, L.; Gray, R.; Gray, S. W.; Hartill, D. L.; Heltsley, B. K.; Hertz, D.; Jones, C. D.; Kandaswamy, J.; Kreinick, D. L.; Kuznetsov, V. E.; Mahlke-Krüger, H.; Mohapatra, D.; Onyisi, P. U. E.; Patterson, J. R.; Peterson, D.; Pivarski, J.; Riley, D.; Ryd, A.; Sadoff, A. J.; Schwarthoff, H.; Shi, X.; Stroiney, S.; Sun, W. M.; Wilksen, T.; Athar, S. B.; Patel, R.; Yelton, J.; Rubin, P.; Cawlfield, C.; Eisenstein, B. I.; Karliner, I.; Kim, D.; Lowrey, N.; Selen, M.; White, E. J.; Wiss, J.; Mitchell, R. E.; Shepherd, M. R.; Besson, D.; Pedlar, T. K.

2007-10-01

We present measurements of decay matrix elements for hadronic transitions of the form Υ(nS)→Υ(mS)ππ, where (n,m)=(3,1),(2,1),(3,2). We reconstruct charged and neutral pion modes with the final state Upsilon decaying to either μ+μ- or e+e-. Dalitz plot distributions for the 12 decay modes are fit individually as well as jointly assuming isospin symmetry, thereby measuring the matrix elements of the decay amplitude. We observe and account for the anomaly previously noted in the dipion invariant mass distribution for the Υ(3S)→Υ(1S)ππ transition and obtain good descriptions of the dynamics of the decay using the most general decay amplitude allowed by partial conservation of the axial-vector current considerations. The fits further indicate that the Υ(2S)→Υ(1S)ππ and Υ(3S)→Υ(2S)ππ transitions also show the presence of terms in the decay amplitude that were previously ignored, although at a relatively suppressed level.

Ultrafast dynamics of photoexcited charge and spin currents in semiconductor nanostructures

NASA Astrophysics Data System (ADS)

Meier, Torsten; Pasenow, Bernhard; Duc, Huynh Thanh; Vu, Quang Tuyen; Haug, Hartmut; Koch, Stephan W.

2007-02-01

Employing the quantum interference among one- and two-photon excitations induced by ultrashort two-color laser pulses it is possible to generate charge and spin currents in semiconductors and semiconductor nanostructures on femtosecond time scales. Here, it is reviewed how the excitation process and the dynamics of such photocurrents can be described on the basis of a microscopic many-body theory. Numerical solutions of the semiconductor Bloch equations (SBE) provide a detailed description of the time-dependent material excitations. Applied to the case of photocurrents, numerical solutions of the SBE for a two-band model including many-body correlations on the second-Born Markov level predict an enhanced damping of the spin current relative to that of the charge current. Interesting effects are obtained when the scattering processes are computed beyond the Markovian limit. Whereas the overall decay of the currents is basically correctly described already within the Markov approximation, quantum-kinetic calculations show that memory effects may lead to additional oscillatory signatures in the current transients. When transitions to coupled heavy- and light-hole valence bands are incorporated into the SBE, additional charge and spin currents, which are not described by the two-band model, appear.

Statistical fluctuations as the origin of nontopological solitons

NASA Technical Reports Server (NTRS)

Griest, Kim; Kolb, Edward W.; Masarotti, Alessandro

1989-01-01

Nontopological solitons can be formed during a phase transition in the early universe as long as some net charge can be trapped in regions of false vacuum. It has been previously suggested that a particle-antiparticle asymmetry would provide a source for such trapped charge. It is pointed out that, for the model and parameters considered, statistical fluctuations provide a much larger concentration of charge, and are therefore, the dominant source of charge fluctuations in solitogenesis.

First-principles characterization of native-defect-related optical transitions in ZnO

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

Lyons, J. L.; Varley, J. B.; Steiauf, D.

We investigate the electrical and optical properties of oxygen vacancies (VO), zinc vacancies (V Zn), hydrogenated V Zn, and isolated dangling bonds in ZnO using hybrid functional calculations. While the formation energy of V O is high in n-type ZnO, indicating that this center is unlikely to form, our results for optical absorption signals associated with V O are consistent with those observed in irradiated samples, and give rise to emission with a peak at less than 1 eV. Under realistic growth conditions, we find that VZn is the lowest-energy native defect in n-type ZnO, acting as an acceptor thatmore » is likely to compensate donor doping. Turning to optical transitions, we first examine N O as a case study, since N-related transitions have been identified in experiments on ZnO. Here, we also examine how hydrogen, often unintentionally present in ZnO, forms stable complexes with V Zn and modifies its optical properties. Compared with isolated V Zn, V Zn-H complexes have charge-state transition levels lower in the band gap as well as have lower formation energies. These complexes also lead to characteristic vibrational frequencies which compare favorably with experiment. Oxygen dangling bonds show behavior mostly consistent with V Zn, while zinc dangling bonds give rise to transition levels near the ZnO conduction-band minimum and emission peaking near 2.4 eV. Lastly, we discuss our results in view of the available experimental literature.« less

First-principles characterization of native-defect-related optical transitions in ZnO

DOE PAGES

Lyons, J. L.; Varley, J. B.; Steiauf, D.; ...

2017-07-21

We investigate the electrical and optical properties of oxygen vacancies (VO), zinc vacancies (V Zn), hydrogenated V Zn, and isolated dangling bonds in ZnO using hybrid functional calculations. While the formation energy of V O is high in n-type ZnO, indicating that this center is unlikely to form, our results for optical absorption signals associated with V O are consistent with those observed in irradiated samples, and give rise to emission with a peak at less than 1 eV. Under realistic growth conditions, we find that VZn is the lowest-energy native defect in n-type ZnO, acting as an acceptor thatmore » is likely to compensate donor doping. Turning to optical transitions, we first examine N O as a case study, since N-related transitions have been identified in experiments on ZnO. Here, we also examine how hydrogen, often unintentionally present in ZnO, forms stable complexes with V Zn and modifies its optical properties. Compared with isolated V Zn, V Zn-H complexes have charge-state transition levels lower in the band gap as well as have lower formation energies. These complexes also lead to characteristic vibrational frequencies which compare favorably with experiment. Oxygen dangling bonds show behavior mostly consistent with V Zn, while zinc dangling bonds give rise to transition levels near the ZnO conduction-band minimum and emission peaking near 2.4 eV. Lastly, we discuss our results in view of the available experimental literature.« less

Transit Operator Guidelines for Transfer Policy Design

DOT National Transportation Integrated Search

1980-06-01

This report provides guidelines to aid transit operators in the design of policies to accomodate bus and/or rail transfers policy may range from a complete set of operator actions involving vehicle routing and scheduling, transfer charges, passenger ...

Maxwell's equal area law for black holes in power Maxwell invariant

NASA Astrophysics Data System (ADS)

Li, Huai-Fan; Guo, Xiong-ying; Zhao, Hui-Hua; Zhao, Ren

2017-08-01

In this paper, we consider the phase transition of black hole in power Maxwell invariant by means of Maxwell's equal area law. First, we review and study the analogy of nonlinear charged black hole solutions with the Van der Waals gas-liquid system in the extended phase space, and obtain isothermal P- v diagram. Then, using the Maxwell's equal area law we study the phase transition of AdS black hole with different temperatures. Finally, we extend the method to the black hole in the canonical (grand canonical) ensemble in which charge (potential) is fixed at infinity. Interestingly, we find the phase transition occurs in the both ensembles. We also study the effect of the parameters of the black hole on the two-phase coexistence. The results show that the black hole may go through a small-large phase transition similar to those of usual non-gravity thermodynamic systems.

Evolution and control of the phase competition morphology in a manganite film

NASA Astrophysics Data System (ADS)

Zhou, Haibiao; Wang, Lingfei; Hou, Yubin; Huang, Zhen; Lu, Qingyou; Wu, Wenbin

2015-11-01

The competition among different phases in perovskite manganites is pronounced since their energies are very close under the interplay of charge, spin, orbital and lattice degrees of freedom. To reveal the roles of underlying interactions, many efforts have been devoted towards directly imaging phase transitions at microscopic scales. Here we show images of the charge-ordered insulator (COI) phase transition from a pure ferromagnetic metal with reducing field or increasing temperature in a strained phase-separated manganite film, using a home-built magnetic force microscope. Compared with the COI melting transition, this reverse transition is sharp, cooperative and martensitic-like with astonishingly unique yet diverse morphologies. The COI domains show variable-dimensional growth at different temperatures and their distribution can illustrate the delicate balance of the underlying interactions in manganites. Our findings also display how phase domain engineering is possible and how the phase competition can be tuned in a controllable manner.

Evolution and control of the phase competition morphology in a manganite film.

PubMed

Zhou, Haibiao; Wang, Lingfei; Hou, Yubin; Huang, Zhen; Lu, Qingyou; Wu, Wenbin

2015-11-25

The competition among different phases in perovskite manganites is pronounced since their energies are very close under the interplay of charge, spin, orbital and lattice degrees of freedom. To reveal the roles of underlying interactions, many efforts have been devoted towards directly imaging phase transitions at microscopic scales. Here we show images of the charge-ordered insulator (COI) phase transition from a pure ferromagnetic metal with reducing field or increasing temperature in a strained phase-separated manganite film, using a home-built magnetic force microscope. Compared with the COI melting transition, this reverse transition is sharp, cooperative and martensitic-like with astonishingly unique yet diverse morphologies. The COI domains show variable-dimensional growth at different temperatures and their distribution can illustrate the delicate balance of the underlying interactions in manganites. Our findings also display how phase domain engineering is possible and how the phase competition can be tuned in a controllable manner.

Electrically active induced energy levels and metastability of B and N vacancy-complexes in 4H-SiC.

PubMed

Igumbor, E; Olaniyan, O; Mapasha, R E; Danga, H T; Omotoso, E; Meyer, W E

2018-05-10

Electrically active induced energy levels in semiconductor devices could be beneficial to the discovery of an enhanced p or n-type semiconductor. Nitrogen (N) implanted into 4H-SiC is a high energy process that produced high defect concentrations which could be removed during dopant activation annealing. On the other hand, boron (B) substituted for silicon in SiC causes a reduction in the number of defects. This scenario leads to a decrease in the dielectric properties and induced deep donor and shallow acceptor levels. Complexes formed by the N, such as the nitrogen-vacancy centre, have been reported to play a significant role in the application of quantum bits. In this paper, results of charge states thermodynamic transition level of the N and B vacancy-complexes in 4H-SiC are presented. We explore complexes where substitutional N[Formula: see text]/N[Formula: see text] or B[Formula: see text]/B[Formula: see text] sits near a Si (V[Formula: see text]) or C (V[Formula: see text]) vacancy to form vacancy-complexes (N[Formula: see text]V[Formula: see text], N[Formula: see text]V[Formula: see text], N[Formula: see text]V[Formula: see text], N[Formula: see text]V[Formula: see text], B[Formula: see text]V[Formula: see text], B[Formula: see text]V[Formula: see text], B[Formula: see text]V[Formula: see text] and B[Formula: see text]V[Formula: see text]). The energies of formation of the N related vacancy-complexes showed the N[Formula: see text]V[Formula: see text] to be energetically stable close to the valence band maximum in its double positive charge state. The N[Formula: see text]V[Formula: see text] is more energetically stable in the double negative charge state close to the conduction band minimum. The N[Formula: see text]V[Formula: see text] on the other hand, induced double donor level and the N[Formula: see text]V[Formula: see text] induced a double acceptor level. For B related complexes, the B[Formula: see text]V[Formula: see text] and B[Formula: see text]V[Formula: see text] were energetically stable in their single positive charge state close to the valence band maximum. As the Fermi energy is varied across the band gap, the neutral and single negative charge states of the B[Formula: see text]V[Formula: see text] become more stable at different energy levels. B and N related complexes exhibited charge state controlled metastability behaviour.

Method of preparing an electrochemical cell in uncharged state

DOEpatents

Shimotake, Hiroshi; Bartholme, Louis G.; Arntzen, John D.

1977-02-01

A secondary electrochemical cell is assembled in an uncharged state for the preparation of a lithium alloy-transition metal sulfide cell. The negative electrode includes a material such as aluminum or silicon for alloying with lithium as the cell is charged. The positive electrode is prepared by blending particulate lithium sulfide, transition metal powder and electrolytic salt in solid phase. The mixture is simultaneously heated to a temperature in excess of the melting point of the electrolyte and pressed onto an electrically conductive substrate to form a plaque. The plaque is assembled as a positive electrode within the cell. During the first charge cycle lithium alloy is formed within the negative electrode and transition metal sulfide such as iron sulfide is produced within the positive electrode.

Photon orbits and thermodynamic phase transition of d -dimensional charged AdS black holes

NASA Astrophysics Data System (ADS)

Wei, Shao-Wen; Liu, Yu-Xiao

2018-05-01

We study the relationship between the null geodesics and thermodynamic phase transition for the charged AdS black hole. In the reduced parameter space, we find that there exist nonmonotonic behaviors of the photon sphere radius and the minimum impact parameter for the pressure below its critical value. The study also shows that the changes of the photon sphere radius and the minimum impact parameter can serve as order parameters for the small-large black hole phase transition. In particular, these changes have an universal exponent of 1/2 near the critical point for any dimension d of spacetime. These results imply that there may exist universal critical behavior of gravity near the thermodynamic critical point of the black hole system.

Davies Critical Point and Tunneling

NASA Astrophysics Data System (ADS)

La, Hoseong

2012-04-01

From the point of view of tunneling, the physical meaning of the Davies critical point of a second-order phase transition in the black hole thermodynamics is clarified. At the critical point, the nonthermal contribution vanishes so that the black hole radiation is entirely thermal. It separates two phases: one with radiation enhanced by the nonthermal contribution, the other suppressed by the nonthermal contribution. We show this in both charged and rotating black holes. The phase transition is also analyzed in the cases in which emissions of charges and angular momenta are incorporated.

Substitution effects on the absorption spectra of nitrophenolate isomers.

PubMed

Wanko, Marius; Houmøller, Jørgen; Støchkel, Kristian; Suhr Kirketerp, Maj-Britt; Petersen, Michael Åxman; Nielsen, Mogens Brøndsted; Nielsen, Steen Brøndsted; Rubio, Angel

2012-10-05

Charge-transfer excitations highly depend on the electronic coupling between the donor and acceptor groups. Nitrophenolates are simple examples of charge-transfer systems where the degree of coupling differs between ortho, meta and para isomers. Here we report the absorption spectra of the isolated anions in vacuo to avoid the complications of solvent effects. Gas-phase action spectroscopy was done with two different setups, an electrostatic ion storage ring and an accelerator mass spectrometer. The results are interpreted on the basis of CC2 quantum chemical calculations. We identified absorption maxima at 393, 532, and 399 nm for the para, meta, and ortho isomer, respectively, with the charge-transfer transition into the lowest excited singlet state. In the meta isomer, this π-π* transition is strongly redshifted and its oscillator strength reduced, which is related to the pronounced charge-transfer character, as a consequence of the topology of the conjugated π-system. Each isomer's different charge distribution in the ground state leads to a very different solvent shift, which in acetonitrile is bathochromic for the para and ortho, but hypsochromic for the meta isomer.

Electronic and magnetic properties of transition metal doped graphyne

NASA Astrophysics Data System (ADS)

Gangan, Abhijeet Sadashiv; Yadav, Asha S.; Chakraborty, Brahmananda; Ramaniah, Lavanya M.

2017-05-01

We have theoretically investigated the interaction of few 3d (V,Mn) and 4d (Y,Zr) transition metals with the γ-graphyne structure using the spin-polarized density functional theory for its potentials application in Hydrogen storage, spintronics and nano-electronics. By doping different TMs we have observed that the system can be either metallic(Y), semi-conducting or half metallic. The system for Y and Zr doped graphyne becomes non-magnetic while V and Mn doped graphyne have a magnetic moments of l μB and 3 μB respectively From bader charge analysis it is seen that there is a charge transfer from the TM atom to the graphyne. Zr and Y have a net charge transfer of 2.15e and 1.73e respectively. Charge density analysis also shows the polarization on the carbon skeleton which becomes larger as the charge transfer for the TM atom increases. Thus we see Y and Zr are better candidates for hydrogen storage devices since they are non-magnetic and have less d electrons which is ideal for kubas-type interactions between hydrogen molecule and TM.

Collective Dynamics and Strong Pinning near the Onset of Charge Order in La1.48Nd0.4Sr0.12CuO4

NASA Astrophysics Data System (ADS)

Baity, P. G.; Sasagawa, T.; Popović, Dragana

2018-04-01

The dynamics of charge-ordered states is one of the key issues in underdoped cuprate high-temperature superconductors, but static short-range charge-order (CO) domains have been detected in almost all cuprates. We probe the dynamics across the CO (and structural) transition in La1.48Nd0.4Sr0.12CuO4 by measuring nonequilibrium charge transport, or resistance R as the system responds to a change in temperature and to an applied magnetic field. We find evidence for metastable states, collective behavior, and criticality. The collective dynamics in the critical regime indicates strong pinning by disorder. Surprisingly, nonequilibrium effects, such as avalanches in R , are revealed only when the critical region is approached from the charge-ordered phase. Our results on La1.48Nd0.4Sr0.12CuO4 provide the long-sought evidence for the fluctuating order across the CO transition, and also set important constraints on theories of dynamic stripes.

Dynamic conductivity from audio to optical frequencies of semiconducting manganites approaching the metal-insulator transition

NASA Astrophysics Data System (ADS)

Lunkenheimer, P.; Mayr, F.; Loidl, A.

2006-07-01

We report the frequency-dependent conductivity of the manganite system La1-xSrxMnO3 (x0.2) when approaching the metal-insulator transition from the insulating side. Results from low-frequency dielectric measurements are combined with spectra in the infrared region. For low doping levels the behavior is dominated by hopping transport of localized charge carriers at low frequencies and by phononic and electronic excitations in the infrared region. For the higher Sr contents the approach of the metallic state is accompanied by the successive suppression of the hopping contribution at low frequencies and by the development of polaronic excitations in the infrared region, which finally become superimposed by a strong Drude contribution in the fully metallic state.

Stimulated electronic transition concept for an erasable optical memory

NASA Technical Reports Server (NTRS)

Albin, Sacharia; Satira, James D.; Livingston, David L.; Shull, Thomas A.

1992-01-01

A new concept for an erasable optical memory is demonstrated using stimulated electronic transition (SET). Large bandgap semiconductors are suitable materials for the SET medium. The properties of MgS:Eu,Sm and SrS:Eu,Sm as possible media for the SET process are investigated. Quantum storage is achieved in the form of charges in deep levels in the medium and stimulated radiative recombination is used as the reading process. Unlike magneto-optic (M-O) and phase change (PC) processes, optical writing, reading and erasing are achieved without localized heating. The SET process will have an inherently faster data transfer rate and a higher storage density, and the medium will be more durable than the M-O and PC media. A possible application of the SET process in neural networks is also discussed.

Identifying topological-band insulator transitions in silicene and other 2D gapped Dirac materials by means of Rényi-Wehrl entropy

NASA Astrophysics Data System (ADS)

Calixto, M.; Romera, E.

2015-02-01

We propose a new method to identify transitions from a topological insulator to a band insulator in silicene (the silicon equivalent of graphene) in the presence of perpendicular magnetic and electric fields, by using the Rényi-Wehrl entropy of the quantum state in phase space. Electron-hole entropies display an inversion/crossing behavior at the charge neutrality point for any Landau level, and the combined entropy of particles plus holes turns out to be maximum at this critical point. The result is interpreted in terms of delocalization of the quantum state in phase space. The entropic description presented in this work will be valid in general 2D gapped Dirac materials, with a strong intrinsic spin-orbit interaction, isostructural with silicene.

Direct visualization of a two-dimensional topological insulator in the single-layer 1 T'-WT e2

NASA Astrophysics Data System (ADS)

Jia, Zhen-Yu; Song, Ye-Heng; Li, Xiang-Bing; Ran, Kejing; Lu, Pengchao; Zheng, Hui-Jun; Zhu, Xin-Yang; Shi, Zhi-Qiang; Sun, Jian; Wen, Jinsheng; Xing, Dingyu; Li, Shao-Chun

2017-07-01

We have grown nearly freestanding single-layer 1 T'-WT e2 on graphitized 6 H -SiC(0001) by using molecular beam epitaxy (MBE), and characterized its electronic structure with scanning tunneling microscopy/spectroscopy (STM/STS). The existence of topological edge states at the periphery of single-layer WT e2 islands was confirmed. Surprisingly, a bulk band gap at the Fermi level and insulating behaviors were also found in single-layer WT e2 at low temperature, which are likely associated with an incommensurate charge order transition. The realization of two-dimensional topological insulators (2D TIs) in single-layer transition-metal dichalcogenide provides a promising platform for further exploration of the 2D TIs' physics and related applications.

Microscopic signature of insulator-to-metal transition in highly doped semicrystalline conducting polymers in ionic-liquid-gated transistors

NASA Astrophysics Data System (ADS)

Tanaka, Hisaaki; Nishio, Satoshi; Ito, Hiroshi; Kuroda, Shin-ichi

2015-12-01

Electronic state of charge carriers, in particular, in highly doped regions, in thin-film transistors of a semicrystalline conducting polymer poly(2,5-bis(3-alkylthiophene-2-yl)thieno[3,2-b]thiophene), has been studied by using field-induced electron spin resonance (ESR) spectroscopy. By adopting an ionic-liquid gate insulator, a gate-controlled reversible electrochemical hole-doping of the polymer backbone is achieved, as confirmed from the change of the optical absorption spectra. The edge-on molecular orientation in the pristine film is maintained even after the electrochemical doping, which is clarified from the angular dependence of the g value. As the doping level increases, spin 1/2 polarons transform into spinless bipolarons, which is demonstrated from the spin-charge relation showing a spin concentration peak around 1%, contrasting to the monotonic increase in the charge concentration. At high doping levels, a drastic change in the linewidth anisotropy due to the generation of conduction electrons is observed, indicating the onset of metallic state, which is also supported by the temperature dependence of the spin susceptibility and the ESR linewidth. Our results suggest that semicrystalline conducting polymers become metallic with retaining their molecular orientational order, when appropriate doping methods are chosen.

Theoretical investigation of stabilities and optical properties of Si12C12 clusters

NASA Astrophysics Data System (ADS)

Duan, Xiaofeng F.; Burggraf, Larry W.

2015-01-01

By sorting through hundreds of globally stable Si12C12 isomers using a potential surface search and using simulated annealing, we have identified low-energy structures. Unlike isomers knit together by Si-C bonds, the lowest energy isomers have segregated carbon and silicon regions that maximize stronger C-C bonding. Positing that charge separation between the carbon and silicon regions would produce interesting optical absorption in these cluster molecules, we used time-dependent density functional theory to compare the calculated optical properties of four isomers representing structural classes having different types of silicon and carbon segregation regions. Absorptions involving charge transfer between segregated carbon and silicon regions produce lower excitation energies than do structures having alternating Si-C bonding for which frontier orbital charge transfer is exclusively from separated carbon atoms to silicon atoms. The most stable Si12C12 isomer at temperatures below 1100 K is unique as regards its high symmetry and large optical oscillator strength in the visible blue. Its high-energy and low-energy visible transitions (1.15 eV and 2.56 eV) are nearly pure one-electron silicon-to-carbon transitions, while an intermediate energy transition (1.28 eV) is a nearly pure carbon-to-silicon one-electron charge transfer.

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

Bugaris, Daniel E.; Malliakas, Christos D.; Han, Fei

A new polymorph of the RE 2Ru 3Ge 5 (RE = Pr, Sm, Dy) compounds has been grown as single crystals via an indium flux. These compounds crystallize in tetragonal space group P4/mnc with the Sc 2Fe 3Si 5-type structure, having lattice parameters a = 11.020(2) Å and c = 5.853(1) Å for RE = Pr, a = 10.982(2) Å and c = 5.777(1) Å for RE = Sm, and a = 10.927(2) Å and c = 5.697(1) Å for RE = Dy. These materials exhibit a structural transition at low temperature, which is attributed to an apparent charge densitymore » wave (CDW). Both the high-temperature average crystal structure and the low-temperature incommensurately modulated crystal structure (for Sm 2Ru 3Ge 5 as a representative) have been solved. The charge density wave order is manifested by periodic distortions of the onedimensional zigzag Ge chains. From X-ray diffraction, charge transport (electrical resistivity, Hall effect, magnetoresistance), magnetic measurements, and heat capacity, the ordering temperatures (T CDW) observed in the Pr and Sm analogues are ~200 and ~175 K, respectively. The charge transport measurement results indicate an electronic state transition happening simultaneously with the CDW transition. X-ray absorption near-edge spectroscopy (XANES) and electronic band structure results are also reported.« less

Effect of Allylic Groups on SN2 Reactivity

PubMed Central

2015-01-01

The activating effects of the benzyl and allyl groups on SN2 reactivity are well-known. 6-Chloromethyl-6-methylfulvene, also a primary, allylic halide, reacts 30 times faster with KI/acetone than does benzyl chloride at room temperature. The latter result, as well as new experimental observations, suggests that the fulvenyl group is a particularly activating allylic group in SN2 reactions. Computational work on identity SN2 reactions, e.g., chloride– displacing chloride– and ammonia displacing ammonia, shows that negatively charged SN2 transition states (tss) are activated by allylic groups according to the Galabov–Allen–Wu electrostatic model but with the fulvenyl group especially effective at helping to delocalize negative charge due to some cyclopentadienide character in the transition state (ts). In contrast, the triafulvenyl group is deactivating. However, the positively charged SN2 transition states of the ammonia reactions are dramatically stabilized by the triafulvenyl group, which directly conjugates with a reaction center having SN1 character in the ts. Experiments and calculations on the acidities of a variety of allylic alcohols and carboxylic acids support the special nature of the fulvenyl group in stabilizing nearby negative charge and highlight the ability of fulvene species to dramatically alter the energetics of processes even in the absence of direct conjugation. PMID:24977317

Enhanced charge ordering transition in doped CaFeO3 through steric templating

NASA Astrophysics Data System (ADS)

Jiang, Lai; Saldana-Greco, Diomedes; Schick, Joseph T.; Rappe, Andrew M.

2014-06-01

We report a density functional theory investigation of B-site doped CaFeO3, a prototypical charge ordered perovskite. At 290 K, CaFeO3 undergoes a metal-insulator transition and a charge disproportionation reaction 2Fe4+→Fe5++Fe3+. We observe that when Zr dopants occupy a (001) layer, the band gap of the resulting solid solution increases to 0.93 eV due to a two-dimensional Jahn-Teller-type distortion, where FeO6 cages on the xy plane elongate along x and y alternatively between neighboring Fe sites. Furthermore, we show that the rock-salt ordering of the Fe5+ and Fe3+ cations can be enhanced when the B-site dopants are arranged in a (111) plane due to a collective steric effect that facilitates the size discrepancy between the Fe5+O6 and Fe3+O6 octahedra and therefore gives rise to a larger band gap. The enhanced charge disproportionation in these solid solutions is verified by rigorously calculating the oxidation states of the Fe cations with different octahedral cage sizes. We therefore predict that the corresponding transition temperature will increase due to the enhanced charge ordering and larger band gap. The compositional, structural, and electrical relationships exploited in this paper can be extended to a variety of perovskites and nonperovskite oxides, providing guidance in the structural manipulation of electrical properties of functional materials.

Benchmark studies on the building blocks of DNA. 3. Watson-Crick and stacked base pairs.

PubMed

Szalay, Péter G; Watson, Thomas; Perera, Ajith; Lotrich, Victor; Bartlett, Rodney J

2013-04-18

Excited states of stacked adenine-thymine and guanine-cytosine pairs as well as the Watson-Crick pair of guanine-thymine have been investigated using the equation of motion coupled-cluster (EOM-CC) method with single and double as well as approximate triple excitations. Transitions have been assigned, and the form of the excitations has been analyzed. The majority of the excitations could be classified as localized on the nucleobases, but for all three studied systems, charge-transfer (CT) transitions could also be identified. The main aim of this study was to compare the performance of lower-level methods (ADC(2) and TDDFT) to the high-level EOM-CC ones. It was shown that both ADC(2) and TDDFT with long-range correction have nonsystematic error in excitation energies, causing alternation of the energetic ordering of the excitations. Considering the high costs of the EOM-CC calculations, there is a need for reliable new approximate methods.

A Unifying Perspective on Oxygen Vacancies in Wide Band Gap Oxides.

PubMed

Linderälv, Christopher; Lindman, Anders; Erhart, Paul

2018-01-04

Wide band gap oxides are versatile materials with numerous applications in research and technology. Many properties of these materials are intimately related to defects, with the most important defect being the oxygen vacancy. Here, using electronic structure calculations, we show that the charge transition level (CTL) and eigenstates associated with oxygen vacancies, which to a large extent determine their electronic properties, are confined to a rather narrow energy range, even while band gap and the electronic structure of the conduction band vary substantially. Vacancies are classified according to their character (deep versus shallow), which shows that the alignment of electronic eigenenergies and CTL can be understood in terms of the transition between cavity-like localized levels in the large band gap limit and strong coupling between conduction band and vacancy states for small to medium band gaps. We consider both conventional and hybrid functionals and demonstrate that the former yields results in very good agreement with the latter provided that band edge alignment is taken into account.

Transition-metal dispersion on carbon-doped boron nitride nanostructures: Applications for high-capacity hydrogen storage

NASA Astrophysics Data System (ADS)

Chen, Ming; Zhao, Yu-Jun; Liao, Ji-Hai; Yang, Xiao-Bao

2012-07-01

Using density-functional theory calculations, we investigated the adsorption of transition-metal (TM) atoms (TM = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) on carbon doped hexagonal boron nitride (BN) sheet and the corresponding cage (B12N12). With carbon substitution of nitrogen, Sc, V, Cr, and Mn atoms were energetically favorable to be dispersed on the BN nanostructures without clustering or the formation of TM dimers, due to the strong binding between TM atoms and substrate, which contains the half-filled levels above the valence bands maximum. The carbon doped BN nanostructures with dispersed Sc could store up to five and six H2, respectively, with the average binding energy of 0.3 ˜ 0.4 eV, indicating the possibility of fabricating hydrogen storage media with high capacity. We also demonstrated that the geometrical effect is important for the hydrogen storage, leading to a modulation of the charge distributions of d levels, which dominates the binding between H2 and TM atoms.

Superconducting materials with electron pairs localized on lattice ions

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

Moizhes, B.Y.; Drabkin, I.A.

1983-07-01

We propose the following classification scheme for superconductors, depending on the probable type of electron--electron interaction: A) Semiconductors containing impurities with negative Hubbard energy in which pairs exist in r-space when T>T/sub c/: Pb/sub 1-x/Tl/sub x/Te, Ba(Pb/sub 1-x/Bi/sub x/)O/sub 3/xxx. In this case the superconducting phase transition must compete with the ordering of ions having different charges: Pb/sub 1-x/In/sub x/Te. B) Metals near the metal--insulator transition with virtual two-electron levels near the Fermi level: Na/sub x/WO/sub 3/. C) Metals containing ''active'' atoms (ions) with an odd number of electrons and a small Hubbard energy. We suggest that the contribution ofmore » diamagnetic polar configurations to the total energy of the metal can increase when coherent states are formed: Nb, La/sub 3/S/sub 4/, Nb/sub 1-x/Ti/sub x/xxx.« less

Polarization effects on quantum levels in InN/GaN quantum wells.

PubMed

Lin, Wei; Li, Shuping; Kang, Junyong

2009-12-02

Polarization effects on quantum states in InN/GaN quantum wells have been investigated by means of ab initio calculation and spectroscopic ellipsometry. Through the position-dependent partial densities of states, our results show that the polarization modified by the strain with different well thickness leads to an asymmetry band bending of the quantum well. The quantum levels are identified via the band structures and their square wave function distributions are analyzed by the partial charge densities. Further theoretical and experimental comparison of the imaginary part of the dielectric function show that the overall transition probability increases under larger polarization fields, which can be attributable to the fact that the excited quantum states of 2h have a greater overlap with 1e states and enhance other hole quantum states in the well by a hybridization. These results would provide a new approach to improve the transition probability and light emission by enhancing the polarization fields in a proper way.

Status in calculating electronic excited states in transition metal oxides from first principles.

PubMed

Bendavid, Leah Isseroff; Carter, Emily Ann

2014-01-01

Characterization of excitations in transition metal oxides is a crucial step in the development of these materials for photonic and optoelectronic applications. However, many transition metal oxides are considered to be strongly correlated materials, and their complex electronic structure is challenging to model with many established quantum mechanical techniques. We review state-of-the-art first-principles methods to calculate charged and neutral excited states in extended materials, and discuss their application to transition metal oxides. We briefly discuss developments in density functional theory (DFT) to calculate fundamental band gaps, and introduce time-dependent DFT, which can model neutral excitations. Charged excitations can be described within the framework of many-body perturbation theory based on Green's functions techniques, which predominantly employs the GW approximation to the self-energy to facilitate a feasible solution to the quasiparticle equations. We review the various implementations of the GW approximation and evaluate each approach in its calculation of fundamental band gaps of many transition metal oxides. We also briefly review the related Bethe-Salpeter equation (BSE), which introduces an electron-hole interaction between GW-derived quasiparticles to describe accurately neutral excitations. Embedded correlated wavefunction theory is another framework used to model localized neutral or charged excitations in extended materials. Here, the electronic structure of a small cluster is modeled within correlated wavefunction theory, while its coupling to its environment is represented by an embedding potential. We review a number of techniques to represent this background potential, including electrostatic representations and electron density-based methods, and evaluate their application to transition metal oxides.

Consequences of acid strength for isomerization and elimination catalysis on solid acids.

PubMed

Macht, Josef; Carr, Robert T; Iglesia, Enrique

2009-05-13

We address here the manner in which acid catalysis senses the strength of solid acids. Acid strengths for Keggin polyoxometalate (POM) clusters and zeolites, chosen because of their accurately known structures, are described rigorously by their deprotonation energies (DPE). Mechanistic interpretations of the measured dynamics of alkane isomerization and alkanol dehydration are used to obtain rate and equilibrium constants and energies for intermediates and transition states and to relate them to acid strength. n-Hexane isomerization rates were limited by isomerization of alkoxide intermediates on bifunctional metal-acid mixtures designed to maintain alkane-alkene equilibrium. Isomerization rate constants were normalized by the number of accessible protons, measured by titration with 2,6-di-tert-butylpyridine during catalysis. Equilibrium constants for alkoxides formed by protonation of n-hexene increased slightly with deprotonation energies (DPE), while isomerization rate constants decreased and activation barriers increased with increasing DPE, as also shown for alkanol dehydration reactions. These trends are consistent with thermochemical analyses of the transition states involved in isomerization and elimination steps. For all reactions, barriers increased by less than the concomitant increase in DPE upon changes in composition, because electrostatic stabilization of ion-pairs at the relevant transition states becomes more effective for weaker acids, as a result of their higher charge density at the anionic conjugate base. Alkoxide isomerization barriers were more sensitive to DPE than for elimination from H-bonded alkanols, the step that limits 2-butanol and 1-butanol dehydration rates; the latter two reactions showed similar DPE sensitivities, despite significant differences in their rates and activation barriers, indicating that slower reactions are not necessarily more sensitive to acid strength, but instead reflect the involvement of more unstable organic cations at their transition states. These compensating effects from electrostatic stabilization depend on how similar the charge density in these organic cations is to that in the proton removed. Cations with more localized charge favor strong electrostatic interactions with anions and form more stable ionic structures than do cations with more diffuse charges. Ion-pairs at elimination transition states contain cations with higher local charge density at the sp(2) carbon than for isomerization transition states; as a result, these ion-pairs recover a larger fraction of the deprotonation energy, and, consequently, their reactions become less sensitive to acid strength. These concepts lead us to conclude that the energetic difficulty of a catalytic reaction, imposed by gas-phase reactant proton affinities in transition state analogues, does not determine its sensitivity to the acid strength of solid catalysts.

Strong compensation hinders the p-type doping of ZnO: a glance over surface defect levels

NASA Astrophysics Data System (ADS)

Huang, B.

2016-07-01

We propose a surface doping model of ZnO to elucidate the p-type doping and compensations in ZnO nanomaterials. With an N-dopant, the effects of N on the ZnO surface demonstrate a relatively shallow acceptor level in the band gap. As the dimension of the ZnO materials decreases, the quantum confinement effects will increase and render the charge transfer on surface to influence the shifting of Fermi level, by evidence of transition level changes of the N-dopant. We report that this can overwhelm the intrinsic p-type conductivity and transport of the ZnO bulk system. This may provide a possible route of using surface doping to modify the electronic transport and conductivity of ZnO nanomaterials.

Cost Effectiveness Analysis of Quasi-In-Motion Wireless Power Transfer for Plug-In Hybrid Electric Transit Buses from Fleet Perspective

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

Wang, Lijuan; Gonder, Jeff; Brooker, Aaron

This study evaluated the costs and benefits associated with the use of stationary-wireless-power-transfer-enabled plug-in hybrid electric buses and determined the cost effectiveness relative to conventional buses and hybrid electric buses. A factorial design was performed over a number of different battery sizes, charging power levels, and f bus stop charging stations. The net present costs were calculated for each vehicle design and provided the basis for design evaluation. In all cases, given the assumed economic conditions, the conventional bus achieved the lowest net present cost while the optimal plug-in hybrid electric bus scenario beat out the hybrid electric comparison scenario.more » The parameter sensitivity was also investigated under favorable and unfavorable market penetration assumptions.« less

Finite frequency current noise in the Holstein model

NASA Astrophysics Data System (ADS)

Stadler, P.; Rastelli, G.; Belzig, W.

2018-05-01

We investigate the effects of local vibrational excitations in the nonsymmetrized current noise S (ω ) of a nanojunction. For this purpose, we analyze a simple model—the Holstein model—in which the junction is described by a single electronic level that is coupled to two metallic leads and to a single vibrational mode. Using the Keldysh Green's function technique, we calculate the nonsymmetrized current noise to the leading order in the charge-vibration interaction. For the noise associated to the latter, we identify distinct terms corresponding to the mean-field noise and the vertex correction. The mean-field result can be further divided into an elastic correction to the noise and in an inelastic correction, the second one being related to energy exchange with the vibration. To illustrate the general behavior of the noise induced by the charge-vibration interaction, we consider two limit cases. In the first case, we assume a strong coupling of the dot to the leads with an energy-independent transmission, whereas in the second case we assume a weak tunneling coupling between the dot and the leads such that the transport occurs through a sharp resonant level. We find that the noise associated to the vibration-charge interaction shows a complex pattern as a function of the frequency ω and of the transmission function or of the dot's energy level. Several transitions from enhancement to suppression of the noise occurs in different regions, which are determined, in particular, by the vibrational frequency. Remarkably, in the regime of an energy-independent transmission, the zero-order elastic noise vanishes at perfect transmission and at positive frequency, whereas the noise related to the charge-vibration interaction remains finite, enabling the analysis of the pure vibrational-induced current noise.

Time-dependent transition density matrix for visualizing charge-transfer excitations in photoexcited organic donor-acceptor systems

NASA Astrophysics Data System (ADS)

Li, Yonghui; Ullrich, Carsten

2013-03-01

The time-dependent transition density matrix (TDM) is a useful tool to visualize and interpret the induced charges and electron-hole coherences of excitonic processes in large molecules. Combined with time-dependent density functional theory on a real-space grid (as implemented in the octopus code), the TDM is a computationally viable visualization tool for optical excitation processes in molecules. It provides real-time maps of particles and holes which gives information on excitations, in particular those that have charge-transfer character, that cannot be obtained from the density alone. Some illustration of the TDM and comparison with standard density difference plots will be shown for photoexcited organic donor-acceptor molecules. This work is supported by NSF Grant DMR-1005651

Observation of extreme ultraviolet transitions in highly charged Ba{sup 16+} to Ba{sup 23+} ions with electron beam ion trap

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

Ali, S.; Shimizu, E.; Nakamura, N.

2016-03-15

We have investigated extreme ultraviolet emission from highly charged barium using a compact electron beam ion trap at the Tokyo EBIT laboratory. The spectra were recorded for several beam energies ranging from 440 to 740 eV, while keeping the electron beam current constant at 10 mA. Radiation from charge states Zr-like Ba{sup 16+} to As-like Ba{sup 23+} were recorded and identified by varying the electron beam energy across the ionization thresholds and comparing with calculated results. The calculations were performed with a detailed relativistic configuration interaction approach using the Flexible Atomic Code. Several new lines belonging to electric dipole transitions were observedmore » and identified.« less

Change in the frequency and intensity of the spectral lines of a hydrogen-like atom in the field of a point charge

NASA Astrophysics Data System (ADS)

Ovsyannikov, V. D.; Kamenskii, A. A.

2002-03-01

The changes in the wave functions and the energies of a hydrogen-like atom in the static field of a structureless charged particle are calculated in the asymptotic approximation. The corrections to the energy of states, as well as to the dipole matrix elements of radiative transitions caused by the interaction of the atom with the point charge at long range are calculated using the perturbation theory and the Sturm series for a reduced Coulomb Green’s function in parabolic coordinates. The analytical expressions are derived and tables of numerical values of the coefficients of asymptotic series that determine the corrections to the matrix elements and the intensities of transitions of the Lyman and Balmer series are presented.

Local Real-Space View of the Achiral 1 T -TiSe2 2 ×2 ×2 Charge Density Wave

NASA Astrophysics Data System (ADS)

Hildebrand, B.; Jaouen, T.; Mottas, M.-L.; Monney, G.; Barreteau, C.; Giannini, E.; Bowler, D. R.; Aebi, P.

2018-03-01

The transition metal dichalcogenide 1 T -TiSe2 -two-dimensional layered material undergoing a commensurate 2 ×2 ×2 charge density wave (CDW) transition with a weak periodic lattice distortion (PLD) below ≈200 K . Scanning tunneling microscopy (STM) combined with intentionally introduced interstitial Ti atoms allows us to go beyond the usual spatial resolution of STM and to intimately probe the three-dimensional character of the PLD. Furthermore, the inversion-symmetric achiral nature of the CDW in the z direction is revealed, contradicting the claimed existence of helical CDW stacking and associated chiral order. This study paves the way to a simultaneous real-space probing of both charge and structural reconstructions in CDW compounds.

Fine-tuning the Mott metal-insulator transition and critical charge carrier dynamics in molecular conductors

NASA Astrophysics Data System (ADS)

Müller, Jens; Hartmann, Benedikt; Sasaki, Takahiko

2017-12-01

The unique possibilities of fine-tuning their physical properties in the vicinity of the Mott metal-insulator transition make the quasi-two-dimensional organic charge-transfer salts ?-(BEDT-TTF)?X unprecedented model systems for studying the fundamentals of electron-electron correlations and the coupling between charge, spin and lattice degrees of freedom in reduced dimensions. The critical properties and the universality class of the Mott transition, however, are controversially debated for these materials, and information on the low-frequency dynamical properties of the correlated electrons is rather limited. By introducing fluctuation (noise) spectroscopy as a powerful new tool for studying the slow dynamics of charge carriers, in the past years we have been able to extract spectroscopic information on the coupling of charge carriers to the vibrational degrees of freedom of the crystal lattice. This is related to a glassy freezing of the BEDT-TTF molecules' ethylene end-group (EEG) rotations at elevated temperatures, which (i) results in a small amount of (intrinsic) disorder and (ii) crucially influences the ratio of bandwidth to on-site Coulomb repulsion (W / U) and therefore the samples' position in the phase diagram, i.e. the electronic ground state. The low-frequency resistance fluctuations show a dramatic enhancement and divergent behaviour when tuning the sample close to the critical point of the Mott transition, accompanied by a strong shift of spectral weight to low frequencies and the onset of non-Gaussian behaviour. This indicates the critical slowing down of the order-parameter (doublon density) fluctuations and suggests a collective dynamics of the correlated electrons. In order to enable detailed investigations of this hypothesis in future experiments, by exploiting the structural EEG relaxation, a 'warming cycle' protocol can be established that allows for fine-tuning the sample across the Mott transition and therefore precisely accessing the finite-temperature critical endpoint. We 'calibrate' this procedure by a comparison to pressure-tuning experiments on the same sample. This method will allow to map out the region of ergodicity breaking around the critical endpoint and its dependence on disorder.

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the electrochemical cycling effect, electrolyte exposure also shows non-negligible influence on cathode surface degradation. These chemical and structural changes of the NMC cathode could contribute to the first-cycle coulombic inefficiency, restrict the charge transfer characteristics and ultimately impact the cell capacity.

Charge and spin control of ultrafast electron and hole dynamics in single CdSe/ZnSe quantum dots

NASA Astrophysics Data System (ADS)

Hinz, C.; Gumbsheimer, P.; Traum, C.; Holtkemper, M.; Bauer, B.; Haase, J.; Mahapatra, S.; Frey, A.; Brunner, K.; Reiter, D. E.; Kuhn, T.; Seletskiy, D. V.; Leitenstorfer, A.

2018-01-01

We study the dynamics of photoexcited electrons and holes in single negatively charged CdSe/ZnSe quantum dots with two-color femtosecond pump-probe spectroscopy. An initial characterization of the energy level structure is performed at low temperatures and magnetic fields of up to 5 T. Emission and absorption resonances are assigned to specific transitions between few-fermion states by a theoretical model based on a configuration interaction approach. To analyze the dynamics of individual charge carriers, we initialize the quantum system into excited trion states with defined energy and spin. Subsequently, the time-dependent occupation of the trion ground state is monitored by spectrally resolved differential transmission measurements. We observe subpicosecond dynamics for a hole excited to the D shell. The energy dependence of this D -to-S shell intraband transition is investigated in quantum dots of varying size. Excitation of an electron-hole pair in the respective p shells leads to the formation of singlet and triplet spin configurations. Relaxation of the p -shell singlet is observed to occur on a time scale of a few picoseconds. Pumping of p -shell triplet transitions opens up two pathways with distinctly different scattering times. These processes are shown to be governed by the mixing of singlet and triplet states due to exchange interactions enabling simultaneous electron and hole spin flips. To isolate the relaxation channels, we align the spin of the residual electron by a magnetic field and employ laser pulses of defined helicity. This step provides ultrafast preparation of a fully inverted trion ground state of the quantum dot with near unity probability, enabling deterministic addition of a single photon to the probe pulse. Therefore our experiments represent a significant step towards using single quantum emitters with well-controled inversion to manipulate the photon statistics of ultrafast light pulses.

Structural change and charge ordering correlated ultrasonic anomalies in La1-xCaxMnO3 (x=0.5,0.83) perovskite

NASA Astrophysics Data System (ADS)

Zheng, R. K.; Zhu, C. F.; Xie, J. Q.; Li, X. G.

2001-01-01

Ultrasonic sound velocity and attenuation have been measured in polycrystalline manganese oxide La1-xCaxMnO3 (x=0.5,0.83,1.0) at a frequency of 10 MHz. For x=0.5, on cooling down from high temperature, a slight softening of the sound velocity above the charge ordering transition temperature TCO and dramatic stiffening below TCO coincided with big attenuation peaks for both longitudinal and transverse waves were observed. It was found that these ultrasonic anomalies near TCO are correlated with the fine structure (i.e., the lattice parameters) change caused by the Jahn-Teller effect. For x=0.83, the sound velocity starts to soften dramatically with decreasing temperature from higher temperature to TS (180 K), and stiffens dramatically below TS. The large softening and stiffening of the sound velocity accompanied by a big attenuation peak are strongly correlated with a cubic-to-tetragonal structural phase transition at TS, which is confirmed by the low-temperature powder x-ray diffraction measurements. It is suggested that this structural phase transition be due to the Jahn-Teller distortion of the Mn3+O6 octahedra and related to the charge ordering transition. For CaMnO3, the anomaly in sound velocity is small.

Spin polarization properties of benzene/graphene with transition metals as dopants: First principles calculations

NASA Astrophysics Data System (ADS)

Yuan, X. B.; Tian, Y. L.; Zhao, X. W.; Yue, W. W.; Hu, G. C.; Ren, J. F.

2018-05-01

First principles calculations are used to study the spin polarization properties of benzene molecule adsorbed on the graphene surface which doped with transition metals including Mn, Cr, Fe, Co, and Ni. The densities of states (DOS) of the benzene molecule can be induced to be spin split at the Fermi level only when it is adsorbed on Mn-, and Cr-doped graphene. The p-orbital of the benzene molecule will interact with the d orbital of the doped atoms, which will generate new spin coupling states and lead to obvious spin polarization of the benzene molecule. The spin-polarized density distributions as well as the differential charge density distributions of the systems also suggest that Mn-doped graphene will induce bigger spin polarization than that of Cr-doped graphene. Benzene molecule could be spin-polarized when it is adsorbed on the graphene surface with transition metal dopants, which could be a new method for researching graphene-based organic spintronic devices.

Electronic structure of Fe- vs. Ru-based dye molecules

NASA Astrophysics Data System (ADS)

Johnson, Phillip S.; Cook, Peter L.; Zegkinoglou, Ioannis; García-Lastra, J. M.; Rubio, Angel; Ruther, Rose E.; Hamers, Robert J.; Himpsel, F. J.

2013-01-01

In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe- and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-π* transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-π* transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

Tunable charge transfer properties in metal-phthalocyanine heterojunctions.

PubMed

Siles, P F; Hahn, T; Salvan, G; Knupfer, M; Zhu, F; Zahn, D R T; Schmidt, O G

2016-04-28

Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

Detection of singly- and doubly-charged quaternary ammonium drugs in equine urine by liquid chromatography/tandem mass spectrometry.

PubMed

Ho, Emmie N M; Kwok, W H; Wong, April S Y; Wan, Terence S M

2012-01-13

Quaternary ammonium drugs (QADs) are anticholinergic agents some of which are known to have been abused or misused in equine sports. A recent review of literature shows that the screening methods reported thus far for QADs mainly cover singly-charged QADs. Doubly-charged QADs are extremely polar substances which are difficult to be extracted and poorly retained on reversed-phase columns. It would be ideal if a comprehensive method can be developed which can detect both singly- and doubly-charged QADs. This paper describes an efficient liquid chromatography/tandem mass spectrometry (LC/MS/MS) method for the simultaneous detection and confirmation of 38 singly- and doubly-charged QADs at sub-parts-per-billion (ppb) to low-ppb levels in equine urine after solid-phase extraction. Quaternary ammonium drugs were extracted from equine urine by solid-phase extraction (SPE) using an ISOLUTE(®) CBA SPE column and analysed by LC/MS/MS in the positive electrospray ionisation mode. Separation of the 38 QADs was achieved on a polar group embedded C18 LC column with a mixture of aqueous ammonium formate (pH 3.0, 10 mM) and acetonitrile as the mobile phase. Detection and confirmation of the 38 QADs at sub-ppb to low-ppb levels in equine urine could be achieved within 16 min using selected reaction monitoring (SRM). Matrix interference of the target transitions at the expected retention times was not observed. Other method validation data, including precision and recovery, were acceptable. The method was successfully applied to the analyses of drug-administration samples. Copyright © 2011 Elsevier B.V. All rights reserved.

Fluctuations and correlations of conserved charges in QCD at finite temperature with effective models

NASA Astrophysics Data System (ADS)

Fu, Wei-Jie; Liu, Yu-Xin; Wu, Yue-Liang

2010-01-01

We study fluctuations of conserved charges including baryon number, electric charge, and strangeness as well as the correlations among these conserved charges in the 2+1 flavor Polyakov-Nambu-Jona-Lasinio model at finite temperature. The calculated results are compared with those obtained from recent lattice calculations performed with an improved staggered fermion action at two values of the lattice cutoff with almost physical up and down quark masses and a physical value for the strange quark mass. We find that our calculated results are well consistent with those obtained in lattice calculations except for some quantitative differences for fluctuations related with strange quarks. Our calculations indicate that there is a pronounced cusp in the ratio of the quartic to quadratic fluctuations of baryon number, i.e. χ4B/χ2B, at the critical temperature during the phase transition, which confirms that χ4B/χ2B is a useful probe of the deconfinement and chiral phase transition.

Simple phenomenological modeling of transition-region capacitance of forward-biased p-n junction diodes and transistor diodes

NASA Technical Reports Server (NTRS)

Lindholm, F. A.

1982-01-01

The derivation of a simple expression for the capacitance C(V) associated with the transition region of a p-n junction under a forward bias is derived by phenomenological reasoning. The treatment of C(V) is based on the conventional Shockley equations, and simpler expressions for C(V) result that are in general accord with the previous analytical and numerical results. C(V) consists of two components resulting from changes in majority carrier concentration and from free hole and electron accumulation in the space-charge region. The space-charge region is conceived as the intrinsic region of an n-i-p structure for a space-charge region markedly wider than the extrinsic Debye lengths at its edges. This region is excited in the sense that the forward bias creates hole and electron densities orders of magnitude larger than those in equilibrium. The recent Shirts-Gordon (1979) modeling of the space-charge region using a dielectric response function is contrasted with the more conventional Schottky-Shockley modeling.

Dynamic control of a homogeneous charge compression ignition engine

DOEpatents

Duffy, Kevin P [Metamora, IL; Mehresh, Parag [Peoria, IL; Schuh, David [Peoria, IL; Kieser, Andrew J [Morton, IL; Hergart, Carl-Anders [Peoria, IL; Hardy, William L [Peoria, IL; Rodman, Anthony [Chillicothe, IL; Liechty, Michael P [Chillicothe, IL

2008-06-03

A homogenous charge compression ignition engine is operated by compressing a charge mixture of air, exhaust and fuel in a combustion chamber to an autoignition condition of the fuel. The engine may facilitate a transition from a first combination of speed and load to a second combination of speed and load by changing the charge mixture and compression ratio. This may be accomplished in a consecutive engine cycle by adjusting both a fuel injector control signal and a variable valve control signal away from a nominal variable valve control signal. Thereafter in one or more subsequent engine cycles, more sluggish adjustments are made to at least one of a geometric compression ratio control signal and an exhaust gas recirculation control signal to allow the variable valve control signal to be readjusted back toward its nominal variable valve control signal setting. By readjusting the variable valve control signal back toward its nominal setting, the engine will be ready for another transition to a new combination of engine speed and load.

Layer Splitting in a Complex Plasma

NASA Astrophysics Data System (ADS)

Smith, Bernard; Hyde, Truell; Matthews, Lorin; Johnson, Megan; Cook, Mike; Schmoke, Jimmy

2009-11-01

Dust particle clouds are found in most plasma processing environments and many astrophysical environments. Dust particles suspended within such plasmas often acquire an electric charge from collisions with free electrons in the plasma. Depending upon the ratio of interparticle potential energy to average kinetic energy, charged dust particles can form a gaseous, liquid or crystalline structure with short to longer range ordering. An interesting facet of complex plasma behavior is that particle layers appear to split as the DC bias is increased. This splitting of layers points to a phase transition differing from the normal phase transitions found in two-dimensional solids. In 1993, Dubin noted that as the charged particle density of an initially two-dimensional Coulomb crystal increases the system's layers split at specific charge densities. This work modeled ions in a Paul or Penning trap, but may be applicable to dusty plasma systems as well. This work will discuss this possibility along with splitting observed in the CASPER GEC rf Reference Cell at specific pressures and powers.

Mottness Collapse in 1 T -TaS2 -xSex Transition-Metal Dichalcogenide: An Interplay between Localized and Itinerant Orbitals

NASA Astrophysics Data System (ADS)

Qiao, Shuang; Li, Xintong; Wang, Naizhou; Ruan, Wei; Ye, Cun; Cai, Peng; Hao, Zhenqi; Yao, Hong; Chen, Xianhui; Wu, Jian; Wang, Yayu; Liu, Zheng

2017-10-01

The layered transition-metal dichalcogenide 1 T -TaS2 has been recently found to undergo a Mott-insulator-to-superconductor transition induced by high pressure, charge doping, or isovalent substitution. By combining scanning tunneling microscopy measurements and first-principles calculations, we investigate the atomic scale electronic structure of the 1 T -TaS2 Mott insulator and its evolution to the metallic state upon isovalent substitution of S with Se. We identify two distinct types of orbital textures—one localized and the other extended—and demonstrate that the interplay between them is the key factor that determines the electronic structure. In particular, we show that the continuous evolution of the charge gap visualized by scanning tunneling microscopy is due to the immersion of the localized-orbital-induced Hubbard bands into the extended-orbital-spanned Fermi sea, featuring a unique evolution from a Mott gap to a charge-transfer gap. This new mechanism of Mottness collapse revealed here suggests an interesting route for creating novel electronic states and designing future electronic devices.

Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

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

Bisogni, Valentina; Catalano, Sara; Green, Robert J.

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. However, a complete understanding of these materials remains elusive. Here, taking a NdNiO 3 thin film as a representative example, we utilize a combination of x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculationsmore » and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d 8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a “conventional” positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.« less

Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

DOE PAGES

Bisogni, Valentina; Catalano, Sara; Green, Robert J.; ...

2016-10-11

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. However, a complete understanding of these materials remains elusive. Here, taking a NdNiO 3 thin film as a representative example, we utilize a combination of x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculationsmore » and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d 8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a “conventional” positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.« less

Bipartite charge fluctuations in one-dimensional Z2 superconductors and insulators

NASA Astrophysics Data System (ADS)

Herviou, Loïc; Mora, Christophe; Le Hur, Karyn

2017-09-01

Bipartite charge fluctuations (BCFs) have been introduced to provide an experimental indication of many-body entanglement. They have proved themselves to be a very efficient and useful tool to characterize quantum phase transitions in a variety of quantum models conserving the total number of particles (or magnetization for spin systems) and can be measured experimentally. We study the BCFs in generic one-dimensional Z2 (topological) models including the Kitaev superconducting wire model, the Ising chain, or various topological insulators such as the Su-Schrieffer-Heeger model. The considered charge (either the fermionic number or the relative density) is no longer conserved, leading to macroscopic fluctuations of the number of particles. We demonstrate that at phase transitions characterized by a linear dispersion, the BCFs probe the change in a winding number that allows one to pinpoint the transition and corresponds to the topological invariant for standard models. Additionally, we prove that a subdominant logarithmic contribution is still present at the exact critical point. Its quantized coefficient is universal and characterizes the critical model. Results are extended to the Rashba topological nanowires and to the X Y Z model.

Heteroleptic monometallic and trimetallic ruthenium(II) complexes incorporating a π-extended dipyrrin ligand: Light-activated reactions with the A549 lung cancer cell line.

PubMed

Swavey, Shawn; Morford, Krista; Tsao, Max; Comfort, Kristen; Kilroy, Mary Kate

2017-10-01

A heteroleptic monometallic ruthenium(II) and a heteroleptic trimetallic ruthenium(II) complex have been synthesized and characterized. Both complexes have an overall 3+ charge, with the charge density greater for the monometallic complex. The electronic spectra of the monometallic ruthenium(II) complex exhibits intense π-π* transitions associated with the bipyridyl groups along with overlapping metal to ligand charge transfer (MLCT) and ligand centered π-π* transitions ranging from 520nm to approximately 600nm. The trimetallic ruthenium(II) complex, on the other hand, displays more well defined transitions with the expected π-π* transition of the bipyridyl groups at 294nm and Ru(dπ) to bpy(π*) MLCT transitions at 355nm and 502nm. In addition to these absorption bands an intense transition, 578nm, resulting from overlapping dipyrrin (π-π*) and Ru(dπ) to dipyrrin(π*) transitions is observed. Electrochemical and spectroelectrochemical experiments were used to help in assigning these transitions. Irradiation of the complexes in the presence of plasmid DNA within the photodynamic therapy window (600nm to 850nm) reveal, using electrophoresis, that both complexes are capable of causing photo-damage to the DNA backbone. The trimetallic ruthenium(II) complex; however, also shows the ability to generate photoinduced DNA damage in the absence of oxygen, suggesting a photo-oxidative process. Studies of the complexes toward lung cancer cells (A549 cell line) in the absence of light indicate little cytotoxicity up to 50μM. Upon irradiation of the cells with a low power 420nm light source the trimetallic complex showed considerably greater photo-cytotoxicity compared to the monometallic analog. A dose-dependent response curve gives an IC50 of 92μM for complex B. Copyright © 2017 Elsevier Inc. All rights reserved.

Pairing Symmetry Transitions in the Even-Denominator FQHE System

NASA Astrophysics Data System (ADS)

Nomura, Kentaro; Yoshioka, Daijiro

2001-12-01

Transitions from a paired quantum Hall state to another quantum Hall state in bilayer systems are discussed in the framework of the edge theory. Starting from the edge theory for the Haldane Rezayi state, it is shown that the charging effect of a bilayer system which breaks the SU(2) symmetry of the pseudospin shifts the central charge and the conformal dimensions of the fermionic fields which describe the pseudospin sector in the edge theory. This corresponds to the transition from the Haldane Rezayi state to Halperin's 331 state, or from a singlet d-wave to a triplet p-wave ABM type paired state in the composite fermion picture. Considering interlayer tunneling, the tunneling rate-capacitance phase diagram for the ν=5/2 paired bilayer system is discussed.

Possible mechanism to enhance spin-fluctuation-mediated superconductivity in two-dimensional organic conductor

NASA Astrophysics Data System (ADS)

Nonoyama, Yoshito; Maekawa, Yukiko; Kobayashi, Akito; Suzumura, Yoshikazu; Yamada, Jun-ichi

2008-10-01

Mechanisms of superconductivity in quasi-two-dimensional organic conductors have been investigated using an extended Hubbard model by using the transfer energies between BDA-TTP molecules for β-(BDA-TTP)2I3 based on the X-ray experiment data and the extended Hückel calculation. We obtain several mean-field solutions with charge orderings which may represent short-range orderings or low-energy fluctuations in the low-dimensional electronic system. In the pressure-temperature phase diagram, a charge ordered metal state almost degenerates with a normal metal state between an insulating phase with charge ordering and the normal metal phase. Using the random phase approximation (RPA) and the linearized gap equation, the transition temperature of the superconducting state is estimated for the charge-ordered metal state and the normal metal state. It is found that transition temperature of the superconductivity induced by spin fluctuations in the charge-ordered metal state is much higher than that of the normal metal state and that the superconductivity in the charge-ordered metal state is the gapless d-wave. This suggests that the short range charge ordering may also contribute to an enhancement of spin-fluctuation-mediated superconductivity. The difference in the superconducting states between β-(BDA-TTP)2I3 and β-(BDA-TTP)2SbF6 are briefly discussed.

Spectroscopic Investigations of Highly Charged Tungsten Ions - Atomic Spectroscopy and Fusion Plasma Diagnostics

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

Clementson, Joel

2010-05-01

The spectra of highly charged tungsten ions have been investigated using x-ray and extreme ultraviolet spectroscopy. These heavy ions are of interest in relativistic atomic structure theory, where high-precision wavelength measurements benchmark theoretical approaches, and in magnetic fusion research, where the ions may serve to diagnose high-temperature plasmas. The work details spectroscopic investigations of highly charged tungsten ions measured at the Livermore electron beam ion trap (EBIT) facility. Here, the EBIT-I and SuperEBIT electron beam ion traps have been employed to create, trap, and excite tungsten ions of M- and L-shell charge states. The emitted spectra have been studied inmore » high resolution using crystal, grating, and x-ray calorimeter spectrometers. In particular, wavelengths of n = 0 M-shell transitions in K-like W 55+ through Ne-like W 64+, and intershell transitions in Zn-like W 44+ through Co-like W 47+ have been measured. Special attention is given to the Ni-like W46+ ion, which has two strong electric-dipole forbidden transitions that are of interest for plasma diagnostics. The EBIT measurements are complemented by spectral modeling using the Flexible Atomic Code (FAC), and predictions for tokamak spectra are presented. The L-shell tungsten ions have been studied at electron-beam energies of up to 122 keV and transition energies measured in Ne-like W 64+ through Li-like W 71+. These spectra constitute the physics basis in the design of the ion-temperature crystal spectrometer for the ITER tokamak. Tungsten particles have furthermore been introduced into the Sustained Spheromak Physics Experiment (SSPX) spheromak in Livermore in order to investigate diagnostic possibilities of extreme ultraviolet tungsten spectra for the ITER divertor. The spheromak measurement and spectral modeling using FAC suggest that tungsten ions in charge states around Er-like W 6+ could be useful for plasma diagnostics.« less

Photocurrent spectroscopy of exciton and free particle optical transitions in suspended carbon nanotube pn-junctions

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

Chang, Shun-Wen; Theiss, Jesse; Hazra, Jubin

2015-08-03

We study photocurrent generation in individual, suspended carbon nanotube pn-junction diodes formed by electrostatic doping using two gate electrodes. Photocurrent spectra collected under various electrostatic doping concentrations reveal distinctive behaviors for free particle optical transitions and excitonic transitions. In particular, the photocurrent generated by excitonic transitions exhibits a strong gate doping dependence, while that of the free particle transitions is gate independent. Here, the built-in potential of the pn-junction is required to separate the strongly bound electron-hole pairs of the excitons, while free particle excitations do not require this field-assisted charge separation. We observe a sharp, well defined E{sub 11}more » free particle interband transition in contrast with previous photocurrent studies. Several steps are taken to ensure that the active charge separating region of these pn-junctions is suspended off the substrate in a suspended region that is substantially longer than the exciton diffusion length and, therefore, the photocurrent does not originate from a Schottky junction. We present a detailed model of the built-in fields in these pn-junctions, which, together with phonon-assistant exciton dissociation, predicts photocurrents on the same order of those observed experimentally.« less

Single crystal growth and structural evolution across the 1st order valence transition in (Pr 1–yY y) 1–xCa xCoO 3-δ

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

Schreiber, N. J.; Zhang, Junjie; Zheng, Hong

Here, praseodymium-containing cobalt perovskites, such as (Pr 1-yY y) 1-xCa xCoO 3-δ, have been argued to undergo a first-order charge shift between Pr and hybridized Co-O orbitals that leads to a metal-insulator transition at a temperature, T VT. Magnetization and x-ray absorption spectroscopy measurements on single crystals of (Pr 0.85Y 0.15) 0.7Ca 0.3CoO 3-δ grown in an IR image furnace under 40-60 bar of oxygen confirm the presence of this valence transition. Single crystal x-ray synchrotron diffraction measurements are consistent with an isomorphic phase transition at T VT. No evidence of charge ordering was revealed by the single crystal diffraction.more » Dissimilar to analytical transmission electron microscopy measurements performed on a grain from a polycrystalline sample that revealed an oxygen vacancy order-disorder transition at T VT, the present single-crystal measurements did not evidence such a transition, likely reflecting a lower density of oxygen vacancies in the high-pO 2 grown single crystals.« less

Nontrivial transition of transmission in a highly open quantum point contact in the quantum Hall regime

NASA Astrophysics Data System (ADS)

Hong, Changki; Park, Jinhong; Chung, Yunchul; Choi, Hyungkook; Umansky, Vladimir

2017-11-01

Transmission through a quantum point contact (QPC) in the quantum Hall regime usually exhibits multiple resonances as a function of gate voltage and high nonlinearity in bias. Such behavior is unpredictable and changes sample by sample. Here, we report the observation of a sharp transition of the transmission through an open QPC at finite bias, which was observed consistently for all the tested QPCs. It is found that the bias dependence of the transition can be fitted to the Fermi-Dirac distribution function through universal scaling. The fitted temperature matches quite nicely to the electron temperature measured via shot-noise thermometry. While the origin of the transition is unclear, we propose a phenomenological model based on our experimental results that may help to understand such a sharp transition. Similar transitions are observed in the fractional quantum Hall regime, and it is found that the temperature of the system can be measured by rescaling the quasiparticle energy with the effective charge (e*=e /3 ). We believe that the observed phenomena can be exploited as a tool for measuring the electron temperature of the system and for studying the quasiparticle charges of the fractional quantum Hall states.

Single crystal growth and structural evolution across the 1st order valence transition in (Pr 1–yY y) 1–xCa xCoO 3-δ

DOE PAGES

Schreiber, N. J.; Zhang, Junjie; Zheng, Hong; ...

2017-06-27

Here, praseodymium-containing cobalt perovskites, such as (Pr 1-yY y) 1-xCa xCoO 3-δ, have been argued to undergo a first-order charge shift between Pr and hybridized Co-O orbitals that leads to a metal-insulator transition at a temperature, T VT. Magnetization and x-ray absorption spectroscopy measurements on single crystals of (Pr 0.85Y 0.15) 0.7Ca 0.3CoO 3-δ grown in an IR image furnace under 40-60 bar of oxygen confirm the presence of this valence transition. Single crystal x-ray synchrotron diffraction measurements are consistent with an isomorphic phase transition at T VT. No evidence of charge ordering was revealed by the single crystal diffraction.more » Dissimilar to analytical transmission electron microscopy measurements performed on a grain from a polycrystalline sample that revealed an oxygen vacancy order-disorder transition at T VT, the present single-crystal measurements did not evidence such a transition, likely reflecting a lower density of oxygen vacancies in the high-pO 2 grown single crystals.« less

High magnetic field studies of the charge density wave state of the quasi-two-dimensional conductor KMO 6O 17

NASA Astrophysics Data System (ADS)

Dumas, Jean; Guyot, Hervé; Balaska, Hafid; Marcus, Jacques; Vignolles, David; Sheikin, Ilya; Audouard, Alain; Brossard, Luc; Schlenker, Claire

2004-04-01

Magnetic torque and magnetoresistance measurements have been performed in high magnetic field on the quasi-two-dimensional charge density wave (CDW) oxide bronze KMo 6O 17 . Several anomalies have been found below 28 T either on the torque or on the magnetoresistance data. They can be attributed predominantly to orbital effects. Magnetoresistance data obtained up to 55 T show that a transition takes place above 30 T. This transition may be due to the Pauli coupling. The new field-induced density wave state exhibits Shubnikov-de Haas (SdH) oscillations.

Signatures of pair-density wave order via measurement of the current-phase relation in La2-xBaxCuO4 Josephson junctions

NASA Astrophysics Data System (ADS)

Hamilton, David; Weis, Adam; Gu, Genda; van Harlingen, Dale

La2-xBaxCuO4 (LBCO) exhibits a sharp drop in the transition temperature near x = 1 / 8 doping. In this regime, charge, spin and superconducting orders are intertwined and superconductivity is believed to exist in a pair-density wave (PDW) state, an ordered stripe phase characterized by sign changes in the superconducting order parameter between adjacent stripes. We present direct measurements of the current-phase relation (CPR) of Josephson junctions patterned onto crystals of LBCO at x = 1 / 8 and x = 0 . 155 (optimal doping) using a phase-sensitive Josephson interferometry technique. In contrast to the approximately sinusoidal CPR observed at optimal doping, we find the proportion of higher harmonics in the CPR increases at x = 1 / 8 doping, consistent with the formation of a PDW state. In parallel, we are carrying out measurements of the resistance noise in thin films of LBCO of various doping levels to identify features that signify the onset of charge order and changes in the dynamics of charge stripes.

Electrochemical reaction mechanisms under various charge-discharge operating conditions for Li1.2Ni0.13Mn0.54Co0.13O2 in a lithium-ion battery

NASA Astrophysics Data System (ADS)

Konishi, Hiroaki; Hirano, Tatsumi; Takamatsu, Daiko; Gunji, Akira; Feng, Xiaoliang; Furutsuki, Sho; Okumura, Takefumi; Terada, Shohei; Tamura, Kazuhisa

2018-06-01

The potential in each state of charge (SOC) during charging of Li1.2Ni0.13Mn0.54Co0.13O2 is higher than that during discharging. In other words, the potential hysteresis occurs between charging and discharging. Furthermore, the potential in each SOC changes according to the charge-discharge operating conditions, indicating that the charge-discharge reaction mechanism is also affected. To clarify the effect of charge-discharge operating conditions on the electrochemical reaction, Li1.2Ni0.13Mn0.54Co0.13O2 was charged and discharged under various charge-discharge operating ranges, and open-circuit potential (OCP), crystal structure, and oxidation states of the transition metals were evaluated by electrochemical measurement, X-ray diffraction (XRD), and X-ray absorption fine structure (XAFS). These results indicate that OCP, lattice parameters, and oxidation states of the transition metals of Li1.2Ni0.13Mn0.54Co0.13O2 in each SOC are not constant. The XRD results indicate that two phases, namely, LiNi0.33Mn0.33Co0.33O2-like and Li2MnO3-like, exist in Li1.2Ni0.13Mn0.54Co0.13O2. For the LiNi0.33Mn0.33Co0.33O2-like phase, the relationship between OCP, lattice parameters, and oxidation states of the transition metals in each SOC is not affected by the charge-discharge operating conditions, indicating that extraction and insertion of lithium ions for the LiNi0.33Mn0.33Co0.33O2-like phase progresses at almost the same potential. Although the extraction and insertion of lithium ions for the Li2MnO3-like phase progresses at almost the same potential in the low-SOC region, the OCP and lattice parameter in each SOC in the high-SOC region are not constant. Therefore, the extraction of lithium ions from the Li2MnO3-like phase in the high-SOC region causes the potential hysteresis of Li1.2Ni0.13Mn0.54Co0.13O2.

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Universality of the Berezinskii-Kosterlitz-Thouless type of phase transition in the dipolar XY-model

NASA Astrophysics Data System (ADS)

Vasiliev, A. Yu; Tarkhov, A. E.; Menshikov, L. I.; Fedichev, P. O.; Fischer, Uwe R.

2014-05-01

We investigate the nature of the phase transition occurring in a planar XY-model spin system with dipole-dipole interactions. It is demonstrated that a Berezinskii-Kosterlitz-Thouless (BKT) type of phase transition always takes place at a finite temperature separating the ordered (ferro) and the disordered (para) phases. The low-temperature phase corresponds to an ordered state with thermal fluctuations, composed of a ‘gas’ of bound vortex-antivortex pairs, which would, when considered isolated, be characterized by a constant vortex-antivortex attraction force which is due to the dipolar interaction term in the Hamiltonian. Using a topological charge model, we show that small bound pairs are easily polarized, and screen the vortex-antivortex interaction in sufficiently large pairs. Screening changes the linear attraction potential of vortices to a logarithmic one, and leads to the familiar pair dissociation mechanism of the BKT type phase transition. The topological charge model is confirmed by numerical simulations, in which we demonstrate that the transition temperature slightly increases when compared with the BKT result for short-range interactions.

Localized Electron Trap Modification as a Result of Space Weather Exposure in Highly Disordered Insulating Materials

DTIC Science & Technology

2017-03-06

4 Pre-transit discharge region (phase II) ........................................................................... 5 Post...transit Discharge Region (phase III) ...................................................................... 5 2.2. Optical Signature...3 Figure 2 Schematic of a charge/ discharge curve of an electron irradiated insulating material. .. 4

42 CFR 414.44 - Transition rules.

Code of Federal Regulations, 2010 CFR

2010-10-01

... § 414.44 Transition rules. (a) Adjusted historical payment basis—(1) All services other than radiology and nuclear medicine services. For all physician services other than radiology services, furnished in... charge, adjusted by the update established for CY 1992. (2) Radiology services. For radiology services...

Boron difluoride dibenzoylmethane derivatives: Electronic structure and luminescence

NASA Astrophysics Data System (ADS)

Tikhonov, Sergey A.; Vovna, Vitaliy I.; Osmushko, Ivan S.; Fedorenko, Elena V.; Mirochnik, Anatoliy G.

2018-01-01

Electronic structure and optical properties of boron difluoride dibenzoylmethanate and four of its derivatives have been studied by X-ray photoelectron spectroscopy, absorption and luminescence spectroscopy and quantum chemistry (DFT, TDDFT). The relative quantum luminescence yields have been revealed to correlate with charge transfers of HOMO-LUMO transitions, energy barriers of aromatic substituents rotation and the lifetime of excited states in the investigated complexes. The bathochromic shift of intensive bands in the optical spectra has been observed to occur when the functional groups are introduced into p-positions of phenyl cycles due to destabilizing HOMO levels. Calculated energy intervals between electronic levels correlate well with XPS spectra structure of valence and core electrons.

Spectral lines behavior of Be I and Na I isoelectronic sequence in Debye plasma environment

NASA Astrophysics Data System (ADS)

Chaudhuri, Rajat K.; Chattopadhyay, Sudip; Sinha Mahapatra, Uttam

2012-08-01

We report the plasma screening effect on the first ionization potential (IP) and [He]2s2(1S0)→[He]2s2p /2s3p allowed (P11) and inter-combination transitions (P31) in some selected Be-like ions. In addition, we investigate the spectral properties of [Ne]3s (2S1/2)→[Ne]np(2P1/2 and P23/2 for n = 3, 4) transitions in Ca X and Fe XVI ions (Na I isoelectronic sequence) and [He]3s(2S1/2)→[He]np(2P1/2 and P23/2 for n = 2, 3) transitions in Li, B II, and N IV (Li I isoelectronic sequence) under plasma environment. The state-of-the-art relativistic coupled cluster calculations using the Debye model of plasma for electron-nucleus interaction show that (a) the ionization potential decreases sharply with increasing plasma strength and (b) the gap between the [He]2s2(1S0)→[He]2s2p(1,3P1) energy levels increases with increasing plasma potential and nuclear charge. It is found that the [He]2s2 (1S0)→2s3p(1,3P1) transition energy decreases uniformly with increasing plasma potential and nuclear charge. In other words, the spectral lines associated with 2s-2p (i.e., Δn=0, where n corresponds to principle quantum number) transitions in Be I isoelectronic sequence exhibit a blue-shift (except for Be I, B II, and the lowest inter-combination line in C III, which exhibit a red-shift), whereas those associated with 2s-3p (i.e., Δn≠0) transitions are red-shifted. Similar trend is observed in Li I and Na I isoelectronic sequences, where spectral lines associated with Δn=0 (Δn≠0) are blue-shifted (red-shifted). The effect of Coulomb screening on the spectral lines of ions subjected to plasma is also addressed.

Black p-branes versus black holes in non-asymptotically flat Einstein-Yang-Mills theory

NASA Astrophysics Data System (ADS)

Habib Mazharimousavi, S.; Halilsoy, M.

2016-09-01

We present a class of non-asymptotically flat (NAF) charged black p-branes (BpB) with p-compact dimensions in higher-dimensional Einstein-Yang-Mills theory. Asymptotically the NAF structure manifests itself as an anti-de sitter spacetime. We determine the total mass/energy enclosed in a thin shell located outside the event horizon. By comparing the entropies of BpB with those of black holes in the same dimensions we derive transition criteria between the two types of black objects. Given certain conditions satisfied, our analysis shows that BpB can be considered excited states of black holes. An event horizon r+ versus charge square Q2 plot for the BpB reveals such a transition where r+ is related to the horizon radius rh of the black hole (BH) both with the common charge Q.

Fast Charge Battery Electric Transit Bus In-Use Fleet Evaluation

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

Prohaska, Robert; Kelly, Kenneth; Eudy, Leslie

2016-07-25

The focus of this interim fleet evaluation is to characterize and evaluate the operating behavior of Foothill Transit's fast charge battery electric buses (BEBs). Future research will compare the BEBs' performance to conventional vehicles. In an effort to better understand the impacts of drive cycle characteristics on advanced vehicle technologies, researchers at the National Renewable Energy Laboratory analyzed over 148,000 km of in-use operational data, including driving and charging events. This analysis provides an unbiased evaluation of advanced vehicle technologies in real-world operation demonstrating the importance of understanding the effects of road grade and heating, ventilating and air conditioning requirementsmore » when deploying electric vehicles. The results of this analysis show that the Proterra BE35 demonstrated an operating energy efficiency of 1.34 kWh/km over the data reporting period.« less

Fast Charge Battery Electric Transit Bus In-Use Fleet Evaluation: Preprint

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

Prohaska, Robert; Eudy, Leslie; Kelly, Kenneth

2016-05-06

The focus of this interim fleet evaluation is to characterize and evaluate the operating behavior of Foothill Transit's fast charge battery electric buses (BEBs). Future research will compare the BEBs' performance to conventional vehicles. In an effort to better understand the impacts of drive cycle characteristics on advanced vehicle technologies, researchers at the National Renewable Energy Laboratory analyzed over 148,000 km of in-use operational data, including driving and charging events. This analysis provides an unbiased evaluation of advanced vehicle technologies in real-world operation demonstrating the importance of understanding the effects of road grade and heating, ventilating and air conditioning requirementsmore » when deploying electric vehicles. The results of this analysis show that the Proterra BE35 demonstrated an operating energy efficiency of 1.34 kWh/km over the data reporting period.« less

Energy, Transportation, Air Quality, Climate Change, Health Nexus: Sustainable Energy is Good for Our Health.

PubMed

Erickson, Larry E; Jennings, Merrisa

2017-01-01

The Paris Agreement on Climate Change has the potential to improve air quality and human health by encouraging the electrification of transportation and a transition from coal to sustainable energy. There will be human health benefits from reducing combustion emissions in all parts of the world. Solar powered charging infrastructure for electric vehicles adds renewable energy to generate electricity, shaded parking, and a needed charging infrastructure for electric vehicles that will reduce range anxiety. The costs of wind power, solar panels, and batteries are falling because of technological progress, magnitude of commercial activity, production experience, and competition associated with new trillion dollar markets. These energy and transportation transitions can have a very positive impact on health. The energy, transportation, air quality, climate change, health nexus may benefit from additional progress in developing solar powered charging infrastructure.

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

Xu, Jing; Hu, Enyuan; Nordlund, Dennis

The phase transition, charge compensation, and local chemical environment of Ni in LiNiO 2 were investigated to understand the degradation mechanism. The electrode was subjected to a variety of bulk and surface-sensitive characterization techniques under different charge–discharge cycling conditions. We observed the phase transition from the original hexagonal H1 phase to another two hexagonal phases (H2 and H3) upon Li deintercalation. Moreover, the gradual loss of H3-phase features was revealed during the repeated charges. The reduction in Ni redox activity occurred at both the charge and the discharge states, and it appeared both in the bulk and at the surfacemore » over the extended cycles. In conclusion, the degradation of crystal structure significantly contributes to the reduction of Ni redox activity, which in turn causes the cycling performance decay of LiNiO 2.« less

Point-Defect Nature of the Ultraviolet Absorption Band in AlN

NASA Astrophysics Data System (ADS)

Alden, D.; Harris, J. S.; Bryan, Z.; Baker, J. N.; Reddy, P.; Mita, S.; Callsen, G.; Hoffmann, A.; Irving, D. L.; Collazo, R.; Sitar, Z.

2018-05-01

We present an approach where point defects and defect complexes are identified using power-dependent photoluminescence excitation spectroscopy, impurity data from SIMS, and density-functional-theory (DFT)-based calculations accounting for the total charge balance in the crystal. Employing the capabilities of such an experimental computational approach, in this work, the ultraviolet-C absorption band at 4.7 eV, as well as the 2.7- and 3.9-eV luminescence bands in AlN single crystals grown via physical vapor transport (PVT) are studied in detail. Photoluminescence excitation spectroscopy measurements demonstrate the relationship between the defect luminescent bands centered at 3.9 and 2.7 eV to the commonly observed absorption band centered at 4.7 eV. Accordingly, the thermodynamic transition energy for the absorption band at 4.7 eV and the luminescence band at 3.9 eV is estimated at 4.2 eV, in agreement with the thermodynamic transition energy for the CN- point defect. Finally, the 2.7-eV PL band is the result of a donor-acceptor pair transition between the VN and CN point defects since nitrogen vacancies are predicted to be present in the crystal in concentrations similar to carbon-employing charge-balance-constrained DFT calculations. Power-dependent photoluminescence measurements reveal the presence of the deep donor state with a thermodynamic transition energy of 5.0 eV, which we hypothesize to be nitrogen vacancies in agreement with predictions based on theory. The charge state, concentration, and type of impurities in the crystal are calculated considering a fixed amount of impurities and using a DFT-based defect solver, which considers their respective formation energies and the total charge balance in the crystal. The presented results show that nitrogen vacancies are the most likely candidate for the deep donor state involved in the donor-acceptor pair transition with peak emission at 2.7 eV for the conditions relevant to PVT growth.

Effect of NO annealing on charge traps in oxide insulator and transition layer for 4H-SiC metal-oxide-semiconductor devices

NASA Astrophysics Data System (ADS)

Jia, Yifan; Lv, Hongliang; Niu, Yingxi; Li, Ling; Song, Qingwen; Tang, Xiaoyan; Li, Chengzhan; Zhao, Yanli; Xiao, Li; Wang, Liangyong; Tang, Guangming; Zhang, Yimen; Zhang, Yuming

2016-09-01

The effect of nitric oxide (NO) annealing on charge traps in the oxide insulator and transition layer in n-type 4H-SiC metal-oxide-semiconductor (MOS) devices has been investigated using the time-dependent bias stress (TDBS), capacitance-voltage (C-V), and secondary ion mass spectroscopy (SIMS). It is revealed that two main categories of charge traps, near interface oxide traps (Nniot) and oxide traps (Not), have different responses to the TDBS and C-V characteristics in NO-annealed and Ar-annealed samples. The Nniot are mainly responsible for the hysteresis occurring in the bidirectional C-V characteristics, which are very close to the semiconductor interface and can readily exchange charges with the inner semiconductor. However, Not is mainly responsible for the TDBS induced C-V shifts. Electrons tunneling into the Not are hardly released quickly when suffering TDBS, resulting in the problem of the threshold voltage stability. Compared with the Ar-annealed sample, Nniot can be significantly suppressed by the NO annealing, but there is little improvement of Not. SIMS results demonstrate that the Nniot are distributed within the transition layer, which correlated with the existence of the excess silicon. During the NO annealing process, the excess Si atoms incorporate into nitrogen in the transition layer, allowing better relaxation of the interface strain and effectively reducing the width of the transition layer and the density of Nniot. Project supported by the National Natural Science Foundation of China (Grant Nos. 61404098 and 61274079), the Doctoral Fund of Ministry of Education of China (Grant No. 20130203120017), the National Key Basic Research Program of China (Grant No. 2015CB759600), the National Grid Science & Technology Project, China (Grant No. SGRI-WD-71-14-018), and the Key Specific Project in the National Science & Technology Program, China (Grant Nos. 2013ZX02305002-002 and 2015CB759600).

The Iron Project and the Rmax Project: X-ray Spectroscopy of Highly Charged Ions

NASA Astrophysics Data System (ADS)

Oelgoetz, Justin; Pradhan, Anil; Nahar, Sultana; Montenegro, Maximiliano; Eissner, Werner

2006-05-01

We will describe recent work on (1) the modeling of spectra arising from highly charged ions, and (2) the data that goes into such models. Emission from the Kα, and in some cases, Kβ lines of the Li, He, and H-like states of ions is of great interest in X-ray astronomy and high-temperature laboratory sources such as fusion devices. Current results at modeling these lines including all relevant atomic processes for the elements Fe, Ni and Ca will be presented, along with a discussion of the computational methods employed and the possible implications of the work. An extensive set of oscillator strengths, line strengths and radiative decay rates for the allowed and forbidden transitions in Fe XVIII have been obtained in the relativistic Briet-Pauli R-Matrix approximation. The results include 1174 fine structure levels of total angular momenta J= 12 - 172 and n le 10 and about 171,500 transitions among them. Sample results will be presented. Parts of this work were supported under grants from the NSF and the NASA Astrophysical Theory Program as well as by Los Alamos National Laboratory which is operated under Department of Energy contract W-7405-ENG-36 by the University of California. Many of the calculations were carried out at the Ohio Supercomputer Center.

DFT Study of Optical Properties of Pt-based Complexes

NASA Astrophysics Data System (ADS)

Oprea, Corneliu I.; Dumbravǎ, Anca; Moscalu, Florin; Nicolaides, Atnanassios; Gîrţu, Mihai A.

2010-01-01

We report Density Functional Theory (DFT) calculations providing the geometrical and electronic structures, as well as the vibrational and optical properties of the homologous series of Pt-pyramidalized olefin complexes (CH2)n-(C8H10)Pt(PH3)2, where n = 0, 1, and 2, in their neutral and oxidized states. All complexes were geometry optimized for the singlet ground state in vacuum using DFT methods with B3LYP exchange-correlation functional and the Effective Core Potential LANL2DZ basis set, within the frame of Gaussian03 quantum chemistry package. We find the coordination geometry of Pt to be distorted square planar, with dihedral angles ranging from 0°, for n = 0 and 1, which have C2V symmetry to 3.4°, for n = 2 with C2 symmetry. The Mulliken charge analysis allows a discussion of the oxidation state of the Pt ion. Electronic transitions were calculated at the same level of theory by means of Time Dependant-DFT. For n = 2 the electronic absorption bands are located in the UV region of the spectrum, the transitions being assigned to metal to ligand charge transfers. The relevance of these Pt-based compounds as possible pigments for dye-sensitized solar cells is discussed.

Decoupling the Lattice Distortion and Charge Doping Effects on the Phase Transition Behavior of VO2 by Titanium (Ti4+) Doping

PubMed Central

Wu, Yanfei; Fan, Lele; Liu, Qinghua; Chen, Shi; Huang, Weifeng; Chen, Feihu; Liao, Guangming; Zou, Chongwen; Wu, Ziyu

2015-01-01

The mechanism for regulating the critical temperature (TC) of metal-insulator transition (MIT) in ions-doped VO2 systems is still a matter of debate, in particular, the unclear roles of lattice distortion and charge doping effects. To rule out the charge doping effect on the regulation of TC, we investigated Ti4+-doped VO2 (TixV1-xO2) system. It was observed that the TC of TixV1-xO2 samples first slightly decreased and then increased with increasing Ti concentration. X-ray absorption fine structure (XAFS) spectroscopy was used to explore the electronic states and local lattice structures around both Ti and V atoms in TixV1-xO2 samples. Our results revealed the local structure evolution from the initial anatase to the rutile-like structure around the Ti dopants. Furthermore, the host monoclinic VO2 lattice, specifically, the VO6 octahedra would be subtly distorted by Ti doping. The distortion of VO6 octahedra and the variation of TC showed almost the similar trend, confirming the direct effect of local structural perturbations on the phase transition behavior. By comparing other ion-doping systems, we point out that the charge doping is more effective than the lattice distortion in modulating the MIT behavior of VO2 materials. PMID:25950809

Contribution of Jahn-Teller and charge transfer excitations to the photovoltaic effect of manganite/titanite heterojunctions

NASA Astrophysics Data System (ADS)

Ifland, Benedikt; Hoffmann, Joerg; Kressdorf, Birte; Roddatis, Vladimir; Seibt, Michael; Jooss, Christian

2017-06-01

The effect of correlation effects on photovoltaic energy conversion at manganite/titanite heterojunctions is investigated. As a model system we choose a heterostructure consisting of the small polaron absorber Pr0.66Ca0.34MnO3 (PCMO) epitaxially grown on single-crystalline Nb-doped SrTi0.998Nb0.002O3 (STNO) substrates. The high structural and chemical quality of the interfaces is proved by detailed characterization using high-resolution transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) studies. Spectrally resolved and temperature-dependent photovoltaic measurements show pronounced contributions of both the Jahn-Teller (JT) excitations and the charge transfer (CT) transitions to the photovoltaic effect at different photon energies. A linear temperature dependence of the open-circuit voltage for an excitation in the PCMO manganite is only observed below the charge-ordering temperature, indicating that the diffusion length of the photocarrier exceeds the size of the space charge region. The photovoltaic response is compared to that of a heterojunction of lightly doped Pr0.05Ca0.95MnO3 (CMO)/STNO, where the JT transition is absent. Here, significant contributions of the CT transition to the photovoltaic effect set in below the Neel temperature. We conclude that polaronic correlations and ordering effects are essentials for photovoltaic energy conversion in manganites.

Influence of Coherent Tunneling and Incoherent Hopping on the Charge Transfer Mechanism in Linear Donor-Bridge-Acceptor Systems.

PubMed

Li, Guangqi; Govind, Niranjan; Ratner, Mark A; Cramer, Christopher J; Gagliardi, Laura

2015-12-17

The mechanism of charge transfer has been observed to change from tunneling to hopping with increasing numbers of DNA base pairs in polynucleotides and with the length of molecular wires. The aim of this paper is to investigate this transition by examining the population dynamics using a tight-binding Hamiltonian with model parameters to describe a linear donor-bridge-acceptor (D-B-A) system. The model includes a primary vibration and an electron-vibration coupling at each site. A further coupling of the primary vibration with a secondary phonon bath allows the system to dissipate energy to the environment and reach a steady state. We apply the quantum master equation (QME) approach, based on second-order perturbation theory in a quantum dissipative system, to examine the dynamical processes involved in charge-transfer and follow the population transfer rate at the acceptor, ka, to shed light on the transition from tunneling to hopping. With a small tunneling parameter, V, the on-site population tends to localize and form polarons, and the hopping mechanism dominates the transfer process. With increasing V, the population tends to be delocalized and the tunneling mechanism dominates. The competition between incoherent hopping and coherent tunneling governs the mechanism of charge transfer. By varying V and the total number of sites, we also examine the onset of the transition from tunneling to hopping with increasing length.

On the calculation of charge transfer transitions with standard density functionals using constrained variational density functional theory.

PubMed

Ziegler, Tom; Krykunov, Mykhaylo

2010-08-21

It is well known that time-dependent density functional theory (TD-DFT) based on standard gradient corrected functionals affords both a quantitative and qualitative incorrect picture of charge transfer transitions between two spatially separated regions. It is shown here that the well known failure can be traced back to the use of linear response theory. Further, it is demonstrated that the inclusion of higher order terms readily affords a qualitatively correct picture even for simple functionals based on the local density approximation. The inclusion of these terms is done within the framework of a newly developed variational approach to excitation energies called constrained variational density functional theory (CV-DFT). To second order [CV(2)-DFT] this theory is identical to adiabatic TD-DFT within the Tamm-Dancoff approximation. With inclusion of fourth order corrections [CV(4)-DFT] it affords a qualitative correct description of charge transfer transitions. It is finally demonstrated that the relaxation of the ground state Kohn-Sham orbitals to first order in response to the change in density on excitation together with CV(4)-DFT affords charge transfer excitations in good agreement with experiment. The new relaxed theory is termed R-CV(4)-DFT. The relaxed scheme represents an effective way in which to introduce double replacements into the description of single electron excitations, something that would otherwise require a frequency dependent kernel.

Resonant Coherent Excitation of Hydrogen-Like Ar Ions to the n =: 3 States

NASA Astrophysics Data System (ADS)

Azuma, T.; Ito, T.; Takabayashi, Y.; Komaki, K.; Yamazaki, Y.; Yamazaki, Y.; Takada, E.; Murakami, T.

We have succeeded in observing resonant coherent excitaion (RCE) of 1s electrons to the n = 3 states in 390 MeV/u hydrogen-like Ar17+ ions planar channeled in a silicon crystal through measurements of the charge-state distribution of ions transmitting the crystal. Furthermore, we directly confirmed RCE to the n = 3 states by observing the enhancement of the de-excitation X-rays, i.e., Kβ X-rays under the resonance condition. The resonance profiles of the charge-state distribution as functions of the incident angle to the crystal, which uniquely relates with the transition energy, have a characteristic structure consisting of several peaks. Compared with the profile of RCE to the n = 2 states, the present profiles show a large peak shift from the j = 1/2 and 3/2 levels in vacuum, and the profiles are much wider than those expected from the Stark-split level structure of the n = 3 manifolds due to the position- (distance from the channel center in the planar channel) dependent strong static field in the crystal.

Interface designed MoS2/GaAs heterostructure solar cell with sandwich stacked hexagonal boron nitride

PubMed Central

Lin, Shisheng; Li, Xiaoqiang; Wang, Peng; Xu, Zhijuan; Zhang, Shengjiao; Zhong, Huikai; Wu, Zhiqian; Xu, Wenli; Chen, Hongsheng

2015-01-01

MoS2 is a layered two-dimensional semiconductor with a direct band gap of 1.8 eV. The MoS2/bulk semiconductor system offers a new platform for solar cell device design. Different from the conventional bulk p-n junctions, in the MoS2/bulk semiconductor heterostructure, static charge transfer shifts the Fermi level of MoS2 toward that of bulk semiconductor, lowering the barrier height of the formed junction. Herein, we introduce hexagonal boron nitride (h-BN) into MoS2/GaAs heterostructure to suppress the static charge transfer, and the obtained MoS2/h-BN/GaAs solar cell exhibits an improved power conversion efficiency of 5.42%. More importantly, the sandwiched h-BN makes the Fermi level tuning of MoS2 more effective. By employing chemical doping and electrical gating into the solar cell device, PCE of 9.03% is achieved, which is the highest among all the reported monolayer transition metal dichalcogenide based solar cells. PMID:26458358

Observation of Mollow Triplets with Tunable Interactions in Double Lambda Systems of Individual Hole Spins

NASA Astrophysics Data System (ADS)

Lagoudakis, K. G.; Fischer, K. A.; Sarmiento, T.; McMahon, P. L.; Radulaski, M.; Zhang, J. L.; Kelaita, Y.; Dory, C.; Müller, K.; Vučković, J.

2017-01-01

Although individual spins in quantum dots have been studied extensively as qubits, their investigation under strong resonant driving in the scope of accessing Mollow physics is still an open question. Here, we have grown high quality positively charged quantum dots embedded in a planar microcavity that enable enhanced light-matter interactions. Under a strong magnetic field in the Voigt configuration, individual positively charged quantum dots provide a double lambda level structure. Using a combination of above-band and resonant excitation, we observe the formation of Mollow triplets on all optical transitions. We find that when the strong resonant drive power is used to tune the Mollow-triplet lines through each other, we observe anticrossings. We also demonstrate that the interaction that gives rise to the anticrossings can be controlled in strength by tuning the polarization of the resonant laser drive. Quantum-optical modeling of our system fully captures the experimentally observed spectra and provides insight on the complicated level structure that results from the strong driving of the double lambda system.

Correlating electronic and vibrational motions in charge transfer systems

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

Khalil, Munira

2014-06-27

The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

Semiconductor-to-metal transition in rutile TiO 2 induced by tensile strain

DOE PAGES

Benson, Eric E.; Miller, Elisa M.; Nanayakkara, Sanjini U.; ...

2017-02-10

Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO 2 thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n-type semiconductor for unstrained TiO 2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectramore » show that samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n-type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies ( n-type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.« less

Energy exchange between a laser beam and charged particles using inverse transition radiation and method for its use

DOEpatents

Kimura, Wayne D.; Romea, Richard D.; Steinhauer, Loren C.

1998-01-01

A method and apparatus for exchanging energy between relativistic charged particles and laser radiation using inverse diffraction radiation or inverse transition radiation. The beam of laser light is directed onto a particle beam by means of two optical elements which have apertures or foils through which the particle beam passes. The two apertures or foils are spaced by a predetermined distance of separation and the angle of interaction between the laser beam and the particle beam is set at a specific angle. The separation and angle are a function of the wavelength of the laser light and the relativistic energy of the particle beam. In a diffraction embodiment, the interaction between the laser and particle beams is determined by the diffraction effect due to the apertures in the optical elements. In a transition embodiment, the interaction between the laser and particle beams is determined by the transition effect due to pieces of foil placed in the particle beam path.

Equation of State of Structured Matter at Finite Temperature

NASA Astrophysics Data System (ADS)

Maruyama, T.; Yasutake, N.; Tatsumi, T.

We investigate the properties of nuclear matter at the first-order phase transitions such as liquid-gas phase transition and hadron-quark phase transition. As a general feature of the first-order phase transitions of matter consisting of many species of charged particles, there appears a mixed phases with geometrical structures called ``pasta'' due to the balance of the Coulomb repulsion and the surface tension between two phases [G.~D.~Ravenhall, C.~J.~Pethick and J.~R.~Wilson, Phys. Rev. Lett. 50 (1983), 2066. M.~Hashimoto, H.~Seki and M.~Yamada, Prog. Theor. Phys. 71 (1984), 320.] The equation of state (EOS) of mixed phase is different from the one obtained by a bulk application of the Gibbs conditions or by the Maxwell construction due to the effects of the non-uniform structure. We show that the charge screening and strong surface tension make the EOS close to that of the Maxwell construction. The thermal effects are elucidated as well as the above finite-size effects.

Theoretical studies on effective metal-to-ligand charge transfer characteristics of novel ruthenium dyes for dye sensitized solar cells.

PubMed

Wang, Huei-Tang; Taufany, Fadlilatul; Nachimuthu, Santhanamoorthi; Jiang, Jyh-Chiang

2014-05-01

The development of ruthenium dye-sensitizers with highly effective metal-to-ligand charge transfer (MLCT) characteristics and narrowed transition energy gaps are essential for the new generation of dye-sensitized solar cells. Here, we designed a novel anchoring ligand by inserting the cyanovinyl-branches inside the anchoring ligands of selected highly efficient dye-sensitizers and studied their intrinsic optical properties using theoretical methods. Our calculated results show that the designed ruthenium dyes provide good performances as sensitizers compared to the selected efficient dyes, because of their red-shift in the UV-visible absorption spectra with an increase in the absorption intensity, smaller energy gaps and thereby enhancing MLCT transitions. We found that, the designed anchoring ligand acts as an efficient "electron-acceptor" which boosts electron-transfer from a -NCS ligand to this ligand via a Ru-bridge, thus providing a way to lower the transition energy gap and enhance the MLCT transitions.

Insulator-semimetallic transition in quasi-1D charged impurity-infected armchair boron-nitride nanoribbons

NASA Astrophysics Data System (ADS)

Dinh Hoi, Bui; Yarmohammadi, Mohsen

2018-04-01

We address control of electronic phase transition in charged impurity-infected armchair-edged boron-nitride nanoribbons (ABNNRs) with the local variation of Fermi energy. In particular, the density of states of disordered ribbons produces the main features in the context of pretty simple tight-binding model and Green's functions approach. To this end, the Born approximation has been implemented to find the effect of π-band electron-impurity interactions. A modulation of the π-band depending on the impurity concentrations and scattering potentials leads to the phase transition from insulator to semimetallic. We present here a detailed physical meaning of this transition by studying the treatment of massive Dirac fermions. From our findings, it is found that the ribbon width plays a crucial role in determining the electronic phase of disordered ABNNRs. The obtained results in controllable gap engineering are useful for future experiments. Also, the observations in this study have also fueled interest in the electronic properties of other 2D materials.

Kinetic mechanism for reversible structural transition in MoTe2 induced by excess charge carriers

NASA Astrophysics Data System (ADS)

Rubel, O.

2018-06-01

Kinetic of a reversible structural transition between insulating (2H) and metallic (1T ') phases in a monolayer MoTe2 due to an electrostatic doping is studied using first-principle calculations. The driving force for the structural transition is the energy gained by transferring excess electrons from the bottom of the conduction band to lower energy gapless states in the metallic phase as have been noticed in earlier studies. The corresponding structural transformation involves dissociation of Mo-Te bonds (one per formula unit), which results in a kinetic energy barrier of 0.83 eV. The transformation involves a consecutive movement of atoms similar to a domain wall motion. The presence of excess charge carriers modifies not only the total energy of the initial and final states, but also lowers an energy of the transition state. An experimentally observed hysteresis in the switching process can be attributed to changes in the kinetic energy barrier due to its dependence on the excess carrier density.

Experimental and computational studies on the electronic excited states of nitrobenzene

NASA Astrophysics Data System (ADS)

Krishnakumar, Sunanda; Das, Asim Kumar; Singh, Param Jeet; Shastri, Aparna; Rajasekhar, B. N.

2016-11-01

The gas phase electronic absorption spectrum of nitrobenzene (C6H5NO2) in the 4.5-11.2 eV region is recorded using synchrotron radiation with a view to comprehend the nature of the excited states. Electronic excited states of nitrobenzene are mainly classified as local excitations within the benzene ring or nitro group and charge transfer excitations between the benzene and nitro group, with some transitions showing percentage from both. The nature of molecular orbitals, their orderings and energies are obtained from density functional theory calculations which help in assigning partially assigned/unassigned features in earlier photoelectron spectroscopy studies. Optimized geometry of ionic nitrobenzene predicts redistribution of charge density in the benzene ring rather than the nitro group resulting in stabilization of the benzene ring π orbitals in comparison to the neutral molecule. Time dependent density functional theory computations are found to describe the experimental spectra well with respect to energies, relative intensities and nature of the observed transitions in terms of valence, Rydberg or charge transfer type. New insights into the interpretation of 1B2u←1A1g and 1B1u←1A1g shifted benzene transitions in light of the present computational calculations are presented. The first few members of the ns, np and nd type Rydberg series in nitrobenzene, converging to the first six ionization potentials, identified in the spectra as weak but sharp peaks are reported for the first time. In general, transitions to the lowest three unoccupied molecular orbitals 4b1, 3a2 and 5b1 are valence or charge transfer in nature, while excitations to higher orbitals are predominantly Rydberg in nature. This work presents a consolidated experimental study and theoretical interpretation of the electronic absorption spectrum of nitrobenzene.

Evidence for charge-trapping inducing polymorphic structural-phase transition in pentacene.

PubMed

Ando, Masahiko; Kehoe, Tom B; Yoneya, Makoto; Ishii, Hiroyuki; Kawasaki, Masahiro; Duffy, Claudia M; Minakata, Takashi; Phillips, Richard T; Sirringhaus, Henning

2015-01-07

Trapped-charge-induced transformation of pentacene polymorphs is observed by using in situ Raman spectroscopy and molecular dynamics simulations reveal that the charge should be localized in pentacene molecules at the interface with static intermolecular disorder along the long axis. Quantum chemical calculations of the intermolecular transfer integrals suggest the disorder to be large enough to induce Anderson-type localization. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

New Physical Mechanism for Lightning

NASA Astrophysics Data System (ADS)

Artekha, Sergey N.; Belyan, Andrey V.

2018-02-01

The article is devoted to electromagnetic phenomena in the atmosphere. The set of experimental data on the thunderstorm activity is analyzed. It helps to identify a possible physical mechanism of lightning flashes. This mechanism can involve the formation of metallic bonds in thunderclouds. The analysis of the problem is performed at a microphysical level within the framework of quantum mechanics. The mechanism of appearance of metallic conductivity includes the resonant tunneling of electrons along resonance-percolation trajectories. Such bonds allow the charges from the vast cloud charged subsystems concentrate quickly in lightning channel. The formation of metal bonds in the thunderstorm cloudiness is described as the second-order phase transition. A successive mechanism for the process of formation and development of the lightning channel is suggested. This mechanism is associated with the change in the orientation of crystals in growing electric field. Possible consequences of the quantum-mechanical mechanism under discussion are compared with the results of observations.

Topological Triply Degenerate Points Induced by Spin-Tensor-Momentum Couplings

NASA Astrophysics Data System (ADS)

Hu, Haiping; Hou, Junpeng; Zhang, Fan; Zhang, Chuanwei

2018-06-01

The recent discovery of triply degenerate points (TDPs) in topological materials has opened a new perspective toward the realization of novel quasiparticles without counterparts in quantum field theory. The emergence of such protected nodes is often attributed to spin-vector-momentum couplings. We show that the interplay between spin-tensor- and spin-vector-momentum couplings can induce three types of TDPs, classified by different monopole charges (C =±2 , ±1 , 0). A Zeeman field can lift them into Weyl points with distinct numbers and charges. Different TDPs of the same type are connected by intriguing Fermi arcs at surfaces, and transitions between different types are accompanied by level crossings along high-symmetry lines. We further propose an experimental scheme to realize such TDPs in cold-atom optical lattices. Our results provide a framework for studying spin-tensor-momentum coupling-induced TDPs and other exotic quasiparticles.

The perspectives of femtosecond imaging and spectroscopy of complex materials using electrons

NASA Astrophysics Data System (ADS)

Ruan, Chong-Yu; Duxbury, Phiilp M.; Berz, Martin

2014-09-01

The coexistence of various electronic and structural phases that are close in free-energy is a hallmark in strongly correlated electron systems with emergent properties, such as metal-insulator transition, colossal magnetoresistance, and high-temperature superconductivity. The cooperative phase transitions from one functional state to another can involve entanglements between the electronically and structurally ordered states, hence deciphering the fundamental mechanisms is generally difficult and remains very active in condensed matter physics and functional materials research. We outline the recent ultrafast characterizations of 2D charge-density wave materials, including the nonequilibrium electron dynamics unveiled by ultrafast optical spectroscopy-based techniques sensitive to the electronic order parameter. We also describe the most recent findings from ultrafast electron crystallography, which provide structural aspects to correlate lattice dynamics with electronic evolutions to address the two sides of a coin in the ultrafast switching of a cooperative state. Combining these results brings forth new perspectives and a fuller picture in understanding lightmatter interactions and various switching mechanisms in cooperative systems with many potential applications. We also discuss the prospects of implementing new ultrafast electron imaging as a local probe incorporated with femtosecond select-area diffraction, imaging and spectroscopy to provide a full scope of resolution to tackle the more challenging complex phase transitions on the femtosecond-nanometer scale all at once based on a recent understanding of the spacespace- charge-driven emittance limitation on the ultimate performance of these devices. The projection shows promising parameter space for conducting ultrafast electron micordiffraction at close to single-shot level, which is supported by the latest experimental characterization of such a system.

Local excitation of the 5-bromouracil chromophore in DNA. Computational and UV spectroscopic studies.

PubMed

Storoniak, Piotr; Rak, Janusz; Polska, Katarzyna; Blancafort, Lluís

2011-04-21

The UV electronic transition energies and their oscillator strengths for two stacked dimers having B-DNA geometries and consisting of 5-bromouracil ((Br)U) and a purine base were studied at the MS-CASPT2/6-311G(d) level with an active space of 12 orbitals and 12 electrons. The calculated energy of the first vertical (π,π*) transitions for the studied dimers remain in fair agreement with the maxima in the difference spectra measured for duplexes with the 5'-A(Br)U-3' or 5'-G(Br)U-3' sequences. Our MS-CASPT2 results show that the charge transfer (CT) states in which an electron is transferred from A/G to (Br)U are located at much higher energies than the first (π,π*) transitions, which involve local excitation (LE) of (Br)U. Moreover, CT transitions are characterized by small oscillator strengths, which implies that they could not be excited directly. The results of the current studies suggest that the formation of the reactive uracil-5-yl radical in DNA is preceded by the formation of the highly oxidative LE state of (Br)U, which is followed by electron transfer, presumably from guanine.