Photodissociation and charge transfer dynamics of negative ions studied with femtosecond photoelectron spectroscopy

International Nuclear Information System (INIS)

Zanni, Martin T.

1999-01-01

This dissertation presents studies aimed at understanding the potential energy surfaces and dynamics of isolated negative ions, and the effects of solvent on each. Although negative ions play important roles in atmospheric and solution phase chemistry, to a large extent the ground and excited state potential energy surfaces of gas phase negative ions are poorly characterized, and solvent effects even less well understood. In an effort to fill this gap, the author's coworkers and the author have developed a new technique, anion femtosecond photoelectron spectroscopy, and applied it to gas phase photodissociation and charge transfer processes. Studies are presented that (1) characterize the ground and excited states of isolated and clustered anions, (2) monitor the photodissociation dynamics of isolated and clustered anions, and (3) explore the charge-transfer-to-solvent states of atomic iodide clustered with polar and non-polar solvents

Failures of TDDFT in describing the lowest intramolecular charge-transfer excitation in para-nitroanilin

DEFF Research Database (Denmark)

Eriksen, J.J.; Sauer, S.P.A.; Mikkelsen, K.V.

2013-01-01

We investigate the failure of Time{Dependent Density Functional Theory (TDDFT) with the CAM{B3LYP exchange{correlation (xc) functional coupled to the Polarizable Embedding (PE) scheme (PE-CAM-B3LYP) in reproducing the solvatochromic shift of the lowest intense charge{transfer excitation in para...... the electric dipole moments in the gas phase and for 100 solvent congurations. We find that CAM-B3LYP overestimates the amount of charge separation inherent in the ground state and TDDFT/CAM-B3LYP drastically underestimates this amount in the excited charge-transfer state. As the errors in the solvatochromatic...... to benchmark results of TDDFT calculations with CAM-B3LYP for intramolecular charge{transfer excitations in molecular systems similar to pNA against higher{level ab initio wave function methods, like, e.g., CCSD, prior to their use. Using the calculated change in dipole moment upon excitation as a measure...

Heat transfer enhancement of phase change materials by fins under simultaneous charging and discharging

International Nuclear Information System (INIS)

Joybari, Mahmood Mastani; Haghighat, Fariborz; Seddegh, Saeid; Al-Abidi, Abduljalil A.

2017-01-01

Highlights: • CFD simulation of a finned triplex tube heat exchanger with PCM under simultaneous charging and discharging. • Developed fin configurations for SCD, compatible with natural convection. • More fins enhanced the heat transfer as long as natural convection was not suppressed. • Longer fins enhanced the heat transfer as long as natural convection was not suppressed. • The effect of fin thickness was negligible, similar to non-SCD conditions. - Abstract: Due to the inherent intermittency of renewable energy sources such as solar, latent heat thermal energy storage in phase change materials (PCMs) has received considerable attention. Among several techniques to enhance PCMs’ thermal conductivity, the majority of studies have focused on fin integration due to its simplicity, ease of manufacturing, and low cost. In this study, utilization of extended surfaces (by longitudinal fins) was investigated by development of a numerical model to study the performance of a triplex tube heat exchanger (TTHX) equipped with a PCM under simultaneous charging and discharging (SCD). Governing equations were developed and numerically solved using ANSYS Fluent v16.2. Three conventional fin geometries and six developed fin configurations were compared based on the temperature, liquid fraction, and natural convection behavior under both SCD and non-SCD conditions. The intensity of natural convection was investigated for different fins for the inside heating/outside cooling scenario based on the solid–liquid interface evolution over time. The results indicated that since the buoyancy forces induce upward melted PCM motion, the inner hot tube requires fins on its lower half, while the outer cold one should be extended from its upper half. It was concluded that the case with 3 hot tube fins and 1 cold tube fin is most compatible with natural convection and provides the best performance under SCD conditions.

Charge Transfer into Aqueous Droplets via Kilovolt Potentials

Science.gov (United States)

Hamlin, B. S.; Rosenberg, E. R.; Ristenpart, W. D.

2012-11-01

When an aqueous droplet immersed in an insulating oil contacts an electrified surface, the droplet acquires net charge. For sufficiently large field strengths, the charged droplet is driven back and forth electrophoretically between the electrodes, in essence ``bouncing'' between them. Although it is clear that the droplet acquires charge, the underlying mechanism controlling the charge transfer process has been unclear. Here we demonstrate that the chemical species present in the droplet strongly affect the charge transfer process into the drop. Using two independent charge measurement techniques, high speed video velocimetry and direct current measurement, we show that the charge acquired during contact is strongly influenced by the droplet pH. We also provide physical evidence that the electrodes undergo electroplating or corrosion for droplets with appropriate chemical species present. Together, the observations strongly suggest that electrochemical reactions govern the charge transfer process into the droplet.

Dissociative electron attachment and charge transfer in condensed matter

International Nuclear Information System (INIS)

Bass, A.D.; Sanche, L.

2003-01-01

Experiments using energy-selected beams of electrons incident from vacuum upon thin vapour deposited solids show that, as in the gas-phase, scattering cross sections at low energies are dominated by the formation of temporary negative ions (or resonances) and that molecular damage may be effected via dissociative electron attachment (DEA). Recent results also show that charge transfer between anionic states of target molecules and their environment is often crucial in determining cross sections for electron driven processes. Here, we review recent work from our laboratory, in which charge transfer is observed. For rare gas solids, electron exchange between the electron-exciton complex and either a metal substrate or co-adsorbed molecule enhances the desorption of metastable atoms and/or molecular dissociation. We discuss how transient electron capture by surface electron states of a substrate and subsequent electron transfer to a molecular adsorbate enhances the effective cross sections for DEA. We also consider the case of DEA to CF 2 Cl 2 condensed on water and ammonia ices, where electron exchange between pre-solvated electron states of ice and transient molecular anions can also increase DEA cross sections. Electron transfer from molecular resonances into pre-solvated electron states of ice is also discussed

Bond charges and electronic charge transfer in ternary semiconductors

International Nuclear Information System (INIS)

Pietsch, U.

1986-01-01

By means of a simple molecule-theoretic model of 'linear superposition of two-electron molecules' the bond charges between nearest neighbours and the effective charges of ions are calculated for ternary zinc-blende structure alloys as well as chalcopyrite semiconductors. Taking into account both, the charge transfer among the ions caused by the differences of electronegativities of atoms used and between the bonds created by the internal stress of the lattice a nearly unvaried averaged bond charge amount of the alloy is found, but rather dramatically changed local bond charge parameters in comparison with the respective values of binary compounds used. This fact should influence the noncentral force interaction in such semiconductors. (author)

Temperature dependence of positronium reactivities with charge transfer molecules in bilayer membranes

International Nuclear Information System (INIS)

Jean, Y.C.; Yu, C.; Wang, Y.Y.; Yeh, Y.Y.

1984-01-01

Rate constants for positronium atoms reacting chemically with charge-transfer molecules such as p-benzoquinone, nitrobenzene, and coenzyme Q-10 in a model bilayer membrane, dipalmitoylphosphatidylcholine (DPPC), have been measured at temperatures between 23 and 65 0 C. A strong variation of the positronium chemical reactivities, k/sub Ps/ was observed in these systems: k/sub Ps/ increases with increasing temperature until the pretransition temperature of the membrane reaches a maximum value near the main transition temperature and decreases at temperatures higher than the main transition temperature. This variation is interpreted in terms of fluidity and permeability changes associated with the phase transitions of membranes and in terms of charge-transfer-complex formation between the solubilized molecules and the polar head of the membrane. These results demonstrate that positronium and its annihilation characteristics can be employed to investigate charge transport phenomena and microstructural changes of real biological membranes

Efficient charge generation by relaxed charge-transfer states at organic interfaces

KAUST Repository

Vandewal, Koen

2013-11-17

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

Efficient charge generation by relaxed charge-transfer states at organic interfaces

KAUST Repository

Vandewal, Koen; Albrecht, Steve N.; Hoke, Eric T.; Graham, Kenneth; Widmer, Johannes; Douglas, Jessica D.; Schubert, Marcel; Mateker, William R.; Bloking, Jason T.; Burkhard, George F.; Sellinger, Alan; Frechet, Jean; Amassian, Aram; Riede, Moritz Kilian; McGehee, Michael D.; Neher, Dieter; Salleo, Alberto

2013-01-01

Interfaces between organic electron-donating (D) and electron-accepting (A) materials have the ability to generate charge carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold via weakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer:fullerene, small-molecule:C60 and polymer:polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy. © 2014 Macmillan Publishers Limited.

The charge transfer structure and effective energy transfer in multiplayer assembly film

International Nuclear Information System (INIS)

Li Mingqiang; Jian Xigao

2005-01-01

Charge transfer multiplayer films have been prepared by layer-by-layer self-assembly technique. The films incorporate the rare-earth-containing polyoxometalate K 11 [Eu{PW 11 O 39 } 2 ].nH 2 O and the rich electron polyelectrolyte poly(3-viny-1-methyl-pyridine) quaternary ammonium and display a linear increase in the absorption and film thickness with the number of deposition cycles. Ultraviolet and visible absorption spectra, atomic force micrographs, small-angle X-ray reflectivity measurements, and photoluminescence spectra were used to determine the structure of films. Linear and regular multilayer growth was observed. We can observe the formation of charge transfer complex compound in multiplayer by layer-by-layer assembly method. Most importantly, the luminescence spectra show the charge transfer band in assembly films, which suggest that energy could be effectively transferred to rare earth ions in assembly multiplayer films

Two-Centre Close-Coupling method in charge transfer

Directory of Open Access Journals (Sweden)

Reza Bagheri

2017-09-01

Full Text Available In the present work, the transition matrix elements as well as differential and total scattering cross-sections for positronium formation in Positron-Hydrogen atom collision and hydrogen formation in Positronium-Hydrogen ion collision, through the charge transfer channel by Two-Centre Close-Coupling method up to a first order approximation have been calculated. The charge transfer collision is assumed to be a three-body reaction, while the projectile is a plane wave. Additionally, the hydrogen and positronium atoms are assumed, initially, to be in their ground states. For the case of charge transfer in the scattering of positron by hydrogen atoms, the differential cross sections are plotted for the energy range of 50eV to 10keV, where the Thomas peak is clearly observable. Finally, the total scattering cross-section for the charge transfer in the collision of Positron-Hydrogen and Positronium-Hydrogen ion are plotted as a function of projectile energies and compared with other methods in the literature.

Transfer of momentum, mass and charge in heavy ion collisions

International Nuclear Information System (INIS)

Beck, F.; Feldmeier, H.; Dworzecka, M.

1979-01-01

A model for the first two phases of heavy ion collisions based on the transport of single nucleons through the window between the two scattering nuclei is described in some detail. It is pointed out that the model can account simultaneously for a large portion of the energy transfer from relative to intrinsic motion and for the observed variances in mass and charge numbers for reaction times up to the order of 10 -21 s. (P.L.)

Collisional charging of individual submillimeter particles: Using ultrasonic levitation to initiate and track charge transfer

Science.gov (United States)

Lee, Victor; James, Nicole M.; Waitukaitis, Scott R.; Jaeger, Heinrich M.

2018-03-01

Electrostatic charging of insulating fine particles can be responsible for numerous phenomena ranging from lightning in volcanic plumes to dust explosions. However, even basic aspects of how fine particles become charged are still unclear. Studying particle charging is challenging because it usually involves the complexities associated with many-particle collisions. To address these issues, we introduce a method based on acoustic levitation, which makes it possible to initiate sequences of repeated collisions of a single submillimeter particle with a flat plate, and to precisely measure the particle charge in situ after each collision. We show that collisional charge transfer between insulators is dependent on the hydrophobicity of the contacting surfaces. We use glass, which we modify by attaching nonpolar molecules to the particle, the plate, or both. We find that hydrophilic surfaces develop significant positive charges after contacting hydrophobic surfaces. Moreover, we demonstrate that charging between a hydrophilic and a hydrophobic surface is suppressed in an acidic environment and enhanced in a basic one. Application of an electric field during each collision is found to modify the charge transfer, again depending on surface hydrophobicity. We discuss these results within the context of contact charging due to ion transfer, and we show that they lend strong support to O H- ions as the charge carriers.

Charge-transfer channel in quantum dot-graphene hybrid materials

Science.gov (United States)

Cao, Shuo; Wang, Jingang; Ma, Fengcai; Sun, Mengtao

2018-04-01

The energy band theory of a classical semiconductor can qualitatively explain the charge-transfer process in low-dimensional hybrid colloidal quantum dot (QD)-graphene (GR) materials; however, the definite charge-transfer channels are not clear. Using density functional theory (DFT) and time-dependent DFT, we simulate the hybrid QD-GR nanostructure, and by constructing its orbital interaction diagram, we show the quantitative coupling characteristics of the molecular orbitals (MOs) of the hybrid structure. The main MOs are derived from the fragment MOs (FOs) of GR, and the Cd13Se13 QD FOs merge with the GR FOs in a certain proportion to afford the hybrid system. Upon photoexcitation, electrons in the GR FOs jump to the QD FOs, leaving holes in the GR FOs, and the definite charge-transfer channels can be found by analyzing the complex MOs coupling. The excited electrons and remaining holes can also be localized in the GR or the QD or transfer between the QD and GR with different absorption energies. The charge-transfer process for the selected excited states of the hybrid QD-GR structure are testified by the charge difference density isosurface. The natural transition orbitals, charge-transfer length analysis and 2D site representation of the transition density matrix also verify the electron-hole delocalization, localization, or coherence chacracteristics of the selected excited states. Therefore, our research enhances understanding of the coupling mechanism of low-dimensional hybrid materials and will aid in the design and manipulation of hybrid photoelectric devices for practical application in many fields.

Computational models of an inductive power transfer system for electric vehicle battery charge

Science.gov (United States)

Anele, A. O.; Hamam, Y.; Chassagne, L.; Linares, J.; Alayli, Y.; Djouani, K.

2015-09-01

One of the issues to be solved for electric vehicles (EVs) to become a success is the technical solution of its charging system. In this paper, computational models of an inductive power transfer (IPT) system for EV battery charge are presented. Based on the fundamental principles behind IPT systems, 3 kW single phase and 22 kW three phase IPT systems for Renault ZOE are designed in MATLAB/Simulink. The results obtained based on the technical specifications of the lithium-ion battery and charger type of Renault ZOE show that the models are able to provide the total voltage required by the battery. Also, considering the charging time for each IPT model, they are capable of delivering the electricity needed to power the ZOE. In conclusion, this study shows that the designed computational IPT models may be employed as a support structure needed to effectively power any viable EV.

Computational models of an inductive power transfer system for electric vehicle battery charge

International Nuclear Information System (INIS)

Anele, A O; Hamam, Y; Djouani, K; Chassagne, L; Alayli, Y; Linares, J

2015-01-01

One of the issues to be solved for electric vehicles (EVs) to become a success is the technical solution of its charging system. In this paper, computational models of an inductive power transfer (IPT) system for EV battery charge are presented. Based on the fundamental principles behind IPT systems, 3 kW single phase and 22 kW three phase IPT systems for Renault ZOE are designed in MATLAB/Simulink. The results obtained based on the technical specifications of the lithium-ion battery and charger type of Renault ZOE show that the models are able to provide the total voltage required by the battery. Also, considering the charging time for each IPT model, they are capable of delivering the electricity needed to power the ZOE. In conclusion, this study shows that the designed computational IPT models may be employed as a support structure needed to effectively power any viable EV. (paper)

Charge transfer reactions in Xe plasma expansion

International Nuclear Information System (INIS)

Jiao, C. Q.; Garscadden, A.; Ganguly, B. N.

2007-01-01

Charge transfer reactions of fast Xe ions with hydrocarbons including methane (CH 4 ), ethene (C 2 H 4 ), and propane (C 3 H 8 ) are studied by adding these hydrocarbon gases into a cross flowing Xe plasma expansion. Branching ratios and relative reaction rates for the charge transfers of fast Xe + with each of the three hydrocarbon gases are measured under different rf powers of the inductively coupled Xe discharge. For CH 4 /Xe system, we find that fast Xe + reacts readily with CH 4 generating CH 4 + and CH 3 + in a ratio of 1:0.56, with an estimated rate coefficient of (2.3±0.3)x10 -10 cm 3 /s at 75 W rf power which slowly increases to (2.9±0.3)x10 -10 cm 3 /s at 250 W (error bars reflect only the uncertainties due to the unknown extent of the ion recombination that follows the charge transfer reaction). These observed charge transfer reactions are made possible by the kinetically excited Xe ions produced by free expansion of the plasma. For the C 2 H 4 /Xe system product ions C 2 H 4 + and C 2 H 2 + are observed, and for C 3 H 8 /Xe, C 2 H 4 + and C 2 H 5 + and minor product ions including C 2 H 2 + and C 3 H 7 + are observed

Charge-transfer cross sections in collisions of ground-state Ca and H+

Science.gov (United States)

Dutta, C. M.; Oubre, C.; Nordlander, P.; Kimura, M.; Dalgarno, A.

2006-03-01

We have investigated collisions of Ca(4s2) with H+ in the energy range of 200eV/u-10keV/u using the semiclassical molecular-orbital close-coupling (MOCC) method with 18 coupled molecular states ( 11Σ+1 and seven Π+1 states) to determine charge-transfer cross sections. Except for the incoming channel 6Σ+1 , the molecular states all correspond to charge-transfer channels. Inclusion of Ca2+-H- is crucial in the configuration-interaction calculation for generating the molecular wave functions and potentials. Because of the Coulomb attraction, the state separating to Ca2+-H- creates many avoided crossings, even though at infinite separation it lies energetically above all other states that we included. Because of the avoided crossings between the incoming channel 6Σ+1 and the energetically close charge-transfer channel 7Σ+1 the charge-transfer interaction occurs at long range. This makes calculations of charge-transfer cross sections by the MOCC method very challenging. The total charge-transfer cross sections increase monotonically from 3.4×10-15cm2 at 200eV/u to 4.5×10-15cm2 at 10keV/u . Charge transfer occurs mostly to the excited Ca+(5p) state in the entire energy range, which is the sum of the charge transfer to 7Σ+1 and 4Π+1 . It accounts for ˜47% of the total charge transfer cross sections at 200eV/u . However, as the energy increases, transfer to Ca+(4d) increases, and at 10keV/u the charge-transfer cross sections for Ca+(5p) and Ca+(4d) become comparable, each giving ˜38% of the total cross section.

Charge-transfer cross sections in collisions of ground-state Ca and H+

International Nuclear Information System (INIS)

Dutta, C. M.; Oubre, C.; Nordlander, P.; Kimura, M.; Dalgarno, A.

2006-01-01

We have investigated collisions of Ca(4s 2 ) with H + in the energy range of 200 eV/u-10 keV/u using the semiclassical molecular-orbital close-coupling (MOCC) method with 18 coupled molecular states (11 1 Σ + and seven 1 Π + states) to determine charge-transfer cross sections. Except for the incoming channel 6 1 Σ + , the molecular states all correspond to charge-transfer channels. Inclusion of Ca 2+ -H - is crucial in the configuration-interaction calculation for generating the molecular wave functions and potentials. Because of the Coulomb attraction, the state separating to Ca 2+ -H - creates many avoided crossings, even though at infinite separation it lies energetically above all other states that we included. Because of the avoided crossings between the incoming channel 6 1 Σ + and the energetically close charge-transfer channel 7 1 Σ + the charge-transfer interaction occurs at long range. This makes calculations of charge-transfer cross sections by the MOCC method very challenging. The total charge-transfer cross sections increase monotonically from 3.4x10 -15 cm 2 at 200 eV/u to 4.5x10 -15 cm 2 at 10 keV/u. Charge transfer occurs mostly to the excited Ca + (5p) state in the entire energy range, which is the sum of the charge transfer to 7 1 Σ + and 4 1 Π + . It accounts for ∼47% of the total charge transfer cross sections at 200 eV/u. However, as the energy increases, transfer to Ca + (4d) increases, and at 10 keV/u the charge-transfer cross sections for Ca + (5p) and Ca + (4d) become comparable, each giving ∼38% of the total cross section

Quasi-resonant K-K charge transfer

International Nuclear Information System (INIS)

Hagmann, S.; Cocke, C.L.; Richard, P.; Skutlartz, A.; Kelbch, S.; Schmidt-Boecking, H.; Schuch, R.

1983-01-01

The impact parameter dependence, P(b), of single and double K to K charge transfer have been deduced from the coincidences between K-Auger electrons and scattered particles for F 9+ + Ne and F 9+ + Ne collisions at 10 MeV and 4.4 MeV. The 4.4 MeV single K-K transfer probability exhibits oscillations with b. The P(b) for delta-electron emission is also reported. To obtain more details on the mechanism, K-Auger electron-Ne recoil ion coincidences are measured for both F 8+ and F 9+ projectiles. The relative amounts of recoil ions and of satellite and hypersatellite Auger transitions vary substantially with projectile charge state. 11 references, 11 figures

Mass and charge transfer within a floating water bridge

Science.gov (United States)

Fuchs, Elmar C.; Agostinho, Luewton L. F.; Eisenhut, Mathias; Woisetschläger, Jakob

2010-11-01

When high voltage is applied to pure water filled into two beakers close to each other, a connection forms spontaneously, giving the impression of a floating water bridge 1-8. This phenomenon is of special interest, since it comprises a number of phenomena currently tackled in modern water science. In this work, the charge and mass transfer through the water bridge are investigated with schlieren visualization and laser interferometry. It can be shown that the addition of a pH dye increases the H+ and OH- production with subsequent electrolysis, whereas schlieren and interferometric methods reveal another mechanism where charge and mass transfer appear to be coupled. Whereas this mechanism seems to be responsible for the electrolysis-less charge and mass transfer in the water bridge, it is increasingly superseded by the electrochemical mechanism with rising conductivity. Thus it can be shown that a pH dye does only indirectly visualize the charge transfer in the water bridge since it is dragged along with the water flow like any other dye, and additionally promotes conventional electrochemical conduction mechanisms, thereby enhancing electrolysis and reducing the masscoupled charge transport and thus destabilizing the bridge.

Charge transfer cross sections for dysprosium and cerium

Energy Technology Data Exchange (ETDEWEB)

Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-06-01

Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82{+-}0.14) x 10{sup -14} cm{sup 2} for dysprosium and (0.88{+-}0.12) x 10{sup -14} cm{sup 2} for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

Charge transfer cross sections for dysprosium and cerium

International Nuclear Information System (INIS)

Adachi, Hajime; Tamura, Koji; Okazaki, Tetsuji; Shibata, Takemasa

1998-06-01

Symmetric resonant charge transfer cross sections between singly ionized ions and the parent atoms were measured for dysprosium and cerium in the impact energy of 200-2000eV. The cross sections were determined from the ratio between the number of ions produced by charge transfer and those in primary ion beam. The primary ion beam was produced by a laser ion source in which their atoms were ionized by laser resonant photo-ionization. The slow ions produced by charge transfer and fast primary ions were detected with Faraday cups. The obtained cross sections were (1.82±0.14) x 10 -14 cm 2 for dysprosium and (0.88±0.12) x 10 -14 cm 2 for cerium in the above energy range. The difference of these values can mostly be explained by considering the electron configurations of these atoms and ions. (author)

Charge Transfer and Catalysis at the Metal Support Interface

Energy Technology Data Exchange (ETDEWEB)

Baker, Lawrence Robert [Univ. of California, Berkeley, CA (United States)

2012-07-31

Kinetic, electronic, and spectroscopic characterization of model Pt–support systems are used to demonstrate the relationship between charge transfer and catalytic activity and selectivity. The results show that charge flow controls the activity and selectivity of supported metal catalysts. This dissertation builds on extensive existing knowledge of metal–support interactions in heterogeneous catalysis. The results show the prominent role of charge transfer at catalytic interfaces to determine catalytic activity and selectivity. Further, this research demonstrates the possibility of selectively driving catalytic chemistry by controlling charge flow and presents solid-state devices and doped supports as novel methods for obtaining electronic control over catalytic reaction kinetics.

Voltammetry for the charge transfer at two immiscible electrolyte solutions interface

International Nuclear Information System (INIS)

Kihara, S.; Suzuki, M.; Maeda, K.; Ogura, K.; Matsui, M.; Yoshida, Z.

1989-01-01

The voltammetry for the charge transfer (VCT) at the interface of immicible solutions is a very powerful method for understanding the dynamic features of the charge transfer because of its unmatched advantage that the transfer energy and the number of charges transferred can be measured simultaneously and in situ. In the present paper, several novel systems for electron transfer are outlined, and the following topics are discussed based on results obtained by the current scan polarography at the solution dropping electrode developed as a technique for VCT: the relation between the half-wave potential in VCT for ion transfer and the characteristics of the ion transferred; the relation between the half-wave potential in VCT for electron transfer and the electrochemical nature of a redox couple added in water and that added in organic solution; and the ion transfer through a liquid membrane promoted by electron transfer. Observations are presented and discussion is made on the characteristics of ion transfer polarograms, those of electron transfer polarograms, and ion transfer promoted by electron transfer at a liquid/membrane interface. (N.K.)

Charge-transfer spectra of tetravalent lanthanide ions in oxides

NARCIS (Netherlands)

Hoefdraad, H.E.

The charge-transfer spectra of Ce4+, Pr4+ and Tb4+ in a number of oxides are reported. It is noted that the position of the first charge-transfer band is fixed for the metal ion in an oxygen coordination of VI, but varies in VIII coordination as a function of the host lattice. It is argued that this

Robustness of the charge-ordered phases in IrTe2 against photoexcitation

Science.gov (United States)

Monney, C.; Schuler, A.; Jaouen, T.; Mottas, M.-L.; Wolf, Th.; Merz, M.; Muntwiler, M.; Castiglioni, L.; Aebi, P.; Weber, F.; Hengsberger, M.

2018-02-01

We present a time-resolved angle-resolved photoelectron spectroscopy study of IrTe2, which undergoes two first-order structural and charge-ordered phase transitions on cooling below 270 K and below 180 K. The possibility of inducing a phase transition by photoexcitation with near-infrared femtosecond pulses is investigated in the charge-ordered phases. We observe changes of the spectral function occurring within a few hundreds of femtoseconds and persisting up to several picoseconds, which we interpret as a partial photoinduced phase transition (PIPT). The necessary time for photoinducing these spectral changes increases with increasing photoexcitation density and reaches time scales longer than the rise time of the transient electronic temperature. We conclude that the PIPT is driven by a transient increase of the lattice temperature following the energy transfer from the electrons. However, the photoinduced changes of the spectral function are small, which indicates that the low-temperature phase is particularly robust against photoexcitation. We suggest that the system might be trapped in an out-of-equilibrium state, for which only a partial structural transition is achieved.

Theoretical Investigation of OCN(-) Charge Transfer Complexes in Condensed Phase Media: Spectroscopic Properties in Amorphous Ice

Science.gov (United States)

Park, Jin-Young; Woon, David E.

2004-01-01

Density functional theory (DFT) calculations of cyanate (OCN(-)) charge-transfer complexes were performed to model the "XCN" feature observed in interstellar icy grain mantles. OCN(-) charge-transfer complexes were formed from precursor combinations of HNCO or HOCN with either NH3 or H2O. Three different solvation strategies for realistically modeling the ice matrix environment were explored, including (1) continuum solvation, (2) pure DFT cluster calculations, and (3) an ONIOM DFT/PM3 cluster calculation. The model complexes were evaluated by their ability to reproduce seven spectroscopic measurements associated with XCN: the band origin of the OCN(-) asymmetric stretching mode, shifts in that frequency due to isotopic substitutions of C, N, O, and H, plus two weak features. The continuum solvent field method produced results consistent with some of the experimental data but failed to account for other behavior due to its limited capacity to describe molecular interactions with solvent. DFT cluster calculations successfully reproduced the available spectroscopic measurements very well. In particular, the deuterium shift showed excellent agreement in complexes where OCN(-) was fully solvated. Detailed studies of representative complexes including from two to twelve water molecules allowed the exploration of various possible solvation structures and provided insights into solvation trends. Moreover, complexes arising from cyanic or isocyanic acid in pure water suggested an alternative mechanism for the formation of OCN(-) charge-transfer complexes without the need for a strong base such as NH3 to be present. An extended ONIOM (B3LYP/PM3) cluster calculation was also performed to assess the impact of a more realistic environment on HNCO dissociation in pure water.

Charge transfer induced activity of graphene for oxygen reduction

International Nuclear Information System (INIS)

Shen, Anli; Xia, Weijun; Dou, Shuo; Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai

2016-01-01

Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR. (paper)

Electrosynthesis of Copper-Tetracyanoquinodimethane Based on the Coupling Charge Transfer across Water/1,2-Dichloroethane Interface

International Nuclear Information System (INIS)

Huang, Li; Li, Pei; Pamphile, Ndagijimana; Tian, Zhong-Qun; Zhan, Dongping

2014-01-01

Graphical abstract: - Highlights: • Organic semiconductor CuTCNQ is synthesized through electrochemistry of liquid/liquid interface. • A coupling charge transfer (CCT) mechanism is proposed for organic electrosynthesis. • The obtained CuTCNQ has good electrochemical and electronic properties. - Abstract: The organic salt Copper-Tetracyanoquinodimethane (CuTCNQ) is an important semiconductor used in electronics for field-effect transistors, switches and memory devices. Here we present a novel electrosynthetic method of CuTCNQ microneedles based on the coupling charge transfer across water/1,2-dichloroethane (W/1,2-DCE) interface. A HOPG electrode is covered by a small volume of 1,2-DCE solution, which is further covered by an aqueous solution to construct the W/1,2-DCE interface. When TCNQ in 1,2-DCE phase is reduced on HOPG, Cu 2+ in the aqueous solution will transfer across the W/1,2-DCE interface in order to maintain the electric neutrality. Therein CuTCNQ microneedles are formed which have good solid-state electrochemical and electronic properties. This coupling charge transfer mechanism is valuable and broadens the applications of liquid/liquid interface in organic electrosynthesis

Extraordinary Mechanism of the Diels-Alder Reaction: Investigation of Stereochemistry, Charge Transfer, Charge Polarization, and Biradicaloid Formation.

Science.gov (United States)

Sexton, Thomas; Kraka, Elfi; Cremer, Dieter

2016-02-25

The Diels-Alder reaction between 1,3-butadiene and ethene is investigated from far-out in the entrance channel to the very last step in the exit channel thus passing two bifurcation points and extending the range of the reaction valley studied with URVA (Unified Reaction Valley Approach) by 300% compared to previous studies. For the first time, the pre- and postchemical steps of the reaction are analyzed at the same level of theory as the actual chemical processes utilizing the path curvature and its decomposition into internal coordinate or curvilinear coordinate components. A first smaller charge transfer to the dienophile facilitates the rotation of gauche butadiene into its cis form. The actual chemical processes are initiated by a second larger charge transfer to the dienophile that facilitates pyramidalization of the reacting carbon centers, bond equalization, and biradicaloid formation of the reactants. The transition state is aromatically stabilized and moved by five path units into the entrance channel in line with the Hammond-Leffler postulate. The pseudorotation of the boat form into the halfchair of cyclohexene is analyzed. Predictions are made for the Diels-Alder reaction based on a 11-phase mechanism obtained by the URVA analysis.

Does charge transfer correlate with ignition probability?

International Nuclear Information System (INIS)

Holdstock, Paul

2008-01-01

Flammable or explosive atmospheres exist in many industrial environments. The risk of ignition caused by electrostatic discharges is very real and there has been extensive study of the incendiary nature of sparks and brush discharges. It is clear that in order to ignite a gas, an amount of energy needs to be delivered to a certain volume of gas within a comparatively short time. It is difficult to measure the energy released in an electrostatic discharge directly, but it is possible to approximate the energy in a spark generated from a well defined electrical circuit. The spark energy required to ignite a gas, vapour or dust cloud can be determined by passing such sparks through them. There is a relationship between energy and charge in a capacitive circuit and so it is possible to predict whether or not a spark discharge will cause an ignition by measuring the charge transferred in the spark. Brush discharges are in many ways less well defined than sparks. Nevertheless, some work has been done that has established a relationship between charge transferred in brush discharges and the probability of igniting a flammable atmosphere. The question posed by this paper concerns whether such a relationship holds true in all circumstances and if there is a universal correlation between charge transfer and ignition probability. Data is presented on discharges from textile materials that go some way to answering this question.

Enhancing SERS by Means of Supramolecular Charge Transfer

Science.gov (United States)

Wong, Eric; Flood, Amar; Morales, Alfredo

2009-01-01

In a proposed method of sensing small quantities of molecules of interest, surface enhanced Raman scattering (SERS) spectroscopy would be further enhanced by means of intermolecular or supramolecular charge transfer. There is a very large potential market for sensors based on this method for rapid detection of chemical and biological hazards. In SERS, the Raman signals (vibrational spectra) of target molecules become enhanced by factors of the order of 108 when those molecules are in the vicinities of nanostructured substrate surfaces that have been engineered to have plasmon resonances that enhance local electric fields. SERS, as reported in several prior NASA Tech Briefs articles and elsewhere, has remained a research tool and has not yet been developed into a practical technique for sensing of target molecules: this is because the short range (5 to 20 nm) of the field enhancement necessitates engineering of receptor molecules to attract target molecules to the nanostructured substrate surfaces and to enable reliable identification of the target molecules in the presence of interferants. Intermolecular charge-transfer complexes have been used in fluorescence-, photoluminescence-, and electrochemistry-based techniques for sensing target molecules, but, until now, have not been considered for use in SERS-based sensing. The basic idea of the proposed method is to engineer receptor molecules that would be attached to nanostructured SERS substrates and that would interact with the target molecules to form receptor-target supramolecular charge-transfer complexes wherein the charge transfer could be photoexcited.

Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

KAUST Repository

Gruenewald, Marco; Schirra, Laura K.; Winget, Paul; Kozlik, Michael; Ndione, Paul F.; Sigdel, Ajaya K.; Berry, Joseph J.; Forker, Roman; Bredas, Jean-Luc; Fritz, Torsten; Monti, Oliver L. A.

2015-01-01

with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron

Charge transfer devices and their application in physics

Energy Technology Data Exchange (ETDEWEB)

Soroko, L M [Joint Inst. for Nuclear Research, Dubna (USSR)

1979-01-01

Physical properties and technical specifications of charge transfer devices (CTD) are reviewed. The CTD are semiconductor devices based on silicon single crystals. The limiting charge density of the CTD, their efficiency of charge transfer, the background noise and radiation effects are considered. Fast response and low energy consumption are characteristic features of the devices. The application of the CTD in storage devices, real time spectral data processing systems and in streamer chambers is described. The algorithms of topological transformations in the stage of scanning particle track images, which can be realized with the help of the CTD are shortly considered. It is pointed out that applications of the CTD in different fields of science and technology are numerous and expanding.

Laser-induced charge transfer in the HeH2+ quasimolecule

International Nuclear Information System (INIS)

Errea, L.F.; Mendez, L.; Riera, A.

1983-01-01

In a recent publication, the charge transfer cross section for He 2+ +H(ls) collisions through photon-assisted 2psigma--3dsigma transitions was calculated; this calculation, however, contained several errors whose quantitative--even qualitative effect on the results is not obvious. We present a correct evaluation of this laser-induced cross section, which turns out to be larger, and present a maximum for longer wavelengths, than the values previously reported. In addition, we have checked the applicability of perturbation theory, of the stationary phase, uniform and Landau--Zener approximations, and the importance of potentially competitive photon-assisted reactions

Proton transfer to charged platinum electrodes. A molecular dynamics trajectory study.

Science.gov (United States)

Wilhelm, Florian; Schmickler, Wolfgang; Spohr, Eckhard

2010-05-05

A recently developed empirical valence bond (EVB) model for proton transfer on Pt(111) electrodes (Wilhelm et al 2008 J. Phys. Chem. C 112 10814) has been applied in molecular dynamics (MD) simulations of a water film in contact with a charged Pt surface. A total of seven negative surface charge densities σ between -7.5 and -18.9 µC cm(-2) were investigated. For each value of σ, between 30 and 84 initial conditions of a solvated proton within a water slab were sampled, and the trajectories were integrated until discharge of a proton occurred on the charged surfaces. We have calculated the mean rates for discharge and for adsorption of solvated protons within the adsorbed water layer in contact with the metal electrode as a function of surface charge density. For the less negative values of σ we observe a Tafel-like exponential increase of discharge rate with decreasing σ. At the more negative values this exponential increase levels off and the discharge process is apparently transport limited. Mechanistically, the Tafel regime corresponds to a stepwise proton transfer: first, a proton is transferred from the bulk into the contact water layer, which is followed by transfer of a proton to the charged surface and concomitant discharge. At the more negative surface charge densities the proton transfer into the contact water layer and the transfer of another proton to the surface and its discharge occur almost simultaneously.

Phonons and charge-transfer excitations in HTS superconductors

International Nuclear Information System (INIS)

Bishop, A.R.

1989-01-01

Some of the experimental and theoretical evidence implicating phonons and charge-transfer excitations in HTS superconductors is reviewed. It is suggested that superconductivity may be driven by a synergistic interplay of (anharmonic) phonons and electronic degrees of freedom (e.g., charge fluctuations, excitons). 47 refs., 5 figs

Photoinduced partial charge transfer between conjugated polymer and fullerene in solutions

International Nuclear Information System (INIS)

Lin Hongzhen; Weng Yufeng; Huang Hongmin; He Qingguo; Zheng Min; Bai Fenglian

2004-01-01

Photoinduced charge transfer between a conjugated polymer and C 60 and the related processes were investigated in dilute solutions. The substantial fluorescence quenching is correlated with the efficient exciton diffusion within the polymer chains, according to which a sphere-of-action mechanism is proposed. An emissive exciplex was found formed between the conjugated polymer and fullerene in a nonpolar solvent, indicating the occurrence of a photoinduced partial charge transfer process. The low-energy sites in the polymer are believed to play a crucial role in the partial charge transfer. The asymmetry of the exciplex provides a method for evaluating the tendency of photoinduced charge separation between the donor and the acceptor. This method allows screening candidates for photovoltaic applications

Complexes with charge transfer and ion-radical salts in catalysis

Energy Technology Data Exchange (ETDEWEB)

Krylov, O V [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

1978-01-01

Considered are the data experimentally proving formation of complexes with charge transfer as intermediate complexes in homogeneous and heterogeneous catalysis. Catalytic activity correlations with charge transfer energy (and in heterogeneous catalysis with width of semiconductor forbidden band can be useful while selection of catalysts (MoO/sub 3//MgO; V/sub 2/O/sub 5//MgO; MoO/sub 3//Al/sub 2/O/sub 3/; V/sub 2/O/sub 5//Al/sub 2/O/sub 3/). A review of papers on catalytic activity of the previously prepared complexes with charge transfer and ion-radical salts is given. The use of alkali metal complexes with aromatic compounds showed their high activity in hydrogenation reactions and proved principle possibility of activation of hydrogen and hydrocarbons by the systems which do not contain transfer metals.

Characterisation of a CMOS charge transfer device for TDI imaging

International Nuclear Information System (INIS)

Rushton, J.; Holland, A.; Stefanov, K.; Mayer, F.

2015-01-01

The performance of a prototype true charge transfer imaging sensor in CMOS is investigated. The finished device is destined for use in TDI applications, especially Earth-observation, and to this end radiation tolerance must be investigated. Before this, complete characterisation is required. This work starts by looking at charge transfer inefficiency and then investigates responsivity using mean-variance techniques

Charge-Transfer Supra-Amphiphiles Built by Water-Soluble Tetrathiafulvalenes and Viologen-Containing Amphiphiles: Supramolecular Nanoassemblies with Modifiable Dimensions.

Science.gov (United States)

Lv, Zhong-Peng; Chen, Bin; Wang, Hai-Ying; Wu, Yue; Zuo, Jing-Lin

2015-08-05

In this study, multidimensional nanoassemblies with various morphologies such as nanosheets, nanorods, and nanofibers are developed via charge-transfer interaction and supra-amphiphile self-assembling in aqueous phase. The charge-transfer interactions between tetrathiafulvalene derivatives (TTFs) and methyl viologen derivatives (MVs) have been confirmed by the characteristic charger-transfer absorption. (1) H NMR and electrospray ionizsation mass spectrometry (ESI-MS) analyses also indicate supra-amphiphiles are formed by the combination of TTFs and MVs head group through charge-transfer interaction and Coulombic force. X-ray single crystal structural studies, transmission electron microscopy (TEM), and scanning electron microscopy (SEM) reveal that both linkage pattern of TTFs in hydrophilic part and alkane chain structure in hydrophobic part have significant influence on nanoassemblies morphology and microstructure. Moreover, gold nanoparticles (AuNPs) are introduced in the above supramolecular nanoassemblies to construct a supra-amphiphile-driven organic-AuNPs assembly system. AuNPs could be assembled into 1D-3D structures by adding different amount of MVs. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new technique for the study of charge transfer in multiply charged ion-ion collisions

International Nuclear Information System (INIS)

Shinpaugh, J.L.; Meyer, F.W.; Datz, S.

1994-01-01

While large cross sections (>10 -16 cm 2 ) have been predicted for resonant charge transfer in ion-ion collisions, no experimental data exist for multiply charged systems. A novel technique is being developed at the ORNL ECR facility to allow study of symmetric charge exchange in multiply charged ion-ion collisions using a single ion source. Specific intra-beam charge transfer collisions occurring in a well-defined interaction region labeled by negative high voltage are identified and analyzed by electrostatic analysis in combination with ion time-of-flight coincidence detection of the collision products. Center-of-mass collision energies from 400 to 1000 eV are obtained by varying source and labeling-cell voltages. In addition, by the introduction of a target gas into the high-voltage cell, this labeling-voltage method allows measurement of electron-capture and -loss cross sections for ion-atom collisions. Consequently, higher collision energies can be investigated without the requirement of placing the ECR source on a high-voltage platform

Theoretical treatment of charge transfer processes of relevance to astrophysics

Energy Technology Data Exchange (ETDEWEB)

Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

1997-12-01

Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture.

Theoretical treatment of charge transfer processes of relevance to astrophysics

International Nuclear Information System (INIS)

Krstic, P.S.; Stancil, P.C.; Schultz, D.R.

1997-12-01

Charge transfer is an important process in many astrophysical and atmospheric environments. While numerous experimental and theoretical studies exist for H and He targets, data on other targets, particularly metals and molecules, are sparse. Using a variety of theoretical methods and computational techniques the authors are developing methods to estimate the cross sections for electron capture (charge transfer) in slow collisions of low charge state ions with heavy (Mg, Ca, Fe, Co, Ni and Zn) neutrals. In this ongoing work particular attention is paid to ascertaining the importance of double electron capture

Charge-transfer collisions for polarized ion sources

International Nuclear Information System (INIS)

Schlachter, A.S.

1983-06-01

Charge-transfer processes relevant to polarized ion sources are discussed and results are summarized. The primary atom discussed is hydrogen, with particulr emphasis on H - formation. Heavier negative ions are briefly discussed

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

Science.gov (United States)

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.

The Mixed Phase of Charged AdS Black Holes

Directory of Open Access Journals (Sweden)

Piyabut Burikham

2016-01-01

Full Text Available We study the mixed phase of charged AdS black hole and radiation when the total energy is fixed below the threshold to produce a stable charged black hole branch. The coexistence conditions for the charged AdS black hole and radiation are derived for the generic case when radiation particles carry charge. The phase diagram of the mixed phase is demonstrated for both fixed potential and charge ensemble. In the dual gauge picture, they correspond to the mixed phase of quark-gluon plasma (QGP and hadron gas in the fixed chemical potential and density ensemble, respectively. In the nuclei and heavy-ion collisions at intermediate energies, the mixed phase of exotic QGP and hadron gas could be produced. The mixed phase will condense and evaporate into the hadron gas as the fireball expands.

Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

Directory of Open Access Journals (Sweden)

B. Zygelman

2002-03-01

Full Text Available A survey of theoretical studies of charge transfer involving collisions of multiply-charged ions with atomic neutrals (H and He is presented. The calculations utilized the quantum-mechanical molecular-orbital close-coupling (MOCC approach where the requisite potential curves and coupling matrix elements have been obtained with the spin-coupled valence bond (SCVB method. Comparison is made among various collision partners, for equicharged systems, where it is illustrated that even for total charge transfer cross sections, scaling-laws do not exist for low-energy collisions (i.e. < 1 keV/amu. While various empirical scaling-laws are well known in the intermediateand high-energy regimes, the multi-electron configurations of the projectile ions results in a rich and varied low-energy dependence, requiring an explicit calculation for each collision-partner pair. Future charge transfer problems to be addressed with the combined SCVB-MOCC approach are briefly discussed.

Charge transfer and ionization occurring in proton- and helium ion-atom collisions

International Nuclear Information System (INIS)

DuBois, R.D.

1985-12-01

Two examples are presented where specific channels have been identified that are responsible for single and double target ionization via direct coulomb ionization or charge transfer processes. Using ratios of absolute cross sections that have been measured for these processes it was shown that an independent electron model should be appropriate for calculating direct double target ionization but generally appears to be inadequate in calculating charge transfer plus ionization and double charge transfer cross sections. At present such detailed information can be obtained only in limited cases. However cross sections with detailed final charge state information should provide stringent tests for present and future theoretical work. 22 refs., 2 figs

Computational Approach to Electron Charge Transfer Reactions

DEFF Research Database (Denmark)

Jónsson, Elvar Örn

-molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended...

Charge transfer properties of pentacene adsorbed on silver: DFT study

Energy Technology Data Exchange (ETDEWEB)

N, Rekha T.; Rajkumar, Beulah J. M., E-mail: beulah-rajkumar@yahoo.co.in [PG & Research Department of Physics, Lady Doak College, Madurai 625002 (India)

2015-06-24

Charge transfer properties of pentacene adsorbed on silver is investigated using DFT methods. Optimized geometry of pentacene after adsorption on silver indicates distortion in hexagonal structure of the ring close to the silver cluster and deviations in co-planarity of carbon atoms due to the variations in bond angles and dihedral angles. Theoretically simulated absorption spectrum has a symmetric surface plasmon resonance peak around 486nm corresponding to the transfer of charge from HOMO-2 to LUMO. Theoretical SERS confirms the process of adsorption, tilted orientation of pentacene on silver surface and the charge transfers reported. Localization of electron density arising from redistribution of electrostatic potential together with a reduced bandgap of pentacene after adsorption on silver suggests its utility in the design of electro active organic semiconducting devices.

Photoinduced Charge Transfer from Titania to Surface Doping Site.

Science.gov (United States)

Inerbaev, Talgat; Hoefelmeyer, James D; Kilin, Dmitri S

2013-05-16

We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO 2 . Charge transfer from the photo-excited TiO 2 substrate to the catalytic site triggers the photo-catalytic event (such as water oxidation or reduction half-reaction). We perform ab-initio computational modeling of the charge transfer dynamics on the interface of TiO 2 nanorod and catalytic site. A slab of TiO 2 represents a fragment of TiO 2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO 2 substrate. One molecular layer of adsorbed water is taken into consideration to mimic the experimental conditions. It is found that these adsorbed water molecules saturate dangling surface bonds and drastically affect the electronic properties of systems investigated. The modeling is performed by reduced density matrix method in the basis of Kohn-Sham orbitals. A nano-catalyst modeled through replacement defect contributes energy levels near the bottom of the conduction band of TiO 2 nano-structure. An exciton in the nano-rod is dissipating due to interaction with lattice vibrations, treated through non-adiabatic coupling. The electron relaxes to conduction band edge and then to the Ru cite with faster rate than hole relaxes to the Ru cite. These results are of the importance for an optimal design of nano-materials for photo-catalytic water splitting and solar energy harvesting.

An experimental study of the heat transfer performance of a rectangular two-phase natural circulation loop

International Nuclear Information System (INIS)

Chen, K.S.; Chen, Y.Y.; Tsai, S.T.

1990-01-01

An experimental study is presented for the heat transfer performance of a rectangular, two-phase, natural-circulation loop with water-steam as the working fluid. Local temperature measurements of the core fluid and the wall were made, and the overall heat transfer coefficients of the evaporator, the condenser, and the loop system were obtained and correlated in terms of the fluid properties, heat flux conditions, and the liquid charge level. An overheat phenomenon at very low charge level was also observed. Result of a preliminary analysis shows that if the liquid charge level is below the fractional volume of the connecting tube between the condenser and the evaporator, an overheat phenomenon will occur

Dynamical interaction of He atoms with metal surfaces: Charge transfer processes

International Nuclear Information System (INIS)

Flores, F.; Garcia Vidal, F.J.; Monreal, R.

1993-01-01

A self-consistent Kohn-Sham LCAO method is presented to calculate the charge transfer processes between a He * -atom and metal surfaces. Intra-atomic correlation effects are taken into account by considering independently each single He-orbital and by combining the different charge transfer processes into a set of dynamical rate equations for the different ion charge fractions. Our discussion reproduces qualitatively the experimental evidence and gives strong support to the method presented here. (author). 24 refs, 4 figs

Non-Markovian reduced dynamics of ultrafast charge transfer at an oligothiophene–fullerene heterojunction

Energy Technology Data Exchange (ETDEWEB)

Hughes, Keith H., E-mail: keith.hughes@bangor.ac.uk [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Cahier, Benjamin [School of Chemistry, Bangor University, Bangor, Gwynedd LL57 2UW (United Kingdom); Martinazzo, Rocco [Dipartimento di Chimica Università degli Studi di Milano, v. Golgi 19, 20133 Milano (Italy); Tamura, Hiroyuki [WPI-Advanced Institute for Material Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai 980-8577 (Japan); Burghardt, Irene [Institute of Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt/Main (Germany)

2014-10-17

Highlights: • Quantum dynamical study of exciton dissociation at a heterojunction interface. • The non-Markovian quantum dynamics involves a highly structured spectral density. • Spectral density is reconstructed from an effective mode transformation of the Hamiltonian. • The dynamics is studied using the hierarchical equations of motion approach. • It was found that the temperature has little effect on the charge transfer. - Abstract: We extend our recent quantum dynamical study of the exciton dissociation and charge transfer at an oligothiophene–fullerene heterojunction interface (Tamura et al., 2012) [6] by investigating the process using the non-perturbative hierarchical equations of motion (HEOM) approach. Based upon an effective mode reconstruction of the spectral density the effect of temperature on the charge transfer is studied using reduced density matrices. It was found that the temperature had little effect on the charge transfer and a coherent dynamics persists over the first few tens of femtoseconds, indicating that the primary charge transfer step proceeds by an activationless pathway.

Crystal growth of new charge-transfer salts based on π-conjugated donor molecules

Energy Technology Data Exchange (ETDEWEB)

Morherr, Antonia, E-mail: morherr@stud.uni-frankfurt.de [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Witt, Sebastian [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Chernenkaya, Alisa [Graduate School Materials Science in Mainz, 55128 Mainz (Germany); Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bäcker, Jan-Peter [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Schönhense, Gerd [Institut für Physik, Johannes Gutenberg-Universität, 55099 Mainz (Germany); Bolte, Michael [Institut für anorganische Chemie, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany); Krellner, Cornelius [Physikalisches Institut, Goethe-Universität Frankfurt am Main, 60438 Frankfurt am Main (Germany)

2016-09-01

New charge transfer crystals of π-conjugated, aromatic molecules (phenanthrene and picene) as donors were obtained by physical vapor transport. The melting behavior, optimization of crystal growth and the crystal structure are reported for charge transfer salts with (fluorinated) tetracyanoquinodimethane (TCNQ-F{sub x}, x=0, 2, 4), which was used as acceptor material. The crystal structures were determined by single-crystal X-ray diffraction. Growth conditions for different vapor pressures in closed ampules were applied and the effect of these starting conditions for crystal size and quality is reported. The process of charge transfer was investigated by geometrical analysis of the crystal structure and by infrared spectroscopy on single crystals. With these three different acceptor strengths and the two sets of donor materials, it is possible to investigate the distribution of the charge transfer systematically. This helps to understand the charge transfer process in this class of materials with π-conjugated donor molecules.

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

Science.gov (United States)

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.

Experimental evidence of state-selective charge transfer in inductively coupled plasma-atomic emission spectrometry

International Nuclear Information System (INIS)

Chan, George C.-Y.; Hieftje, Gary M.

2004-01-01

State-selective charge-transfer behavior was observed for Fe, Cr, Mn and Cu in inductively coupled plasma (ICP)-atomic emission spectrometry. Charge transfer from Ar + to Fe, Cr and Mn is state-selective because of inefficient collisional mixing of the quasiresonant charge-transfer energy levels with nearby levels. This low efficiency is the consequence of differences in electronic configuration of the core electrons. The reason for state-selective charge-transfer behavior to Cu is not clear, although a tentative explanation based on efficiency of intramultiplet and intermultiplet mixing for this special case is offered

Laser-induced charge transfer in the HeH/sup 2 +/ quasimolecule

Energy Technology Data Exchange (ETDEWEB)

Errea, L.F.; Mendez, L.; Riera, A.

1983-11-01

In a recent publication, the charge transfer cross section for He/sup 2 +/+H(ls) collisions through photon-assisted 2psigma--3dsigma transitions was calculated; this calculation, however, contained several errors whose quantitative--even qualitative effect on the results is not obvious. We present a correct evaluation of this laser-induced cross section, which turns out to be larger, and present a maximum for longer wavelengths, than the values previously reported. In addition, we have checked the applicability of perturbation theory, of the stationary phase, uniform and Landau--Zener approximations, and the importance of potentially competitive photon-assisted reactions.

Robust Stacking-Independent Ultrafast Charge Transfer in MoS2/WS2 Bilayers.

Science.gov (United States)

Ji, Ziheng; Hong, Hao; Zhang, Jin; Zhang, Qi; Huang, Wei; Cao, Ting; Qiao, Ruixi; Liu, Can; Liang, Jing; Jin, Chuanhong; Jiao, Liying; Shi, Kebin; Meng, Sheng; Liu, Kaihui

2017-12-26

Van der Waals-coupled two-dimensional (2D) heterostructures have attracted great attention recently due to their high potential in the next-generation photodetectors and solar cells. The understanding of charge-transfer process between adjacent atomic layers is the key to design optimal devices as it directly determines the fundamental response speed and photon-electron conversion efficiency. However, general belief and theoretical studies have shown that the charge transfer behavior depends sensitively on interlayer configurations, which is difficult to control accurately, bringing great uncertainties in device designing. Here we investigate the ultrafast dynamics of interlayer charge transfer in a prototype heterostructure, the MoS 2 /WS 2 bilayer with various stacking configurations, by optical two-color ultrafast pump-probe spectroscopy. Surprisingly, we found that the charge transfer is robust against varying interlayer twist angles and interlayer coupling strength, in time scale of ∼90 fs. Our observation, together with atomic-resolved transmission electron characterization and time-dependent density functional theory simulations, reveals that the robust ultrafast charge transfer is attributed to the heterogeneous interlayer stretching/sliding, which provides additional channels for efficient charge transfer previously unknown. Our results elucidate the origin of transfer rate robustness against interlayer stacking configurations in optical devices based on 2D heterostructures, facilitating their applications in ultrafast and high-efficient optoelectronic and photovoltaic devices in the near future.

Reduced Charge Transfer Exciton Recombination in Organic Semiconductor Heterojunctions by Molecular Doping

Science.gov (United States)

Deschler, Felix; da Como, Enrico; Limmer, Thomas; Tautz, Raphael; Godde, Tillmann; Bayer, Manfred; von Hauff, Elizabeth; Yilmaz, Seyfullah; Allard, Sybille; Scherf, Ullrich; Feldmann, Jochen

2011-09-01

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer-fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and results in a favored formation of separated carriers. This is observed by the ultrafast quenching of photoluminescence from charge transfer excitons and the increase in photoinduced polaron density by ˜70%. The results are consistent with a reduced formation of emissive charge transfer excitons, induced by state filling of tail states.

Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

Energy Technology Data Exchange (ETDEWEB)

Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.

2008-12-08

The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

Optical Switching Using Transition from Dipolar to Charge Transfer Plasmon Modes in Ge2Sb2Te5 Bridged Metallodielectric Dimers

Science.gov (United States)

Ahmadivand, Arash; Gerislioglu, Burak; Sinha, Raju; Karabiyik, Mustafa; Pala, Nezih

2017-02-01

Capacitive coupling and direct shuttling of charges in nanoscale plasmonic components across a dielectric spacer and through a conductive junction lead to excitation of significantly different dipolar and charge transfer plasmon (CTP) resonances, respectively. Here, we demonstrate the excitation of dipolar and CTP resonant modes in metallic nanodimers bridged by phase-change material (PCM) sections, material and electrical characteristics of which can be controlled by external stimuli. Ultrafast switching (in the range of a few nanoseconds) between amorphous and crystalline phases of the PCM section (here Ge2Sb2Te5 (GST)) allows for designing a tunable plasmonic switch for optical communication applications with significant modulation depth (up to 88%). Judiciously selecting the geometrical parameters and taking advantage of the electrical properties of the amorphous phase of the GST section we adjusted the extinction peak of the dipolar mode at the telecommunication band (λ~1.55 μm), which is considered as the OFF state. Changing the GST phase to crystalline via optical heating allows for direct transfer of charges through the junction between nanodisks and formation of a distinct CTP peak at longer wavelengths (λ~1.85 μm) far from the telecommunication wavelength, which constitutes the ON state.

Polyoxometalate active charge-transfer material for mediated redox flow battery

Energy Technology Data Exchange (ETDEWEB)

Anderson, Travis Mark; Hudak, Nicholas; Staiger, Chad; Pratt, Harry

2017-01-17

Redox flow batteries including a half-cell electrode chamber coupled to a current collecting electrode are disclosed herein. In a general embodiment, a separator is coupled to the half-cell electrode chamber. The half-cell electrode chamber comprises a first redox-active mediator and a second redox-active mediator. The first redox-active mediator and the second redox-active mediator are circulated through the half-cell electrode chamber into an external container. The container includes an active charge-transfer material. The active charge-transfer material has a redox potential between a redox potential of the first redox-active mediator and a redox potential of the second redox-active mediator. The active charge-transfer material is a polyoxometalate or derivative thereof. The redox flow battery may be particularly useful in energy storage solutions for renewable energy sources and for providing sustained power to an electrical grid.

Electronic, structural and chemical effects of charge-transfer at organic/inorganic interfaces

Science.gov (United States)

Otero, R.; Vázquez de Parga, A. L.; Gallego, J. M.

2017-07-01

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical

Charge transfer in chromium-transition metal alloys

International Nuclear Information System (INIS)

Kulakowski, K.; Maksymowicz, A.

1984-07-01

The average T-matrix approximation is applied for calculations of charge transfer of 3d-electrons in transition metal alloys. The role of concentration, long-range and short-range atomic order is investigated. The results are in reasonable agreement with experimental data. (author)

ARCHITECTURE OF A CHARGE-TRANSFER STATE REGULATING LIGHT HARVESTING IN A PLANT ANTENNA PROTEIN

Energy Technology Data Exchange (ETDEWEB)

Fleming, Graham; Ahn, Tae Kyu; Avenson, Thomas J.; Ballottari, Matteo; Cheng, Yuan-Chung; Niyogi, Krishna K.; Bassi, Roberto; Fleming, Graham R.

2008-04-02

Energy-dependent quenching of excess absorbed light energy (qE) is a vital mechanism for regulating photosynthetic light harvesting in higher plants. All of the physiological characteristics of qE have been positively correlated with charge-transfer between coupled chlorophyll and zeaxanthin molecules in the light-harvesting antenna of photosystem II (PSII). In this work, we present evidence for charge-transfer quenching in all three of the individual minor antenna complexes of PSII (CP29, CP26, and CP24), and we conclude that charge-transfer quenching in CP29 involves a de-localized state of an excitonically coupled chlorophyll dimer. We propose that reversible conformational changes in CP29 can `tune? the electronic coupling between the chlorophylls in this dimer, thereby modulating the energy of the chlorophylls-zeaxanthin charge-transfer state and switching on and off the charge-transfer quenching during qE.

Fabrication and charge/energy-transfer study of 4,7-bis(4-triphenylamino)benzo- 2,1,3-thiadiazole/CuPc composite films

International Nuclear Information System (INIS)

Zhu Yuanyuan; Wei Xiao; Xue Minzhao; Zhang Qing; Sheng Qiaorong; Liu Yangang; Gu Shuangxi

2010-01-01

Composite films of 4,7-bis(4-triphenylamino)benzo-2,1,3-thiadiazole (TBT) and copper phthalocyanine (CuPc) are fabricated via protonation-coelectrophoretic deposition from nitromethane solutions of TBT/CuPc mixture in the presence of trifluoroacetic acid as a protonation reagent. A nanospheres-nanowires interpenetrating network structure is obtained when the molar percentage of TBT is 70%. Furthermore, the existence of TBT makes α-phased CuPc be partly transformed into the β-phase, and simultaneously, CuPc disorganizes the TBT unit cells. The blue shift on the absorption edge of TBT and the significant fluorescence quenching in the composite films indicate energy/charge transfer and donor-acceptor (D-A) heterojunction formation. Then these results are proved from another point of view: the mutual overlap of absorption and emission spectra of TBT and CuPc lead to a bidirectional Foerster resonance energy transfer at the interface; the molecular energy levels calculated from the results of cyclic voltammetry theoretically determine that there exist a D-A heterojunction and charge transfer from TBT to CuPc. Finally, from the investigation of the field-induced surface photovoltage spectra, it can be concluded that this charge transfer results in efficient dissociation of the photoinduced excitons in the composite films, followed by the generation of a strong photovoltage response.

Fabrication and charge/energy-transfer study of 4,7-bis(4-triphenylamino)benzo- 2,1,3-thiadiazole/CuPc composite films

Energy Technology Data Exchange (ETDEWEB)

Zhu Yuanyuan; Wei Xiao; Xue Minzhao; Zhang Qing; Sheng Qiaorong; Liu Yangang [School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Gu Shuangxi, E-mail: mzxue@sjtu.edu.c [Department of Chemistry, Fudan University, Shanghai 200433 (China)

2010-12-15

Composite films of 4,7-bis(4-triphenylamino)benzo-2,1,3-thiadiazole (TBT) and copper phthalocyanine (CuPc) are fabricated via protonation-coelectrophoretic deposition from nitromethane solutions of TBT/CuPc mixture in the presence of trifluoroacetic acid as a protonation reagent. A nanospheres-nanowires interpenetrating network structure is obtained when the molar percentage of TBT is 70%. Furthermore, the existence of TBT makes {alpha}-phased CuPc be partly transformed into the {beta}-phase, and simultaneously, CuPc disorganizes the TBT unit cells. The blue shift on the absorption edge of TBT and the significant fluorescence quenching in the composite films indicate energy/charge transfer and donor-acceptor (D-A) heterojunction formation. Then these results are proved from another point of view: the mutual overlap of absorption and emission spectra of TBT and CuPc lead to a bidirectional Foerster resonance energy transfer at the interface; the molecular energy levels calculated from the results of cyclic voltammetry theoretically determine that there exist a D-A heterojunction and charge transfer from TBT to CuPc. Finally, from the investigation of the field-induced surface photovoltage spectra, it can be concluded that this charge transfer results in efficient dissociation of the photoinduced excitons in the composite films, followed by the generation of a strong photovoltage response.

Proton-coupled electron transfer versus hydrogen atom transfer: generation of charge-localized diabatic states.

Science.gov (United States)

Sirjoosingh, Andrew; Hammes-Schiffer, Sharon

2011-03-24

The distinction between proton-coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms is important for the characterization of many chemical and biological processes. PCET and HAT mechanisms can be differentiated in terms of electronically nonadiabatic and adiabatic proton transfer, respectively. In this paper, quantitative diagnostics to evaluate the degree of electron-proton nonadiabaticity are presented. Moreover, the connection between the degree of electron-proton nonadiabaticity and the physical characteristics distinguishing PCET from HAT, namely, the extent of electronic charge redistribution, is clarified. In addition, a rigorous diabatization scheme for transforming the adiabatic electronic states into charge-localized diabatic states for PCET reactions is presented. These diabatic states are constructed to ensure that the first-order nonadiabatic couplings with respect to the one-dimensional transferring hydrogen coordinate vanish exactly. Application of these approaches to the phenoxyl-phenol and benzyl-toluene systems characterizes the former as PCET and the latter as HAT. The diabatic states generated for the phenoxyl-phenol system possess physically meaningful, localized electronic charge distributions that are relatively invariant along the hydrogen coordinate. These diabatic electronic states can be combined with the associated proton vibrational states to generate the reactant and product electron-proton vibronic states that form the basis of nonadiabatic PCET theories. Furthermore, these vibronic states and the corresponding vibronic couplings may be used to calculate rate constants and kinetic isotope effects of PCET reactions.

Using metal complex-labeled peptides for charge transfer-based biosensing with semiconductor quantum dots

Science.gov (United States)

Medintz, Igor L.; Pons, Thomas; Trammell, Scott A.; Blanco-Canosa, Juan B.; Dawson, Philip E.; Mattoussi, Hedi

2009-02-01

Luminescent colloidal semiconductor quantum dots (QDs) have unique optical and photonic properties and are highly sensitive to charge transfer in their surrounding environment. In this study we used synthetic peptides as physical bridges between CdSe-ZnS core-shell QDs and some of the most common redox-active metal complexes to understand the charge transfer interactions between the metal complexes and QDs. We found that QD emission underwent quenching that was highly dependent on the choice of metal complex used. We also found that quenching traces the valence or number of metal complexes brought into close proximity of the nanocrystal surface. Monitoring of the QD absorption bleaching in the presence of the metal complex provided insight into the charge transfer mechanism. The data suggest that two distinct charge transfer mechanisms can take place. One directly to the QD core states for neutral capping ligands and a second to surface states for negatively charged capping ligands. A basic understanding of the proximity driven charge-transfer and quenching interactions allowed us to construct proteolytic enzyme sensing assemblies with the QD-peptide-metal complex conjugates.

Active pixel sensor with intra-pixel charge transfer

Science.gov (United States)

Fossum, Eric R. (Inventor); Mendis, Sunetra (Inventor); Kemeny, Sabrina E. (Inventor)

2004-01-01

An imaging device formed as a monolithic complementary metal oxide semiconductor integrated circuit in an industry standard complementary metal oxide semiconductor process, the integrated circuit including a focal plane array of pixel cells, each one of the cells including a photogate overlying the substrate for accumulating photo-generated charge in an underlying portion of the substrate, a readout circuit including at least an output field effect transistor formed in the substrate, and a charge coupled device section formed on the substrate adjacent the photogate having a sensing node connected to the output transistor and at least one charge coupled device stage for transferring charge from the underlying portion of the substrate to the sensing node.

Electroluminescence from charge transfer states in Donor/Acceptor solar cells

DEFF Research Database (Denmark)

Sherafatipour, Golenaz; Madsen, Morten

Charge photocurrent generation is a key process in solar energy conversion systems. Effective dissociation of the photo-generated electron-hole pairs (excitons) has a strong influence on the efficiency of the organic solar cells. Charge dissociation takes place at the donor/acceptor interface via...... which the maximum open-circuit voltage can be estimated, and further can be used in the modeling and optimization of the OPV devices. [1] C. Deibe, T. Strobe, and V. Dyakonov, “Role of the charge transfer state in organic donor-acceptor solar cells,” Adv. Mater., vol. 22, pp. 4097–4111, 2010. [2] K...... charge transfer (CT) excitons, which is Coulombically bound interfacial electron- hole pairs residing at the donor/acceptor heterojunctions. The CT state represents an intermediate state between the exciton dissociation and recombination back to the ground state. Since the recombination of photo...

Doping Phosphorene with Holes and Electrons through Molecular Charge Transfer.

Science.gov (United States)

Vishnoi, Pratap; Rajesh, S; Manjunatha, S; Bandyopadhyay, Arkamita; Barua, Manaswee; Pati, Swapan K; Rao, C N R

2017-11-03

An important aspect of phosphorene, the novel two-dimensional semiconductor, is whether holes and electrons can both be doped in this material. Some reports found that only electrons can be preferentially doped into phosphorene. There are some theoretical calculations showing charge-transfer interaction with both tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE). We have carried out an investigation of chemical doping of phosphorene by a variety of electron donor and acceptor molecules, employing both experiment and theory, Raman scattering being a crucial aspect of the study. We find that both electron acceptors and donors interact with phosphorene by charge-transfer, with the acceptors having more marked effects. All the three Raman bands of phosphorene soften and exhibit band broadening on interaction with both donor and acceptor molecules. First-principles calculations establish the occurrence of charge-transfer between phosphorene with donors as well as acceptors. The absence of electron-hole asymmetry is noteworthy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microgravity and Charge Transfer in the Neuronal Membrane: Implications for Computational Neurobiology

Science.gov (United States)

Wallace, Ron

1995-01-01

Evidence from natural and artificial membranes indicates that the neural membrane is a liquid crystal. A liquid-to-gel phase transition caused by the application of superposed electromagnetic fields to the outer membrane surface releases spin-correlated electron pairs which propagate through a charge transfer complex. The propagation generates Rydberg atoms in the lipid bilayer lattice. In the present model, charge density configurations in promoted orbitals interact as cellular automata and perform computations in Hilbert space. Due to the small binding energies of promoted orbitals, their automata are highly sensitive to microgravitational perturbations. It is proposed that spacetime is classical on the Rydberg scale, but formed of contiguous moving segments, each of which displays topological equivalence. This stochasticity is reflected in randomized Riemannian tensor values. Spacetime segments interact with charge automata as components of a computational process. At the termination of the algorithm, an orbital of high probability density is embedded in a more stabilized microscopic spacetime. This state permits the opening of an ion channel and the conversion of a quantum algorithm into a macroscopic frequency code.

Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

Science.gov (United States)

Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

2014-09-18

We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

Charge-transfer properties in the gas electron multiplier

International Nuclear Information System (INIS)

Han, Sanghyo; Kim, Yongkyun; Cho, Hyosung

2004-01-01

The charge transfer properties of a gas electron multiplier (GEM) were systematically investigated over a broad range of electric field configurations. The electron collection efficiency and the charge sharing were found to depend on the external fields, as well as on the GEM voltage. The electron collection efficiency increased with the collection field up to 90%, but was essentially independent of the drift field strength. A double conical GEM has a 10% gain increase with time due to surface charging by avalanche ions whereas this effect was eliminated with the cylindrical GEM. The positive-ion feedback is also estimated. (author)

Process techniques of charge transfer time reduction for high speed CMOS image sensors

International Nuclear Information System (INIS)

Cao Zhongxiang; Li Quanliang; Han Ye; Qin Qi; Feng Peng; Liu Liyuan; Wu Nanjian

2014-01-01

This paper proposes pixel process techniques to reduce the charge transfer time in high speed CMOS image sensors. These techniques increase the lateral conductivity of the photo-generated carriers in a pinned photodiode (PPD) and the voltage difference between the PPD and the floating diffusion (FD) node by controlling and optimizing the N doping concentration in the PPD and the threshold voltage of the reset transistor, respectively. The techniques shorten the charge transfer time from the PPD diode to the FD node effectively. The proposed process techniques do not need extra masks and do not cause harm to the fill factor. A sub array of 32 × 64 pixels was designed and implemented in the 0.18 μm CIS process with five implantation conditions splitting the N region in the PPD. The simulation and measured results demonstrate that the charge transfer time can be decreased by using the proposed techniques. Comparing the charge transfer time of the pixel with the different implantation conditions of the N region, the charge transfer time of 0.32 μs is achieved and 31% of image lag was reduced by using the proposed process techniques. (semiconductor devices)

Simulation of charge transfer and orbital rehybridization in molecular and condensed matter systems

Science.gov (United States)

Nistor, Razvan A.

The mixing and shifting of electronic orbitals in molecules, or between atoms in bulk systems, is crucially important to the overall structure and physical properties of materials. Understanding and accurately modeling these orbital interactions is of both scientific and industrial relevance. Electronic orbitals can be perturbed in several ways. Doping, adding or removing electrons from systems, can change the bond-order and the physical properties of certain materials. Orbital rehybridization, driven by either thermal or pressure excitation, alters the short-range structure of materials and changes their long-range transport properties. Macroscopically, during bond formation, the shifting of electronic orbitals can be interpreted as a charge transfer phenomenon, as electron density may pile up around, and hence, alter the effective charge of, a given atom in the changing chemical environment. Several levels of theory exist to elucidate the mechanisms behind these orbital interactions. Electronic structure calculations solve the time-independent Schrodinger equation to high chemical accuracy, but are computationally expensive and limited to small system sizes and simulation times. Less fundamental atomistic calculations use simpler parameterized functional expressions called force-fields to model atomic interactions. Atomistic simulations can describe systems and time-scales larger and longer than electronic-structure methods, but at the cost of chemical accuracy. In this thesis, both first-principles and phenomenological methods are addressed in the study of several encompassing problems dealing with charge transfer and orbital rehybridization. Firstly, a new charge-equilibration method is developed that improves upon existing models to allow next-generation force-fields to describe the electrostatics of changing chemical environments. Secondly, electronic structure calculations are used to investigate the doping dependent energy landscapes of several high

Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

KAUST Repository

Alsam, Amani Abdu

2017-03-14

Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex dynamical processes, including hydrogen bond formation, energy transfer, and solvation dynamics occurring on similar time scales. In this study, we explore the remarkable impact of hydrogen-bond formation on the interfacial charge transfer between a negatively charged electron donating anionic porphyrin and a positively charged electron accepting pi-conjugated polymer, as a model system in solvents with different polarities and capabilities for hydiogen bonding using femtosecond transient absorption spectroscopy. Unlike the conventional understanding of the key role of hydrogen bonding in promoting the charge-transfer process, our steadystate and time-resolved results reveal that the intervening hydrogen-bonding environment and, consequently, the probable longer spacing between the donor and acceptor molecules significantly hinders the charge-transfer process between them. These results show that site-specific hydrogen bonding and geometric considerations between donor and acceptor can be exploited to control both the charge-transfer dynamics and its efficiency not only at donor acceptor interfaces but also in complex biological systems.

Theory and simulation of charge transfer through DNA - nanotube contacts

International Nuclear Information System (INIS)

Rink, Gunda; Kong Yong; Koslowski, Thorsten

2006-01-01

We address the problem of charge transfer between a single-stranded adenine oligomer and semiconducting boron nitride nanotubes from a theoretical and numerical perspective. The model structures have been motivated by computer simulations; sample geometries are used as the input of an electronic structure theory that is based upon an extended Su-Schrieffer-Heeger Hamiltonian. By analyzing the emerging potential energy surfaces, we obtain hole transfer rates via Marcus' theory of charge transfer. In the presence of nanotubes, these rates exceed those of isolated DNA single strands by a factor of up to 10 4 . This enhancement can be rationalized and quantified as a combination of a template effect and the participation of the tube within a superexchange mechanism

Positron Annihilation in Solid Charge-Transfer Complexes

DEFF Research Database (Denmark)

Lévay, B.; Jansen, P.

1979-01-01

Positron lifetime and angular correlation measurements have been carried out on 1:1 charge-transfer complexes, on their pure donor and acceptor components and on the 1:1 M mechanical mixtures of these components. Complex formation reduced the intensity of the long-lifetime component of the donor...

Top-Down Charge Transfer Dissociation (CTD) of Gas-Phase Insulin: Evidence of a One-Step, Two-Electron Oxidation Mechanism

Science.gov (United States)

Li, Pengfei; Kreft, Iris; Jackson, Glen P.

2018-02-01

Top-down analyses of protonated insulin cations of charge states of 4+, 5+, or 6+ were performed by exposing the isolated precursor ions to a beam of helium cations with kinetic energy of more than 6 keV, in a technique termed charge transfer dissociation (CTD). The 100 ms charge transfer reaction resulted in approximately 20% conversion efficiency to other intact charge exchange products (CTnoD), and a range of low abundance fragment ions. To increase backbone and sulfide cleavages, and to provide better structural information than straightforward MS2 CTD, the CTnoD oxidized products were isolated and subjected to collisional activation at the MS3 level. The MS3 CTD/CID reaction effectively broke the disulfide linkages, separated the two chains, and yielded more structurally informative fragment ions within the inter-chain cyclic region. CTD also provided doubly oxidized intact product ions at the MS2 level, and resonance ejection of the singly oxidized product ion revealed that the doubly oxidized product originates directly from the isolated precursor ion and not from consecutive CTD reactions of a singly oxidized intermediate. MS4 experiments were employed to help identify potential radical cations and diradical cations, but the results were negative or inconclusive. Nonetheless, the two-electron oxidation process is a demonstration of the very large potential energy (>20 eV) available through CTD, and is a notable capability for a 3D ion trap platform.

Effects of acid concentration on intramolecular charge transfer ...

Indian Academy of Sciences (India)

rate. Time-dependent density functional theory calculations have been performed to understand the observed spectroscopic results. Keywords. Intramolecular charge transfer; absorption and fluorescence; time resolved fluorescence measurements; acid concentration dependence; time-dependent density functional theory.

Energy and charge transfer cascade in methylammonium lead bromide perovskite nanoparticle aggregates.

Science.gov (United States)

Bouduban, Marine E F; Burgos-Caminal, Andrés; Ossola, Rachele; Teuscher, Joël; Moser, Jacques-E

2017-06-01

Highly photoluminescent hybrid lead halide perovskite nanoparticles have recently attracted wide interest in the context of high-stake applications, such as light emitting diodes (LEDs), light emitting transistors and lasers. In addition, they constitute ideal model systems to explore energy and charge transport phenomena occurring at the boundaries of nanocrystalline grains forming thin films in high-efficiency perovskite solar cells (PSCs). Here we report a complete photophysical study of CH 3 NH 3 PbBr 3 perovskite nanoparticles suspended in chlorobenzene and highlight some important interaction properties. Colloidal suspensions under study were constituted of dispersed aggregates of quasi-2D platelets of a range of thicknesses, decorated with 3D-like spherical nanoparticles. These types of nanostructures possess different optical properties that afford a handle for probing them individually. The photophysics of the colloidal particles was studied by femtosecond pump-probe spectroscopy and time-correlated single-photon counting. We show here that a cascade of energy and exciton-mediated charge transfer occurs between nanostructures: upon photoexcitation, localized excitons within one nanostructure can either recombine on a ps timescale, yielding a short-lived emission, or form charge-transfer states (CTSs) across adjacent domains, resulting in longer-lived photoluminescence in the millisecond timescale. Furthermore, CTSs exhibit a clear signature in the form of a strong photoinduced electroabsorption evidenced in femtosecond transient absorption measurements. Charge transfer dynamics at the surface of the nanoparticles have been studied with various quenchers in solution. Efficient hole transfer to N , N , N ', N '-tetrakis(4-methoxyphenyl)benzidine (MeO-TPD) and 1,4-bis(diphenyl-amino)benzene (BDB) donors was attested by the quenching of the nanoparticles emission. The charge transfer rate was limited by the organic layer used to stabilize the nanoparticles

Discrete and continuum modeling of solvent effects in a twisted intramolecular charge transfer system: The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule.

Science.gov (United States)

Modesto-Costa, Lucas; Borges, Itamar

2018-08-05

The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule is a prototypical system displaying twisted intramolecular (TICT) charge transfer effects. The ground and the first four electronic excited states (S 1 -S 4 ) in gas phase and upon solvation were studied. Charge transfer values as function of the torsion angle between the donor group (dimethylamine) and the acceptor moiety (benzonitrile) were explicitly computed. Potential energy curves were also obtained. The algebraic diagrammatic construction method at the second-order [ADC(2)] ab initio wave function was employed. Three solvents of increased polarities (benzene, DMSO and water) were investigated using discrete (average solvent electrostatic configuration - ASEC) and continuum (conductor-like screening model - COSMO) models. The results for the S 3 and S 4 excited states and the S 1 -S 4 charge transfer curves were not previously available in the literature. Electronic gas phase and solvent vertical spectra are in good agreement with previous theoretical and experimental results. In the twisted (90°) geometry the optical oscillator strengths have negligible values even for the S 2 bright state. Potential energy curves show two distinct pairs of curves intersecting at decreasing angles or not crossing in the more polar solvents. Charge transfer and electric dipole values allowed the rationalization of these results. The former effects are mostly independent of the solvent model and polarity. Although COSMO and ASEC solvent models mostly lead to similar results, there is an important difference: some crossings of the excitation energy curves appear only in the ASEC solvation model, which has important implications to the photochemistry of DMABN. Copyright © 2018 Elsevier B.V. All rights reserved.

Phase transitions and critical behaviour for charged black holes

International Nuclear Information System (INIS)

Carlip, S; Vaidya, S

2003-01-01

We investigate the thermodynamics of a four-dimensional charged black hole in a finite cavity in asymptotically flat and asymptotically de Sitter spaces. In each case, we find a Hawking-Page-like phase transition between a black hole and a thermal gas very much like the known transition in asymptotically anti-de Sitter space. For a 'supercooled' black hole - a thermodynamically unstable black hole below the critical temperature for the Hawking-Page phase transition - the phase diagram has a line of first-order phase transitions that terminates in a second-order point. For the asymptotically flat case, we calculate the critical exponents at the second-order phase transition and find that they exactly match the known results for a charged black hole in anti-de Sitter space. We find strong evidence for similar phase transitions for the de Sitter black hole as well. Thus many of the thermodynamic features of charged anti-de Sitter black holes do not really depend on asymptotically anti-de Sitter boundary conditions; the thermodynamics of charged black holes is surprisingly universal

Charge transport parameters of HBC at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Kirkpatrick, J. [Max Planck Institut fuer Polymerforschung, Ackermannweg 10, 55128 Mainz (Germany); Department of Physics, Imperial College London, Prince Consort Road, London SW7 2BW (United Kingdom); Marcon, V.; Kremer, K.; Andrienko, D. [Max Planck Institut fuer Polymerforschung, Ackermannweg 10, 55128 Mainz (Germany); Nelson, J. [Department of Physics, Imperial College London, Prince Consort Road, London SW7 2BW (United Kingdom)

2008-05-15

We study the dependence on temperature of the charge transport parameters for hexabenzocoronene (HBC). Following from Marcus theory, two charge transport parameters will be calculated: the transfer integral and the difference in site energies. These parameters are strongly dependent on the orientation and position of molecules. Position and orientation of molecules are determined using molecular dynamics. Transfer integrals are calculated from a simplified INDO method. A technique to compute energetic disorder, that is the spread in site energies for the charge carriers, is developed. In the herringbone phase transfer integrals are higher, but so is energetic disorder. We consider three derivatives of HBC with different side chains, which lead to different phase behaviour and distributions of charge transport parameters. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Photoinduced charge and energy transfer in dye-doped conjugated polymers

International Nuclear Information System (INIS)

Veldman, Dirk; Bastiaansen, Jolanda J.A.M.; Langeveld-Voss, Bea M.W.; Sweelssen, Joergen; Koetse, Marc M.; Meskers, Stefan C.J.; Janssen, Rene A.J.

2006-01-01

Conjugated polymer-molecular dye blends of MDMO-PPV (poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene]) and PF1CVTP (poly[9,9-dioctylfluorene-2,7-diyl-alt-2,5-bis(2-thienyl-1-cyanovinyl) -1-(3',7= '-dimethyloctyloxy)-4-methoxybenzene-5'',5''-diyl]) with three dipyrrometheneboron difluoride (bodipy) dyes were studied by (time-resolved) fluorescence and photoinduced absorption spectroscopy to determine quantitatively the relation between the electronic HOMO and LUMO levels and the occurrence of energy or charge transfer after optical excitation. We find that for MDMO-PPV photoinduced charge transfer to the dyes occurs, while photoexcitation of PF1CVTP exclusively results in energy transfer. The differences can be rationalized by assuming that the energy of the charge separated state is 0.33-0.45 eV higher than the energy determined from oxidation and reduction potentials of donor and acceptor, respectively. This provides an important design rule to identify appropriate materials for polymer solar cells that can have a high open-circuit voltage

Surface Charge Transfer Doping of Monolayer Phosphorene via Molecular Adsorption.

Science.gov (United States)

He, Yuanyuan; Xia, Feifei; Shao, Zhibin; Zhao, Jianwei; Jie, Jiansheng

2015-12-03

Monolayer phosphorene has attracted much attention owing to its extraordinary electronic, optical, and structural properties. Rationally tuning the electrical transport characteristics of monolayer phosphorene is essential to its applications in electronic and optoelectronic devices. Herein, we study the electronic transport behaviors of monolayer phosphorene with surface charge transfer doping of electrophilic molecules, including 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), NO2, and MoO3, using density functional theory combined with the nonequilibrium Green's function formalism. F4TCNQ shows optimal performance in enhancing the p-type conductance of monolayer phosphorene. Static electronic properties indicate that the enhancement is originated from the charge transfer between adsorbed molecule and phosphorene layer. Dynamic transport behaviors demonstrate that additional channels for hole transport in host monolayer phosphorene were generated upon the adsorption of molecule. Our work unveils the great potential of surface charge transfer doping in tuning the electronic properties of monolayer phosphorene and is of significance to its application in high-performance devices.

An abnormally slow proton transfer reaction in a simple HBO derivative due to ultrafast intramolecular-charge transfer events.

Science.gov (United States)

Alarcos, Noemí; Gutierrez, Mario; Liras, Marta; Sánchez, Félix; Douhal, Abderrazzak

2015-07-07

We report on the steady-state, picosecond and femtosecond time-resolved studies of a charge and proton transfer dye 6-amino-2-(2'-hydroxyphenyl)benzoxazole (6A-HBO) and its methylated derivative 6-amino-2-(2'-methoxyphenyl)benzoxazole (6A-MBO), in different solvents. With femtosecond resolution and comparison with the photobehaviour of 6A-MBO, we demonstrate for 6A-HBO in solution, the photoproduction of an intramolecular charge-transfer (ICT) process at S1 taking place in ∼140 fs or shorter, followed by solvent relaxation in the charge transferred species. The generated structure (syn-enol charge transfer conformer) experiences an excited-state intramolecular proton-transfer (ESIPT) reaction to produce a keto-type tautomer. This subsequent proton motion occurs in 1.2 ps (n-heptane), 14 ps (DCM) and 35 ps (MeOH). In MeOH, it is assisted by the solvent molecules and occurs through tunneling for which we got a large kinetic isotope effect (KIE) of about 13. For the 6A-DBO (deuterated sample in CD3OD) the global proton-transfer reaction takes place in 200 ps, showing a remarkable slow KIE regime. The slow ESIPT reaction in DCM (14 ps), not through tunnelling as it is not sensitive to OH/OD exchange, has however to overcome an energy barrier using intramolecular as well as solvent coordinates. The rich ESIPT dynamics of 6A-HBO in the used solutions is governed by an ICT reaction, triggered by the amino group, and it is solvent dependent. Thus, the charge injection to a 6A-HBO molecular frame makes the ICT species more stable, and the phenol group less acidic, slowing down the subsequent ESIPT reaction. Our findings bring new insights into the coupling between ICT and ESIPT reactions on the potential-energy surfaces of several barriers.

Photo-induced charge transfer at heterogeneous interfaces: Dye-sensitized tin disulfide, the theory and the experiment

International Nuclear Information System (INIS)

Lanzafame, J.M.

1993-01-01

The study of photo-induced charge transfer is an endeavor that spans the entire industrial period of man's history. Its great importance demands an ever greater understanding of its underlying principles. The work discussed here attempts to probe elementary aspects of the charge transfer process. Investigations into the theory of charge transfer reactions are made in an attempt to isolate the relevant parameters. An analytical discussion is made of a simple Golden Rule type rate equation to describe the transfer kinetics. Then a quantum simulation is carried out to follow the wavefunction propagation as a test of the applicability of the assumptions made in deriving the simpler rate equation. Investigation of charge transfer at surfaces is bet served by the application of ultrafast optical spectroscopies to probe carrier dynamics. A discussion of the properties of the short pulse laser systems employed is included along with a discussion of the different optical spectroscopies available. These tools are then brought to bear upon dye-sensitized SnS 2 , a model system for the study of charge injection processes. The unique properties of the semiconductor are discussed with respect to the charge transfer process. The unique properties of the semiconductor are discussed with respect to the charge transfer process. The optical experiments performed on the dye/SnS 2 systems elucidate the fundamental carrier dynamics and these dynamics are discussed within the theoretical framework to provide a complete picture of the charge transfer kinetics

Super-iron Nanoparticles with Facile Cathodic Charge Transfer

Energy Technology Data Exchange (ETDEWEB)

M Farmand; D Jiang; B Wang; S Ghosh; D Ramaker; S Licht

2011-12-31

Super-irons contain the + 6 valence state of iron. One advantage of this is that it provides a multiple electron opportunity to store additional battery charge. A decrease of particle size from the micrometer to the nanometer domain provides a higher surface area to volume ratio, and opportunity to facilitate charge transfer, and improve the power, voltage and depth of discharge of cathodes made from such salts. However, super-iron salts are fragile, readily reduced to the ferric state, with both heat and contact with water, and little is known of the resultant passivating and non-passivating ferric oxide products. A pathway to decrease the super-iron particle size to the nano-domain is introduced, which overcomes this fragility, and retains the battery capacity advantage of their Fe(VI) valence state. Time and power controlled mechanosynthesis, through less aggressive, dry ball milling, leads to facile charge transfer of super-iron nanoparticles. Ex-situ X-ray Absorption Spectroscopy is used to explore the oxidation state and structure of these iron oxides during discharge and shows the significant change in stability of the ferrate structure to lower oxidation state when the particle size is in the nano-domain.

Charge transfer between O6+ and atomic hydrogen

Science.gov (United States)

Wu, Y.; Stancil, P. C.; Liebermann, H. P.; Buenker, R. J.; Schultz, D. R.; Hui, Y.

2011-05-01

The charge exchange process has been found to play a dominant role in the production of X-rays and/or EUV photons observed in cometary and planetary atmospheres and from the heliosphere. Charge transfer cross sections, especially state-selective cross sections, are necessary parameters in simulations of X-ray emission. In the present work, charge transfer due to collisions of ground state O6+(1s2 1 S) with atomic hydrogen has been investigated theoretically using the quantum-mechanical molecular-orbital close-coupling method (QMOCC). The multi-reference single- and double-excitation configuration interaction approach (MRDCI) has been applied to compute the adiabatic potential and nonadiabatic couplings, and the atomic basis sets used have been optimized with the method proposed previously to obtain precise potential data. Total and state-selective cross sections are calculated for energies between 10 meV/u and 10 keV/u. The QMOCC results are compared to available experimental and theoretical data as well as to new atomic-orbital close-coupling (AOCC) and classical trajectory Monte Carlo (CTMC) calculations. A recommended set of cross sections, based on the MOCC, AOCC, and CTMC calculations, is deduced which should aid in X-ray modeling studies.

Integer Charge Transfer and Hybridization at an Organic Semiconductor/Conductive Oxide Interface

KAUST Repository

Gruenewald, Marco

2015-02-11

We investigate the prototypical hybrid interface formed between PTCDA and conductive n-doped ZnO films by means of complementary optical and electronic spectroscopic techniques. We demonstrate that shallow donors in the vicinity of the ZnO surface cause an integer charge transfer to PTCDA, which is clearly restricted to the first monolayer. By means of DFT calculations, we show that the experimental signatures of the anionic PTCDA species can be understood in terms of strong hybridization with localized states (the shallow donors) in the substrate and charge back-donation, resulting in an effectively integer charge transfer across the interface. Charge transfer is thus not merely a question of locating the Fermi level above the PTCDA electron-transport level but requires rather an atomistic understanding of the interfacial interactions. The study reveals that defect sites and dopants can have a significant influence on the specifics of interfacial coupling and thus on carrier injection or extraction.

Charge Transfer Channels in Formation of Exciplex in Polymer Blends

Science.gov (United States)

Dou, Fei; Zhang, Xin-Ping

2011-09-01

The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) and poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4- phenylenediamine) (PFB) on the excitation wavelengths and morphology is investigated. The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend film. Furthermore, energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex. This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices.

Charge Transfer Channels in Formation of Exciplex in Polymer Blends

International Nuclear Information System (INIS)

Dou Fei; Zhang Xin-Ping

2011-01-01

The strong dependence of photoluminescence of charge transfer excited states or exciplex in a blend film of poly(9,9'-dioctylfluorene-co-benzothiadiazole) (F8BT) and poly(9,9'-dioctylfluorene-co-bis-N,N'-(4-butylphenyl)-bis-N,N'-phenyl-1,4- phenylenediamine) (PFB) on the excitation wavelengths and morphology is investigated. The experimental results reveal that electron transfer in the LUMOs from PFB to F8BT is more efficient than hole transfer in the HOMOs from PFB to F8BT for the formation of exciplex at the interfacial junctions between these two types of molecules in the blend film. Furthermore, energy transfer from the blue-emitting PFB to the green-emitting F8BT at the interfaces introduces an additional two-step channel and thus enhances the formation of an exciplex. This is important for understanding of charge generation and separation in organic bulk heterojunctions and for design of optoelectronic devices. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

Charge transfer in gold--alkali-metal systems

International Nuclear Information System (INIS)

Watson, R.E.; Weinert, M.

1994-01-01

Based on conventional electronegativity arguments, gold--alkali-metal compounds are expected to be among the most ''ionic'' of metallic compounds. The concepts of ionicity and charge transfer are difficult to quantify. However, the changes in bonding in the 50/50 Au--alkali-metal systems between the elemental metals and the compounds are so severe that observations can readily be made concerning their character. The results, as obtained from self-consistent electronic-structure calculations, lead to the apparently odd observation that the electron density at the alkali-metal sites in the compound increases significantly and this involves high l componennts in the charge density. This increase, however, can be attributed to Au-like orbitals spatially overlapping the alkali-metal sites. In a chemical sense, it is reasonable to consider the alkali-metal transferring charge to these Au orbitals. While normally the difference in heats of formation between muffin-tin and full-potential calculations for transition-metal--transition-metal and transition-metal--main-group (e.g., Al) compounds having high site symmetry are small, for the gold--alkali-metal systems, the changes in bonding in the compounds cause differences of ∼0.5 eV/atom between the two classes of potential. Any serious estimate of the electronic structure in these systems must account for these aspherical bonding charges. The origin of the semiconducting behavior of the heavy-alkali-metal Au compounds is shown to arise from a combination of the Au-Au separations and the ionic character of the compounds; the light-alkali-metal Au compounds, with their smaller Au-Au separations, do not have a semiconducting gap. Core-level shifts and isomer shifts are also briefly discussed

Photoinduced charge transfer phase transition in cesium manganese hexacyanoferrate

International Nuclear Information System (INIS)

Matsuda, Tomoyuki; Tokoro, Hiroko; Hashimoto, Kazuhito; Ohkoshi, Shin-ichi

2007-01-01

Cesium manganese hexacyanoferrate, Cs 1.51 Mn[Fe(CN) 6 ], shows a thermal phase transition between Mn II -NC-Fe III [high-temperature (HT) phase] and Mn III -NC-Fe II [low-temperature (LT) phase] with phase transition temperatures of 170 K (HT→LT) and 230 K (LT→HT). The LT phase shows ferromagnetism with Curie temperature of 7 K and coercive field of 60 Oe. Irradiating with 532 nm laser light converts the LT phase into the photoinduced (PI) phase, which does not have spontaneous magnetization. The electronic state of the PI phase corresponds to that of the HT phase and the relaxation temperature from the PI to the LT phase is observed at 90 K

Resonance Raman and excitation energy dependent charge transfer mechanism in halide-substituted hybrid perovskite solar cells.

Science.gov (United States)

Park, Byung-wook; Jain, Sagar M; Zhang, Xiaoliang; Hagfeldt, Anders; Boschloo, Gerrit; Edvinsson, Tomas

2015-02-24

Organo-metal halide perovskites (OMHPs) are materials with attractive properties for optoelectronics. They made a recent introduction in the photovoltaics world by methylammonium (MA) lead triiodide and show remarkably improved charge separation capabilities when chloride and bromide are added. Here we show how halide substitution in OMHPs with the nominal composition CH3NH3PbI2X, where X is I, Br, or Cl, influences the morphology, charge quantum yield, and local interaction with the organic MA cation. X-ray diffraction and photoluminescence data demonstrate that halide substitution affects the local structure in the OMHPs with separate MAPbI3 and MAPbCl3 phases. Raman spectroscopies as well as theoretical vibration calculations reveal that this at the same time delocalizes the charge to the MA cation, which can liberate the vibrational movement of the MA cation, leading to a more adaptive organic phase. The resonance Raman effect together with quantum chemical calculations is utilized to analyze the change in charge transfer mechanism upon electronic excitation and gives important clues for the mechanism of the much improved photovoltage and photocurrent also seen in the solar cell performance for the materials when chloride compounds are included in the preparation.

Charge transfer through DNA/DNA duplexes and DNA/RNA hybrids: complex theoretical and experimental studies.

Science.gov (United States)

Kratochvílová, Irena; Vala, Martin; Weiter, Martin; Špérová, Miroslava; Schneider, Bohdan; Páv, Ondřej; Šebera, Jakub; Rosenberg, Ivan; Sychrovský, Vladimír

2013-01-01

Oligonucleotides conduct electric charge via various mechanisms and their characterization and understanding is a very important and complicated task. In this work, experimental (temperature dependent steady state fluorescence spectroscopy, time-resolved fluorescence spectroscopy) and theoretical (Density Functional Theory) approaches were combined to study charge transfer processes in short DNA/DNA and RNA/DNA duplexes with virtually equivalent sequences. The experimental results were consistent with the theoretical model - the delocalized nature of HOMO orbitals and holes, base stacking, electronic coupling and conformational flexibility formed the conditions for more effective short distance charge transfer processes in RNA/DNA hybrids. RNA/DNA and DNA/DNA charge transfer properties were strongly connected with temperature affected structural changes of molecular systems - charge transfer could be used as a probe of even tiny changes of molecular structures and settings. © 2013. Published by Elsevier B.V. All rights reserved.

Formation of an intermolecular charge-transfer compound in UHV codeposited tetramethoxypyrene and tetracyanoquinodimethane

DEFF Research Database (Denmark)

Medjanik, K.; Perkert, S.; Naghavi, S.

2010-01-01

Ultrahigh vacuum (UHV)-deposited films of the mixed phase of tetramethoxypyrene and tetracyanoquinodimethane (TMP -TCNQ ) on gold have been studied using ultraviolet photoelectron spectroscopy (UPS), x-ray diffraction (XRD), infrared (IR) spectroscopy, and scanning tunneling spectroscopy (STS......). The formation of an intermolecular charge-transfer (CT) compound is evident from the appearance of new reflexes in XRD (d =0.894nm and d =0.677nm). A softening of the CN stretching vibration (redshift by 7 cm⊃-1) of TCNQ is visible in the IR spectra, being indicative of a CT on the order of 0.3e from TMP...

The Roles of Structural Order and Intermolecular Interactions in Determining Ionization Energies and Charge-Transfer State Energies in Organic Semiconductors

KAUST Repository

Graham, Kenneth

2016-08-17

The energy landscape in organic semiconducting materials greatly influences charge and exciton behavior, which are both critical to the operation of organic electronic devices. These energy landscapes can change dramatically depending on the phases of material present, including pure phases of one molecule or polymer and mixed phases exhibiting different degrees of order and composition. In this work, ultraviolet photoelectron spectroscopy measurements of ionization energies (IEs) and external quantum efficiency measurements of charge-transfer (CT) state energies (ECT) are applied to molecular photovoltaic material systems to characterize energy landscapes. The results show that IEs and ECT values are highly dependent on structural order and phase composition. In the sexithiophene:C60 system both the IEs of sexithiophene and C60 shift by over 0.4 eV while ECT shifts by 0.5 eV depending on molecular composition. By contrast, in the rubrene:C60 system the IE of rubrene and C60 vary by ≤0.11 eV and ECT varies by ≤0.04 eV as the material composition varies. These results suggest that energy landscapes can exist whereby the binding energies of the CT states are overcome by energy offsets between charges in CT states in mixed regions and free charges in pure phases. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge modulation as fingerprints of phase-string triggered interference

Energy Technology Data Exchange (ETDEWEB)

Zhu, Zheng; Tian, Chushun; Jiang, Hong-Chen; Qi, Yang; Weng, Zheng-Yu; Zaanen, Jan

2015-07-07

Charge order appears to be an ubiquitous phenomenon in doped Mott insulators, which is currently under intense experimental and theoretical investigations particularly in the high T _c cuprates. This phenomenon is conventionally understood in terms of Hartree-Fock-type mean-field theory. Here we demonstrate a mechanism for charge modulation which is rooted in the many-particle quantum physics arising in the strong coupling limit. Specifically, we consider the problem of a single hole in a bipartite t - J ladder. As a remnant of the fermion signs, the hopping hole picks up subtle phases pending the fluctuating spins, the so-called phase-string effect. We demonstrate the presence of charge modulations in the density matrix renormalization group solutions which disappear when the phase strings are switched off. This form of charge modulation can be understood analytically in a path-integral language with a mean-field-like approximation adopted, showing that the phase strings give rise to constructive interferences leading to self-localization. When the latter occurs, left- and right-moving propagating modes emerge inside the localization volume and their interference is responsible for the real space charge modulation.

Charge transfer and excitation in high-energy ion-atom collisions

International Nuclear Information System (INIS)

Schlachter, A.S.; Berkner, K.H.; McDonald, R.J.

1986-11-01

Coincidence measurements of charge transfer and simultaneous projectile electron excitation provide insight into correlated two-electron processes in energetic ion-atom collisions. Projectile excitation and electron capture can occur simultaneously in a collision of a highly charged ion with a target atom; this process is called resonant transfer and excitation (RTE). The intermediate excited state which is thus formed can subsequently decay by photon emission or by Auger-electron emission. Results are shown for RTE in both the K shell of Ca ions and the L shell of Nb ions, for simultaneous projectile electron loss and excitation, and for the effect of RTE on electron capture

Phased charging and discharging in capacitive desalinatio

Science.gov (United States)

Stadermann, Michael; Qu, Yatian; Santiago, Juan G.; Hemmatifar, Ali

2017-09-12

A system combines complete, ultra-thin cells into a monolithic and robust framework necessary for desalination applications which yields orders of magnitude faster desalination. The electrode pairs are located so that a flow of feed water flows through or around the electrode pairs with the flow perpendicular to sequentially applied electric potentials. The system is controlled to charge the series of electrode pairs sequentially or phased. That means the charging of the second electrode pair is delayed with regard to the charging of the first electrode pair and the charging of a third electrode pair is delayed with respect to the charging of the second electrode pair.

Radiative charge-transfer lifetime of the excited state of (NaCa)+

International Nuclear Information System (INIS)

Makarov, Oleg P.; Cote, R.; Michels, H.; Smith, W.W.

2003-01-01

New experiments were proposed recently to investigate the regime of cold atomic and molecular ion-atom collision processes in a special hybrid neutral-atom-ion trap under high-vacuum conditions. We study the collisional cooling of laser precooled Ca + ions by ultracold Na atoms. Modeling this process requires knowledge of the radiative lifetime of the excited singlet A 1 Σ + state of the (NaCa) + molecular system. We calculate the rate coefficient for radiative charge transfer using a semiclassical approach. The dipole radial matrix elements between the ground and the excited states, and the potential curves were calculated using complete active space self-consistent field and Moeller-Plesset second-order perturbation theory with an extended Gaussian basis, 6-311+G (3df). The semiclassical charge-transfer rate coefficient was averaged over a thermal Maxwellian distribution. In addition, we also present elastic collision cross sections and the spin-exchange cross section. The rate coefficient for charge transfer was found to be 2.3x10 -16 cm 3 /sec, while those for the elastic and spin-exchange cross sections were found to be several orders of magnitude higher (1.1x10 -8 cm 3 /sec and 2.3x10 -9 cm 3 /sec, respectively). This confirms our assumption that the milli-Kelvin regime of collisional cooling of calcium ions by sodium atoms is favorable with the respect to low loss of calcium ions due to the charge transfer

Charge transfer excitations from excited state Hartree-Fock subsequent minimization scheme

International Nuclear Information System (INIS)

Theophilou, Iris; Tassi, M.; Thanos, S.

2014-01-01

Photoinduced charge-transfer processes play a key role for novel photovoltaic phenomena and devices. Thus, the development of ab initio methods that allow for an accurate and computationally inexpensive treatment of charge-transfer excitations is a topic that nowadays attracts a lot of scientific attention. In this paper we extend an approach recently introduced for the description of single and double excitations [M. Tassi, I. Theophilou, and S. Thanos, Int. J. Quantum Chem. 113, 690 (2013); M. Tassi, I. Theophilou, and S. Thanos, J. Chem. Phys. 138, 124107 (2013)] to allow for the description of intermolecular charge-transfer excitations. We describe an excitation where an electron is transferred from a donor system to an acceptor one, keeping the excited state orthogonal to the ground state and avoiding variational collapse. These conditions are achieved by decomposing the space spanned by the Hartree-Fock (HF) ground state orbitals into four subspaces: The subspace spanned by the occupied orbitals that are localized in the region of the donor molecule, the corresponding for the acceptor ones and two more subspaces containing the virtual orbitals that are localized in the neighborhood of the donor and the acceptor, respectively. Next, we create a Slater determinant with a hole in the subspace of occupied orbitals of the donor and a particle in the virtual subspace of the acceptor. Subsequently we optimize both the hole and the particle by minimizing the HF energy functional in the corresponding subspaces. Finally, we test our approach by calculating the lowest charge-transfer excitation energies for a set of tetracyanoethylene-hydrocarbon complexes that have been used earlier as a test set for such kind of excitations

Incorporation of charge transfer into the explicit polarization fragment method by grand canonical density functional theory.

Science.gov (United States)

Isegawa, Miho; Gao, Jiali; Truhlar, Donald G

2011-08-28

Molecular fragmentation algorithms provide a powerful approach to extending electronic structure methods to very large systems. Here we present a method for including charge transfer between molecular fragments in the explicit polarization (X-Pol) fragment method for calculating potential energy surfaces. In the conventional X-Pol method, the total charge of each fragment is preserved, and charge transfer between fragments is not allowed. The description of charge transfer is made possible by treating each fragment as an open system with respect to the number of electrons. To achieve this, we applied Mermin's finite temperature method to the X-Pol wave function. In the application of this method to X-Pol, the fragments are open systems that partially equilibrate their number of electrons through a quasithermodynamics electron reservoir. The number of electrons in a given fragment can take a fractional value, and the electrons of each fragment obey the Fermi-Dirac distribution. The equilibrium state for the electrons is determined by electronegativity equalization with conservation of the total number of electrons. The amount of charge transfer is controlled by re-interpreting the temperature parameter in the Fermi-Dirac distribution function as a coupling strength parameter. We determined this coupling parameter so as to reproduce the charge transfer energy obtained by block localized energy decomposition analysis. We apply the new method to ten systems, and we show that it can yield reasonable approximations to potential energy profiles, to charge transfer stabilization energies, and to the direction and amount of charge transferred. © 2011 American Institute of Physics

Barrier discharge. The transferred charge and ozone synthesis

International Nuclear Information System (INIS)

Gibalov, V.I.; Samoilovich, V.G.

1991-01-01

We have undertaken an experimental investigation of the influence of the conditions of barrier discharge implementation such as: the discharge gap value, the type of gas, and the polarity and dielectric permittivity of the dielectric electrode on the value of charge transferred in a micro-discharge. It is shown that the increase in the specific capacitance of the electrodes leads to proportional increase in the transferred charge value, reaching 100-200 nC in a discharge gap 1 mm, in air. In this case the amplitude and duration of a current pulse in the microdischarge reach, respectively, 10 to 15 A and 40 ns. It is also demonstrated that in air with increase in the discharge gap value one can observe a decrease in the efficiency of the ozone synthesis whereas in oxygen there exists a more complicated dependence: the maximum of efficiency is observed at a discharge gap value of 0.7 to 1.0 mm. (orig.)

Changes in wetting and contact charge transfer by femtosecond laser-ablation of polyimide

Energy Technology Data Exchange (ETDEWEB)

Guo, X.D., E-mail: xiaodong.guo@uib.no [Department of Physics and Technology, Allegaten 55, 5020 Bergen, University of Bergen (Norway); Dai, Y.; Gong, M. [Department of Physics, Shanghai 200444, Shanghai University (China); Qu, Y.G. [Center for Geobiology, Allegaten 41, 5020 Bergen, University of Bergen (Norway); Helseth, L.E. [Department of Physics and Technology, Allegaten 55, 5020 Bergen, University of Bergen (Norway)

2015-09-15

Highlights: • Laser ablation significantly reduced the triboelectric charging of polyimide films. • Hierarchical micro/nanostructures formed on the surface of the sample. • Structural anisotropy leads to spatially varying contact angles of water droplets. • Raman spectroscopy revealed a carbonization of the polyimide sample. • The corresponding loss of insulation may explain the reduction of charge transfer. - Abstract: In this study it is demonstrated that the triboelectric charging of polyimide thin films is significantly reduced by using a femtosecond laser to nanostructure its. It is found that the contact charge transfer between laser-ablated Kapton and aluminum is almost negligible, and even much lower than the significant current occurring when non-treated Kapton touches the metal. Scanning electron microscopy demonstrates that laser ablation produces a hierarchical micro and nanostructure, and it is found that the structural anisotropy leads to spatially varying contact angles of water droplets residing on the surface. Raman spectra suggest that the centers of the laser-ablated tracks are carbonized; therefore, the loss of insulation can be responsible for the reduction of charge transfer.

Simulation of solution phase electron transfer in a compact donor-acceptor dyad.

Science.gov (United States)

Kowalczyk, Tim; Wang, Lee-Ping; Van Voorhis, Troy

2011-10-27

Charge separation (CS) and charge recombination (CR) rates in photosynthetic architectures are difficult to control, yet their ratio can make or break photon-to-current conversion efficiencies. A rational design approach to the enhancement of CS over CR requires a mechanistic understanding of the underlying electron-transfer (ET) process, including the role of the environment. Toward this goal, we introduce a QM/MM protocol for ET simulations and use it to characterize CR in the formanilide-anthraquinone dyad (FAAQ). Our simulations predict fast recombination of the charge-transfer excited state, in agreement with recent experiments. The computed electronic couplings show an electronic state dependence and are weaker in solution than in the gas phase. We explore the role of cis-trans isomerization on the CR kinetics, and we find strong correlation between the vertical energy gaps of the full simulations and a collective solvent polarization coordinate. Our approach relies on constrained density functional theory to obtain accurate diabatic electronic states on the fly for molecular dynamics simulations, while orientational and electronic polarization of the solvent is captured by a polarizable force field based on a Drude oscillator model. The method offers a unified approach to the characterization of driving forces, reorganization energies, electronic couplings, and nonlinear solvent effects in light-harvesting systems.

Charge-Transfer Complexes Studied by Dynamic Force Spectroscopy

Directory of Open Access Journals (Sweden)

Jurriaan Huskens

2013-03-01

Full Text Available In this paper, the strength and kinetics of two charge-transfer complexes, naphthol-methylviologen and pyrene-methylviologen, are studied using dynamic force spectroscopy. The dissociation rates indicate an enhanced stability of the pyrene-methylviologen complex, which agrees with its higher thermodynamic stability compared to naphthol-methylviologen complex.

Energy and charge transfer in ionized argon coated water clusters

International Nuclear Information System (INIS)

Kočišek, J.; Lengyel, J.; Fárník, M.; Slavíček, P.

2013-01-01

We investigate the electron ionization of clusters generated in mixed Ar-water expansions. The electron energy dependent ion yields reveal the neutral cluster composition and structure: water clusters fully covered with the Ar solvation shell are formed under certain expansion conditions. The argon atoms shield the embedded (H 2 O) n clusters resulting in the ionization threshold above ≈15 eV for all fragments. The argon atoms also mediate more complex reactions in the clusters: e.g., the charge transfer between Ar + and water occurs above the threshold; at higher electron energies above ∼28 eV, an excitonic transfer process between Ar + * and water opens leading to new products Ar n H + and (H 2 O) n H + . On the other hand, the excitonic transfer from the neutral Ar* state at lower energies is not observed although this resonant process was demonstrated previously in a photoionization experiment. Doubly charged fragments (H 2 O) n H 2 2+ and (H 2 O) n 2+ ions are observed and Intermolecular Coulomb decay (ICD) processes are invoked to explain their thresholds. The Coulomb explosion of the doubly charged cluster formed within the ICD process is prevented by the stabilization effect of the argon solvent

Charge transfer in conjugated oligomers encapsulated into carbon nanotubes

Energy Technology Data Exchange (ETDEWEB)

Almadori, Y.; Alvarez, L.; Michel, T.; Le Parc, R.; Bantignies, J.L.; Hermet, P.; Sauvajol, J.L. [Laboratoire Charles Coulomb UMR 5521, Universite Montpellier 2, 34095 Montpellier (France); Laboratoire Charles Coulomb UMR 5521, CNRS, 34095 Montpellier (France); Arenal, R. [Laboratoire d' Etude des Microstructures, CNRS-ONERA, 92322 Chatillon (France); Laboratorio de Microscopias Avanzadas, Instituto de Nanociencia de Aragon, U. Zaragoza, 50018 Zaragoza (Spain); Babaa, R. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France); Chemical Engineering Department, University of Technology PETRONAS, UTP, Ipoh-Perak (Malaysia); Jouselme, B.; Palacin, S. [Laboratoire de Chimie des Surfaces et Interfaces, CEA, IRAMIS, SPCSI, 91191 Gif-sur-Yvette Cedex (France)

2011-11-15

This study deals with a hybrid system consisting in quaterthiophene derivative encapsulated inside single-walled and multi-walled carbon nanotubes. Investigations of the encapsulation step are performed by transmission electron microscopy. Raman spectroscopy data point out different behaviors depending on the laser excitation energy with respect to the optical absorption of quaterthiophene. At low excitation energy (far from the oligomer resonance window) there is no significant modification of the Raman spectra before and after encapsulation. By contrast, at high excitation energy (close to the oligomer resonance window), Raman spectra exhibit a G-band shift together with an important RBM intensity loss, suggesting a significant charge transfer between the inserted molecule and the host nanotubes. Those results suggest a photo induced process leading to a significant charge transfer. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Symmetric resonance double charge transfer in Kr++ + Kr and Xe++ + Xe systems

International Nuclear Information System (INIS)

Okuno, K.; Koizumi, T.; Kaneko, Y.

1978-01-01

Cross sections of processes Kr ++ + Kr → Ke + Kr ++ and Xe ++ + Xe → Xe + Xe ++ were measured by the injected-ion-drift-tube technique from 0.04 to 20 eV. For both cases, the cross section below 1 eV coincides with the orbiting cross sections with a charge-transfer probability 1/2. Above 1 eV, the energy dependence of the cross sectcion is like that for single charge transfer. Mobilities of Kr ++ and Xe ++ in He are presented also

A two-dimensional position sensitive gas chamber with scanned charge transfer readout

Energy Technology Data Exchange (ETDEWEB)

Gomez, F. E-mail: faustgr@usc.es; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodriguez, A

2003-10-21

We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 {mu}m thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8x8 cm{sup 2} with a pixel size of 1.27x1.27 mm{sup 2}. Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring.

A two-dimensional position sensitive gas chamber with scanned charge transfer readout

International Nuclear Information System (INIS)

Gomez, F.; Iglesias, A.; Lobato, R.; Mosquera, J.; Pardo, J.; Pena, J.; Pazos, A.; Pombar, M.; Rodriguez, A.

2003-01-01

We have constructed and tested a two-dimensional position sensitive parallel-plate gas ionization chamber with scanned charge transfer readout. The scan readout method described here is based on the development of a new position-dependent charge transfer technique. It has been implemented by using gate strips perpendicularly oriented to the collector strips. This solution reduces considerably the number of electronic readout channels needed to cover large detector areas. The use of a 25 μm thick kapton etched circuit allows high charge transfer efficiency with a low gating voltage, consequently needing a very simple commutating circuit. The present prototype covers 8x8 cm 2 with a pixel size of 1.27x1.27 mm 2 . Depending on the intended use and beam characteristics a smaller effective pixel is feasible and larger active areas are possible. This detector can be used for X-ray or other continuous beam intensity profile monitoring

Charge transfer in pi-stacked systems including DNA

International Nuclear Information System (INIS)

Siebbeles, L.D.A.

2003-01-01

Charge migration in DNA is a subject of intense current study motivated by long-range detection of DNA damage and the potential application of DNA as a molecular wire in nanoscale electronic devices. A key structural element, which makes DNA a medium for long-range charge transfer, is the array of stacked base pairs in the interior of the double helix. The overlapping pi-orbitals of the nucleobases provide a pathway for motion of charge carriers generated on the stack. This 'pi-pathway' resembles the columnarly stacked macrocyclic cores in discotic materials such as triphenylenes. The structure of these pi-stacked systems is highly disordered with dynamic fluctuations occurring on picosecond to nanosecond time scales. Theoretical calculations, concerning the effects of structural disorder and nucleobase sequence in DNA, on the dynamics of charge carriers are presented. Electronic couplings and localization energies of charge carriers were calculated using density functional theory (DFT). Results for columnarly stacked triphenylenes and DNA nucleobases are compared. The results are used to provide insight into the factors that control the mobility of charge carriers. Further, experimental results on the site-selective oxidation of guanine nucleobases in DNA (hot spots for DNA damage) are analyzed on basis of the theoretical results

Ion-atom charge-transfer system for a heavy-ion-beam pumped laser

International Nuclear Information System (INIS)

Ulrich, A.; Gernhaeuser, R.; Kroetz, W.; Wieser, J.; Murnick, D.E.

1994-01-01

An Ar target to which Cs vapor could be added, excited by a pulsed beam of 100-MeV 32 S ions, was studied as a prototype ion-atom charge-transfer system for pumping short-wavelength lasers. Low-velocity Ar 2+ ions were efficiently produced; a huge increase in the intensity of the Ar II 4d-4p spectral lines was observed when Cs vapor was added to the argon. This observation is explained by a selective charge transfer of the Cs 6s electron into the upper levels of the observed transitions. A rate constant of (1.4±0.2)x10 -9 cm 3 /s for the transfer process was determined

Heat transfer characteristics of building walls using phase change material

Science.gov (United States)

Irsyad, M.; Pasek, A. D.; Indartono, Y. S.; Pratomo, A. W.

2017-03-01

Minimizing energy consumption in air conditioning system can be done with reducing the cooling load in a room. Heat from solar radiation which passes through the wall increases the cooling load. Utilization of phase change material on walls is expected to decrease the heat rate by storing energy when the phase change process takes place. The stored energy is released when the ambient temperature is low. Temperature differences at noon and evening can be utilized as discharging and charging cycles. This study examines the characteristics of heat transfer in walls using phase change material (PCM) in the form of encapsulation and using the sleeve as well. Heat transfer of bricks containing encapsulated PCM, tested the storage and released the heat on the walls of the building models were evaluated in this study. Experiments of heat transfer on brick consist of time that is needed for heat transfer and thermal conductivity test as well. Experiments were conducted on a wall coated by PCM which was exposed on a day and night cycle to analyze the heat storage and heat release. PCM used in these experiments was coconut oil. The measured parameter is the temperature at some points in the brick, walls and ambient temperature as well. The results showed that the use of encapsulation on an empty brick can increase the time for thermal heat transfer. Thermal conductivity values of a brick containing encapsulated PCM was lower than hollow bricks, where each value was 1.3 W/m.K and 1.6 W/m.K. While the process of heat absorption takes place from 7:00 am to 06:00 pm, and the release of heat runs from 10:00 pm to 7:00 am. The use of this PCM layer can reduce the surface temperature of the walls of an average of 2°C and slows the heat into the room.

The influence of electric charge transferred during electro-mechanical reshaping on mechanical behavior of cartilage

Science.gov (United States)

Protsenko, Dimitry E.; Lim, Amanda; Wu, Edward C.; Manuel, Cyrus; Wong, Brian J. F.

2011-03-01

Electromechanical reshaping (EMR) of cartilage has been suggested as an alternative to the classical surgical techniques of modifying the shape of facial cartilages. The method is based on exposure of mechanically deformed cartilaginous tissue to a low level electric field. Electro-chemical reactions within the tissue lead to reduction of internal stress, and establishment of a new equilibrium shape. The same reactions offset the electric charge balance between collagen and proteoglycan matrix and interstitial fluid responsible for maintenance of cartilage mechanical properties. The objective of this study was to investigate correlation between the electric charge transferred during EMR and equilibrium elastic modulus. We used a finite element model based on the triphasic theory of cartilage mechanical properties to study how electric charges transferred in the electro-chemical reactions in cartilage can change its mechanical responses to step displacements in unconfined compression. The concentrations of the ions, the strain field and the fluid and ion velocities within the specimen subject to an applied mechanical deformation were estimated and apparent elastic modulus (the ratio of the equilibrium axial stress to the axial strain) was calculated as a function of transferred charge. The results from numerical calculations showed that the apparent elastic modulus decreases with increase in electric charge transfer. To compare numerical model with experimental observation we measured elastic modulus of cartilage as a function of electric charge transferred in electric circuit during EMR. Good correlation between experimental and theoretical data suggests that electric charge disbalance is responsible for alteration of cartilage mechanical properties.

Theoretical studies of charge transfer and proton transfer complex formation between 3,5-dinitrobenzic acid and 1,2-dimethylimidazole

Science.gov (United States)

Afroz, Ziya; Faizan, Mohd.; Alam, Mohammad Jane; Ahmad, Shabbir; Ahmad, Afaq

2018-05-01

Natural atomic charge analysis and molecular electrostatic potential (MEP) surface analysis of hydrogen bonded charge transfer (HBCT) and proton transfer (PT) complex of 3,5-dinitrobenzoic acid (DNBA) and 1,2-dimethylimidazole (DMI) have been investigated by theoretical modelling using widely employed DFT/B3LYP/6-311G(d,p) level of theory. Along with this analysis, Hirshfeld surface study of the intermolecular interactions and associated 2D finger plot for reported PT complex between DNBA and DMI have been explored.

Charge transfer in gas electron multipliers

Energy Technology Data Exchange (ETDEWEB)

Ottnad, Jonathan; Ball, Markus; Ketzer, Bernhard; Ratza, Viktor; Razzaghi, Cina [HISKP, Bonn University, Nussallee 14-16, D-53115 Bonn (Germany)

2015-07-01

In order to efficiently employ a Time Projection Chamber (TPC) at interaction rates higher than ∝1 kHz, as foreseen e.g. in the ALICE experiment (CERN) and at CB-ELSA (Bonn), a continuous operation and readout mode is required. A necessary prerequisite is to minimize the space charge coming from the amplification system and to maintain an excellent spatial and energy resolution. Unfortunately these two goals can be in conflict to each other. Gas Electron Multipliers (GEM) are one candidate to fulfill these requirements. It is necessary to understand the processes within the amplification structure to find optimal operation conditions. To do so, we measure the charge transfer processes in and between GEM foils with different geometries and field configurations, and use an analytical model to describe the results. This model can then be used to predict and optimize the performance. The talk gives the present status of the measurements and describes the model.

The charge transfer characteristic of tetraphenylporphyrin iron chloride Langmuir–Blodgett films

International Nuclear Information System (INIS)

Du, Y.; Li, Z.H.; Qi, P.; Wang, F.; Liu, D.

2013-01-01

The charge transfer characteristic of tetraphenylporphyrin iron (III) chloride (FeP) Langmuir–Blodgett (LB) films on the surface of the ITO glass electrode was reported. When the cyclic voltammetry (CV) scanning was running, the charge transfer characteristic was controlled by the oxidation–reduction process of Fe(III)/Fe(II). The charge transfer characteristic was related to the following factors: the cross-sectional area, relative to the electrode, of FeP as the electron donor (or acceptor). The greater the cross-sectional area of the aggregation of FeP as the electron donor (or acceptor) was, the larger the number of the donated (or accepted) electrons was. The projected area of the cross-section on the ITO electrode. The greater the projected area was, the larger the number of the donated (or accepted) electrons was. The distance between the center of the electron donor (or acceptor) of FeP and the surface of ITO electrode. The smaller the distance was, the greater the rate of donating (or accepting) electrons was. The monolayer coverage, which formed because of the FeP lying on the ITO surface in the form of the monomer and aggregate, was more sensitive to detect oxygen

A low-spin Fe(III) complex with 100-ps ligand-to-metal charge transfer photoluminescence

DEFF Research Database (Denmark)

Chabera, Pavel; Liu, Yizhu; Prakash, Om

2017-01-01

Transition-metal complexes are used as photosensitizers(1), in light-emitting diodes, for biosensing and in photocatalysis(2). A key feature in these applications is excitation from the ground state to a charge-transfer state(3,4); the long charge-transfer-state lifetimes typical for complexes...

Photoinduced charge transfer within polyaniline-encapsulated quantum dots decorated on graphene.

Science.gov (United States)

Nguyen, Kim Truc; Li, Dehui; Borah, Parijat; Ma, Xing; Liu, Zhaona; Zhu, Liangliang; Grüner, George; Xiong, Qihua; Zhao, Yanli

2013-08-28

A new method to enhance the stability of quantum dots (QDs) in aqueous solution by encapsulating them with conducting polymer polyaniline was reported. The polyaniline-encapsulated QDs were then decorated onto graphene through π-π interactions between graphene and conjugated polymer shell of QDs, forming stable polyaniline/QD/graphene hybrid. A testing electronic device was fabricated using the hybrid in order to investigate the photoinduced charge transfer between graphene and encapsulated QDs within the hybrid. The charge transfer mechanism was explored through cyclic voltammetry and spectroscopic studies. The hybrid shows a clear response to the laser irradiation, presenting a great advantage for further applications in optoelectronic devices.

Cost-Effectiveness Comparison of Coupler Designs of Wireless Power Transfer for Electric Vehicle Dynamic Charging

Directory of Open Access Journals (Sweden)

Weitong Chen

2016-11-01

Full Text Available This paper presents a cost-effectiveness comparison of coupler designs for wireless power transfer (WPT, meant for electric vehicle (EV dynamic charging. The design comparison of three common types of couplers is first based on the raw material cost, output power, transfer efficiency, tolerance of horizontal offset, and flux density. Then, the optimal cost-effectiveness combination is selected for EV dynamic charging. The corresponding performances of the proposed charging system are compared and analyzed by both simulation and experimentation. The results verify the validity of the proposed dynamic charging system for EVs.

Plasma effect on tunnelling, charge transfer and transient quasimolecular states

International Nuclear Information System (INIS)

Fisher, D V

2003-01-01

The influence of a dense plasma environment on electron tunnelling between two ion potential wells in collectivized states and in charge-transfer collisions is studied. We show that the tunnelling probabilities in dilute plasma (in a close ion-ion collision) and in dense plasma differ strongly. The difference is due to the mixing between Stark components of donor-ion energy levels, caused by the field of spectator ions in a dense plasma. The mixing is determined by an angle α between the nearest-neighbour ion field and the total electric field acting on the donor ion. In close ion-ion binary collisions the mixing may be considered weak. However, for most plasma ions charge transfer, electron state collectivization and transient quasimolecule formation are strongly affected by the field of spectator ions. We derive approximate analytical expressions for the distribution function of α in an ideal plasma and perform molecular dynamics simulations to find the distribution function of α in both ideal and nonideal plasmas. Both α-dependent and average mixing coefficients are determined. We have found that the mixing is strong, even in ideal plasmas, and increases further with an increase in plasma nonideality. It is shown that there is no resonant charge transfer in dense plasmas. The applicability of a transient 'dicenter' quasimolecule model for dense plasmas is discussed

Bands dispersion and charge transfer in β-BeH2

Science.gov (United States)

Trivedi, D. K.; Galav, K. L.; Joshi, K. B.

2018-04-01

Predictive capabilities of ab-initio method are utilised to explore bands dispersion and charge transfer in β-BeH2. Investigations are carried out using the linear combination of atomic orbitals method at the level of density functional theory. The crystal structure and related parameters are settled by coupling total energy calculations with the Murnaghan equation of state. Electronic bands dispersion from PBE-GGA is reported. The PBE-GGA, and PBE0 hybrid functional, show that β-BeH2 is a direct gap semiconductor with 1.18 and 2.40 eV band gap. The band gap slowly decreases with pressure and beyond l00 GPa overlap of conduction and valence bands at the r point is observed. Charge transfer is studied by means of Mullikan population analysis.

Transfer of energy or charge between quasi-zero-dimensional nanostructures

Czech Academy of Sciences Publication Activity Database

Král, Karel; Menšík, Miroslav

2016-01-01

Roč. 45, č. 4 (2016), s. 243-255 ISSN 2332-4309 R&D Projects: GA ČR(CZ) GA14-05053S; GA MŠk(CZ) LD14011; GA MŠk LH12236 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : charge transfer * electron-phonon interaction * energy transfer * nanostructures * quantum dots Subject RIV: BM - Solid Matter Physics ; Magnetism; CD - Macromolecular Chemistry (UMCH-V) Impact factor: 0.171, year: 2016

Modeling charge transfer at organic donor-acceptor semiconductor interfaces

NARCIS (Netherlands)

Cakir, Deniz; Bokdam, Menno; de Jong, Machiel Pieter; Fahlman, M.; Brocks, G.

2012-01-01

We develop an integer charge transfer model for the potential steps observed at interfaces between donor and acceptor molecular semiconductors. The potential step can be expressed as the difference between the Fermi energy pinning levels of electrons on the acceptor material and holes on the donor

Charge transfer in photorechargeable composite films of TiO2 and polyaniline

Science.gov (United States)

Nomiyama, Teruaki; Sasabe, Kenichi; Sakamoto, Kenta; Horie, Yuji

2015-07-01

A photorechargeable battery (PRB) is a photovoltaic device having an energy storage function in a single cell. The photoactive electrode of PRB is a bilayer film consisting of bare porous TiO2 and a TiO2-polyaniline (PANi) mixture that work as a photovoltaic current generator and an electrochemical energy storage by ion dedoping, respectively. To study the charge transfer between TiO2 and PANi, the photorechargeable quantum efficiency QE ([electron count on discharge]/[incident photon count on photocharge]) was measured by varying the thickness LS of the TiO2-PANi mixture. The quantum efficiency QEuv for UV photons had a maximum of ˜7% at LS ˜ 7 µm. The time constant τTP for the charge transfer was about 10-1 s, which was longer ten times or more than the lifetime of excited electrons within TiO2. These facts reveal that the main rate-limiting factor in the photocharging process is the charge transfer between TiO2 and PANi.

Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation

Science.gov (United States)

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

Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure.

Science.gov (United States)

Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

2018-05-23

Tin niobate photocatalysts with the phase structures of froodite (SnNb 2 O 6 ) and pyrochlore (Sn 2 Nb 2 O 7 ) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb 2 O 6 to Sn 2 Nb 2 O 7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn 4+ species in Sn 2 Nb 2 O 7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb 2 O 6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H 2 evolution compared with the sample of Sn 2 Nb 2 O 7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O 2 -• , and OH • active species dominate the photodegradation of methyl orange.

An insight into the mechanism of charge transfer properties of hybrid organic (MEH-PPV): Inorganic (TiO2) nanocomposites

International Nuclear Information System (INIS)

Mittal, Tanu; Tiwari, Sangeeta; Mehta, Aarti; Sharma, Shailesh N.

2016-01-01

Now a days, inorganic nanoparticles are gaining importance and are potential candidate in different organic electronic device application like (LEDs, PVs) due to their novel properties and confinement in Nano-dimensions. [1, 2] In the present work, we have compared the properties of titanium di oxide (TiO 2 ) nanoparticles (NPs) synthesized by using two different chemical routes aqueous and ethanol respectively. These synthesized TiO 2 nanoparticles have been characterized by X-ray diffraction spectroscopy (XRD) for phase confirmation. It was observed that synthesized nanoparticles are in anatase phase for both preparation routes. Morphological information was collected by scanning electron microscopy (SEM) which confirms that particles are almost spherical in shape and distributed uniformly which is further ensured by transmission electron microscopy (TEM). Dynamic light scattering (DLS) technique was also used for further confirmation of size distribution of as-synthesized nanoparticles. Optical properties were also investigated by photoluminescence and UV-Vis spectroscopy and calculated bandgap was found to be in the range of 3.3-3.5eV for TiO 2 (aq/eth) nanoparticles. The increase in bandgap values with respect to bulk (3.2 eV) confirms that as- synthesized nanoparticles are confined in nanodimensions. As synthesized nanoparticles were interacted with MEHPPV polymer (donor) matrix to make their respective MEHPPV: TiO 2 nanocomposites and to confirm the charge transfer mechanism from polymer to nanoparticles. It can be observed from photoluminescence (PL) quenching experiments that continuous quenching obtained for respective nanocomposites confirms better charge transfer from polymer to inorganic TiO 2 nanoparticles respectively. Because of, better quenching and simultaneously enhanced charge transfer of respective nanocomposites, ensures that these nanocomposites are greatly applicable for photovoltaics (PVs) especially in Hybrid Solar cells (HSCs).

Heat transfer from the evaporator outlet to the charge of thermostatic expansion valves

DEFF Research Database (Denmark)

Langmaack, Lasse Nicolai; Knudsen, Hans-Jørgen Høgaard

2006-01-01

outlet with a special mounting strap. The heat transfer is quite complex because it takes place both directly through the contact points between bulb and pipe and indirectly through the mounting strap The TXV has to react to temperature changes at the evaporator outlet. Therefore, the dynamic behavior...... of the valve (and thereby the whole refrigeration system) depends greatly on the heat transfer between the evaporator outlet tube and the charge in the bulb. In this paper a model for the overall heat transfer between the pipe and the charge is presented. Geometrical data and material properties have been kept...... been found to predict the time constant for the temperature development in the bulb within 1-10 %. Furthermore it has been found that app. 20% of the heat transfer takes place trough the mounting strap....

Evidence for charge transfer in Bi-based superconductors studied by positron annihilation

International Nuclear Information System (INIS)

Tang, Z.; Wang, S.J.; Gao, X.H.; Ce, G.C.; Zhao, Z.X.

1993-01-01

We have measured Doppler-broadening annihilation radiation (DBAR) spectra and positron lifetimes in normal and superconducting states for three kinds of Bi-based superconductors: Bi2212, Pb-doped Bi2223, Pb- and F-doped Bi2223. The difference spectra after deconvolution between two states show a sharpening effect with increasing temperature; the F-doped sample has the greatest amplitude in difference spectra but nearly the same positron lifetimes as the Pb-doped sample. The results are interpreted in terms of charge transfer between the Cu-O and Bi-O planes. The role of oxygen defects in charge transfer is discussed. (orig.)

Charge-exchange breakup of the deuteron with the production of two protons and spin structure of the amplitude of the nucleon charge transfer reaction

International Nuclear Information System (INIS)

Glagolev, V.V.; Lyuboshits, V.L.; Lyuboshits, V.V.; Piskunov, N.M.

1999-01-01

In the framework of the impulse approximation, the relation between the effective cross section of the charge-exchange breakup of a fast deuteron d + a → (pp) + b and the effective cross section of the charge transfer process n + a → p + b is discussed. In doing so, the effects of the proton identity (Fermi-statistics) and of the Coulomb and strong interactions of protons in the final state are taken into account. The distribution over relative momenta of the protons, produced in the charge-exchange process d + p → (pp) + n in the forward direction, is investigated. At the transfer momenta being close to zero the effective cross section of the charge-exchange breakup of a fast deuteron, colliding with the proton target, is determined only by the spin-flip part of the amplitude of the charge transfer reaction n + p → p + n at the zero angle. It is shown that the study of the process d + p → (pp) + n in a beam of the polarized (aligned) deuterons allows one, in principle, to separate two spin-dependent terms in the amplitude of the charge transfer reaction n + p → p + n, one of which does not conserve and the other one conserves the projection of the nucleon spin onto the direction of momentum at the transition of the neutron into the proton

Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

OpenAIRE

Cooper, D. L.; Stancil, P. C.; Turner, A. R.; Wang, J. G.; Clarke, N. J.; Zygelman, B.

2002-01-01

A survey of theoretical studies of charge transfer involving collisions of multiply-charged ions with atomic neutrals (H and He) is presented. The calculations utilized the quantum-mechanical molecular-orbital close-coupling (MOCC) approach where the requisite potential curves and coupling matrix elements have been obtained with the spin-coupled valence bond (SCVB) method. Comparison is made among various collision partners, for equicharged systems, where it is illustrated that even for total...

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

Science.gov (United States)

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.

Possible charge analogues of spin transfer torques in bulk superconductors

Science.gov (United States)

Garate, Ion

2014-03-01

Spin transfer torques (STT) occur when electric currents travel through inhomogeneously magnetized systems and are important for the motion of magnetic textures such as domain walls. Since superconductors are easy-plane ferromagnets in particle-hole (charge) space, it is natural to ask whether any charge duals of STT phenomena exist therein. We find that the superconducting analogue of the adiabatic STT vanishes in a bulk superconductor with a momentum-independent order parameter, while the superconducting counterpart of the nonadiabatic STT does not vanish. This nonvanishing superconducting torque is induced by heat (rather than charge) currents and acts on the charge (rather than spin) degree of freedom. It can become significant in the vicinity of the superconducting transition temperature, where it generates a net quasiparticle charge and alters the dispersion and linewidth of low-frequency collective modes. This work has been financially supported by Canada's NSERC.

Charge-transfer complexes and their role in exciplex emission and near-infrared photovoltaics.

Science.gov (United States)

Ng, Tsz-Wai; Lo, Ming-Fai; Fung, Man-Keung; Zhang, Wen-Jun; Lee, Chun-Sing

2014-08-20

Charge transfer and interactions at organic heterojunctions (OHJs) are known to have critical influences on various properties of organic electronic devices. In this Research News article, a short review is given from the electronic viewpoint on how the local molecular interactions and interfacial energetics at P/N OHJs contribute to the recombination/dissociation of electron-hole pairs. Very often, the P-type materials donate electrons to the N-type materials, giving rise to charge-transfer complexes (CTCs) with a P(δ+) -N(δ-) configuration. A recently observed opposite charge-transfer direction in OHJs is also discussed (i.e., N-type material donates electrons to P-type material to form P(δ-) -N(δ+) ). Recent studies on the electronic structures of CTC-forming material pairs are also summarized. The formation of P(δ-) -N(δ+) -type CTCs and their correlations with exciplex emission are examined. Furthermore, the potential applications of CTCs in NIR photovoltaic devices are reviewed. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Deflection effects and charge transfer in inner-shell vacancy production

International Nuclear Information System (INIS)

Swafford, G.L.

1978-01-01

A method used in the calculation of inner shell ionization in asymmetric ion-atom collisions is extended to include projectile deflection effects and charge transfer to the projectile. Work is done in an independent electron model (Hartree-Fock) for the target, and the interaction is treated with the projectile as a time-dependent perturbation of the system. It is shown tht the time-dependent problem can be solved for the projectile moving along the classical hyperbolic trajectory that results from the nuclear repulsion. The method is very efficient due to the utilization the target-centered expansion of the system wave function. This means that all the required matrix elements can be pretabulated and are then available for use at all impact parameters. The method is first applied to the impact-parameter dependence of K-shell ionization by protons incident upon copper in the energy range 0.5 to 2 MeV. Excellent agreement with the experiments of Andersen et al., is found at the lower energy. Less satisfactory agreement is obtained in the higher energy region. Next the projectile is considered to move in a straight line path with constant velocity, and extend the method to include charge transfer between the target inner shells and the K-shell of the projectile. A critical feature of the results is the recognition of the importance of target continuum states of energy approximately equal to the kinetic energy (in the target frame) of the electron on the projectile. An approach is developed to properly include such resonance states in our pseudostate calculation. Selected numerical results are presented to illustrate the method and to demonstrate the projectile energy and nuclear charge dependence of the charge transfer cross sections

Charge transfer and band bending at Au/Pb(Zr0.2Ti0.8)O3 interfaces investigated by photoelectron spectroscopy

International Nuclear Information System (INIS)

Apostol, Nicoleta G.; Stoflea, Laura E.; Lungu, George A.; Chirila, Cristina; Trupina, Lucian; Negrea, Raluca F.; Ghica, Corneliu; Pintilie, Lucian; Teodorescu, Cristian M.

2013-01-01

The growth of gold layers on Pb(Zr,Ti)O 3 (PZT) deposited on SrTiO 3 is investigated by X-ray photoelectron spectroscopy in the Au thickness range 2–100 Å. Two phases are identified, with compositions close to nominal PZT. The ‘standard’ phase is represented by all binding energies (Pb 4f, Ti 2p, Zr 3d, O 1s) sensibly equal to the nominal values for PZT, whereas the ‘charged’ phase exhibits all core levels are shifted by ∼1 eV toward higher binding energies. By taking into account also scanning probe microscopy images together with recent photoemission results, the ‘charged’ phase belongs to P (+) regions of PZT, whereas the ‘normal’ phase corresponds to regions with no net ferroelectric polarization perpendicular to the surface. Au deposition proceeds in a band bending of Φ PZT − Φ Au ∼ 0.4–0.5 eV for both phases, identified as similar shifts toward higher binding energies of all Pb, Ti, Zr, O core levels with Au deposition. The Au 4f core level exhibits also an unusually low binding energy component 1 eV below the ‘nominal’ Au 4f binding energy position (metal Au). This implies the existence of negatively charged gold, or electron transfer from PZT to Au, although the ‘normal’ PZT phase have a higher work function, as it is derived from the band bending. Most probably this charge transfer occurs toward Au nanoparticles, which have even higher ionization energies. High resolution transmission electron microscopy evidenced the formation of such isolated nanoparticles.

Effect of Molecular Packing and Charge Delocalization on the Nonradiative Recombination of Charge-Transfer States in Organic Solar Cells

KAUST Repository

Chen, Xiankai

2016-09-05

In organic solar cells, a major source of energy loss is attributed to nonradiative recombination from the interfacial charge transfer states to the ground state. By taking pentacene–C60 complexes as model donor–acceptor systems, a comprehensive theoretical understanding of how molecular packing and charge delocalization impact these nonradiative recombination rates at donor–acceptor interfaces is provided.

Improving radiation hardness in space-based Charge-Coupled Devices through the narrowing of the charge transfer channel

Science.gov (United States)

Hall, D. J.; Skottfelt, J.; Soman, M. R.; Bush, N.; Holland, A.

2017-12-01

Charge-Coupled Devices (CCDs) have been the detector of choice for imaging and spectroscopy in space missions for several decades, such as those being used for the Euclid VIS instrument and baselined for the SMILE SXI. Despite the many positive properties of CCDs, such as the high quantum efficiency and low noise, when used in a space environment the detectors suffer damage from the often-harsh radiation environment. High energy particles can create defects in the silicon lattice which act to trap the signal electrons being transferred through the device, reducing the signal measured and effectively increasing the noise. We can reduce the impact of radiation on the devices through four key methods: increased radiation shielding, device design considerations, optimisation of operating conditions, and image correction. Here, we concentrate on device design operations, investigating the impact of narrowing the charge-transfer channel in the device with the aim of minimising the impact of traps during readout. Previous studies for the Euclid VIS instrument considered two devices, the e2v CCD204 and CCD273, the serial register of the former having a 50 μm channel and the latter having a 20 μm channel. The reduction in channel width was previously modelled to give an approximate 1.6× reduction in charge storage volume, verified experimentally to have a reduction in charge transfer inefficiency of 1.7×. The methods used to simulate the reduction approximated the charge cloud to a sharp-edged volume within which the probability of capture by traps was 100%. For high signals and slow readout speeds, this is a reasonable approximation. However, for low signals and higher readout speeds, the approximation falls short. Here we discuss a new method of simulating and calculating charge storage variations with device design changes, considering the absolute probability of capture across the pixel, bringing validity to all signal sizes and readout speeds. Using this method, we

Integer charge transfer at the tetrakis(dimethylamino)ethylene/Au interface

DEFF Research Database (Denmark)

Lindell, L.; Unge, Mikael; Osikowicz, W.

2008-01-01

In organic-based electronics, interfacial properties have a profound impact on device performance. The lineup of energy levels is usually dependent on interface dipoles, which may arise from charge transfer reactions. In many applications, metal-organic junctions are prepared under ambient...

Heat transfer and thermal storage performance of an open thermosyphon type thermal storage unit with tubular phase change material canisters

International Nuclear Information System (INIS)

Wang, Ping-Yang; Hu, Bo-Wen; Liu, Zhen-Hua

2015-01-01

Highlights: • A novel open heat pipe thermal storage unit is design to improve its performance. • Mechanism of its operation is phase-change heat transfer. • Tubular canisters with phase change material were placed in thermal storage unit. • Experiment and analysis are carried out to investigate its operation properties. - Abstract: A novel open thermosyphon-type thermal storage unit is presented to improve design and performance of heat pipe type thermal storage unit. In the present study, tubular canisters filled with a solid–liquid phase change material are vertically placed in the middle of the thermal storage unit. The phase change material melts at 100 °C. Water is presented as the phase-change heat transfer medium of the thermal storage unit. The tubular canister is wrapped tightly with a layer of stainless steel mesh to increase the surface wettability. The heat transfer mechanism of charging/discharging is similar to that of the thermosyphon. Heat transfer between the heat resource or cold resource and the phase change material in this device occurs in the form of a cyclic phase change of the heat-transfer medium, which occurs on the surface of the copper tubes and has an extremely high heat-transfer coefficient. A series of experiments and theoretical analyses are carried out to investigate the properties of the thermal storage unit, including power distribution, start-up performance, and temperature difference between the phase change material and the surrounding vapor. The results show that the whole system has excellent heat-storage/heat-release performance

An experimental study on the heat transfer characteristics of a heat pipe heat exchanger with latent heat storage. Part II: Simultaneous charging/discharging modes

International Nuclear Information System (INIS)

Liu Zhongliang; Wang Zengyi; Ma Chongfang

2006-01-01

In this part of the paper, the performance of the simultaneous charging/discharging operation modes of the heat pipe heat exchanger with latent heat storage is experimentally studied. The experimental results show that the device may operate under either the fluid to fluid heat transfer with charging heat to the phase change material (PCM) or the fluid to fluid heat transfer with discharging heat from the PCM modes according to the initial temperature of the PCM. The melting/solidification curves, the performances of the heat pipes and the device, the influences of the inlet temperature and the mass flow rate of the cold water on the operation performance are investigated by extensive experiments. The experimental results also disclose that under the simultaneous charging/discharging operation mode, although the heat transfer from the hot water directly to the cold water may vary, it always takes up a major part of the total heat recovered by the cold water due to the very small thermal resistance compared with the thermal resistance of the PCM side. The melting/solidification processes taking place in the simultaneous charging/discharging operation are compared with those in the charging only and discharging only processes. By applying a simplified thermal resistance analysis, a criterion for predicting the exact operation modes was derived and used to explain the observed experimental phenomena

Charge transfer state in DBP:C70 organic solar cells

DEFF Research Database (Denmark)

Sherafatipour, Golenaz; Benduhn, Johannes; Spoltore, Donato

-acceptor interface via delocalized charge-transfer (CT) states, which represents an intermediate state between the exciton dissociation and recombination back to the ground state. In this work we perform the electroluminescence (EL) created by bimolecular free career recombination and sensitive external quantum...

Charge transfer and partial pinning at the contacts as the origin of a double dip in the transfer characteristics of graphene-based field-effect transistors

International Nuclear Information System (INIS)

Di Bartolomeo, Antonio; Giubileo, Filippo; Santandrea, Salvatore; Romeo, Francesco; Citro, Roberta; Schroeder, Thomas; Lupina, Grzegorz

2011-01-01

We discuss the origin of an additional dip other than the charge neutrality point observed in the transfer characteristics of graphene-based field-effect transistors with a Si/SiO 2 substrate used as the back-gate. The double dip is proved to arise from charge transfer between the graphene and the metal electrodes, while charge storage at the graphene/SiO 2 interface can make it more evident. Considering a different Fermi energy from the neutrality point along the channel and partial charge pinning at the contacts, we propose a model which explains all the features observed in the gate voltage loops. We finally show that the double dip enhanced hysteresis in the transfer characteristics can be exploited to realize graphene-based memory devices.

Coupled quantum treatment of vibrationally inelastic and vibronic charge transfer in proton-O2 collisions

International Nuclear Information System (INIS)

Gianturco, F.A.; Palma, A.; Semprini, E.; Stefani, F.; Baer, M.

1990-01-01

A three-dimensional quantum-mechanical study of vibrational, state-resolved differential cross sections (DCS) for the direct inelastic and for the charge-transfer scattering channels has been carried out for the H + +O 2 system. The collision energy considered was E c.m. =23.0 eV, which is the same as that examined by Noll and Toennies in their experiments [J. Chem. Phys. 85, 3313 (1986)]. The scattering treatment employed was the charge-transfer infinite-order sudden approximation (CT IOSA) with the vibrational states correctly expanded over the relevant adiabatic basis for each of the two electronic channels. The state-to-state DCS are found to follow closely the behavior of the experimental quantities, both in the inelastic and the charge-transfer channels. Moreover, a careful comparison between the measured relative probabilities and computed values allows us to test in minute detail the efficiency of the scattering model and the reliability of the potential-energy surfaces employed. It is found that vibrational energy transfer is overestimated in the vibrational inelastic channels while in the charge-transfer inelastic channels the same energy transfer is slightly underestimated by the calculations. The total flux distribution, however, is found to be in very good accord with experiments. Angular distributions are also well reproduced both by the DCS and by the average energy-transfer values. The study of some of the CT IOSA quantities also allows us to establish clearly the importance of nonadiabatic transitions in enhancing vibrational inelasticity in the present system

Classical/quantum correspondence in state selective charge transfer and excitation reactions involving highly charged ions and hydrogen

International Nuclear Information System (INIS)

Purkait, M

2009-01-01

State selective charge transfer and excitation cross sections for collisions of Ne q+ (q = 1-10) with atomic hydrogen are calculated within the framework of Classical Trajectory Monte Carlo (CTMC) method and Boundary Corrected Continuum Intermediate State (BCCIS) approximation.

A schematic model for energy and charge transfer in the chlorophyll complex

DEFF Research Database (Denmark)

Bohr, Henrik; Malik, F.B.

2011-01-01

A theory for simultaneous charge and energy transfer in the carotenoid-chlorophyll-a complex is presented here and discussed. The observed charge transfer process in these chloroplast complexes is reasonably explained in terms of this theory. In addition, the process leads to a mechanism to drive...... an electron in a lower to a higher-energy state, thus providing a mechanism for the ejection of the electron to a nearby molecule (chlorophyll) or into the environment. The observed lifetimes of the electronically excited states are in accord/agreement with the investigations of Sundström et al....... and are in the range of pico-seconds and less. The change in electronic charge distribution in internuclear space as the system undergoes an electronic transition to a higher-energy state could, under appropriate physical conditions, lead to oscillating dipoles capable of transmitting energy from the carotenoid-chlorophylls...

Surface charge sensing by altering the phase transition in VO2

Science.gov (United States)

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.

Evaluation of intramolecular charge transfer state of 4-N, N ...

Indian Academy of Sciences (India)

Abstract. Intramolecular charge transfer of 4-N,N-dimethylamino cinnamaldehyde (DMACA) in vacuum and in five different aprotic solvents has been studied by using time-dependent density functional theory. (TDDFT). Polarizable continuum model (PCM) was employed to consider solvent–solute interactions. The potential ...

Low energy cross section data for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions with atoms and molecules

International Nuclear Information System (INIS)

Okuno, Kazuhiko

2007-04-01

Systematic cross section measurements for ion-molecule reactions in hydrogen systems and for charge transfer of multiply charged ions in low energy collisions with atoms and molecules have been performed continuously by the identical apparatus installed with an octo-pole ion beam guide (OPIG) since 1980 till 2004. Recently, all of accumulated cross section data for a hundred collision systems has been entered into CMOL and CHART of the NIFS atomic and molecular numerical database together with some related cross section data. In this present paper, complicated ion-molecule reactions in hydrogen systems are revealed and the brief outlines of specific properties in low energy charge transfer collisions of multiply charged ions with atoms and molecules are introduced. (author)

Tuning electronic properties of graphene nanoflake polyaromatic hydrocarbon through molecular charge-transfer interactions

Science.gov (United States)

Sharma, Vaishali; Dabhi, Shweta D.; Shinde, Satyam; Jha, Prafulla K.

2018-05-01

By means of first principles calculation we have tuned the electronic properties of graphene nanoflake polyaromatic hydrocarbon via molecular charge transfer. Acceptor/donor Tetracyanoquinodimethane (TCNQ) and Tetrathiafulvalene (TTF) organic molecules are adsorbed on polyaromatic hydrocarbons (PAH) in order to introduce the charge transfer. The substrate's n- or p- type nature depends on the accepting/donating behavior of dopant molecules. Two different classes of PAH (extended form of triangulene) namely Bow-tie graphene nanoflake (BTGNF) and triangular zigzag graphene nanoflake (TZGNF). It is revealed that all the TCNQ and TTF modified graphene nanoflakes exhibit significant changes in HOMO-LUMO gap in range from 0.58 eV to 0.64 eV and 0.01 eV to 0.05 eV respectively. The adsorption energies are in the range of -0.05 kcal/mol to -2.6 kcal/mol. The change in work function is also calculated and discussed, the maximum charge transfer is for TCNQ adsorbed BTGNF. These alluring findings in the tuning of electronic properties will be advantageous for promoting graphene nanoflake polyaromatic hydrocarbon for their applications in electronic devices.

Financial time series analysis based on effective phase transfer entropy

Science.gov (United States)

Yang, Pengbo; Shang, Pengjian; Lin, Aijing

2017-02-01

Transfer entropy is a powerful technique which is able to quantify the impact of one dynamic system on another system. In this paper, we propose the effective phase transfer entropy method based on the transfer entropy method. We use simulated data to test the performance of this method, and the experimental results confirm that the proposed approach is capable of detecting the information transfer between the systems. We also explore the relationship between effective phase transfer entropy and some variables, such as data size, coupling strength and noise. The effective phase transfer entropy is positively correlated with the data size and the coupling strength. Even in the presence of a large amount of noise, it can detect the information transfer between systems, and it is very robust to noise. Moreover, this measure is indeed able to accurately estimate the information flow between systems compared with phase transfer entropy. In order to reflect the application of this method in practice, we apply this method to financial time series and gain new insight into the interactions between systems. It is demonstrated that the effective phase transfer entropy can be used to detect some economic fluctuations in the financial market. To summarize, the effective phase transfer entropy method is a very efficient tool to estimate the information flow between systems.

Turn-on fluorescence probes based on pyranine/viologen charge-transfer complexes for the determination of nucleotides

Energy Technology Data Exchange (ETDEWEB)

Schäferling, Michael, E-mail: Michael.schaeferling@utu.fi; Lang, Thomas; Schnettelker, Annette

2014-10-15

The formation of ground state charge-transfer complexes between pyranine (8-hydroxypyrene-1,3,6-trisulfonic acid) and viologen (paraquat) derivatives is utilized for the design of novel fluoroionophores for the determination of phosphate species, particularly of nucleotides. The strong quenching of the pyranine fluorescence by viologen-type charge transfer acceptors can be countermanded if these are functionalized with triethylammonium groups that serve as recognition elements for phosphate anions. We report on the fluorogenic responses of these water-soluble molecular probes in presence of different phosphates. Absorbance measurements give additional information on the charge transfer complex formation and the interaction with nucleotides. The experimental data show that these aggregates form attractive, simple and versatile fluorescence turn-on probes for nucleoside triphosphates. The reversibility of the fluorescence response is demonstrated by means of an enzymatic model assay using ATPase for the decomposition of adenosine triphosphate. - Highlights: • Pyranine/viologen charge-transfer complexes as molecular probe for ATP recognition. • Fluorescence turn on mechanism. • Selective compared to other nucleotides and phosphate anions. • Fast and reversible response applicable to monitor enzymatic reactions.

Study of charge transfer reactions in a microbial fuel cell

Energy Technology Data Exchange (ETDEWEB)

Martin, E.; Savadogo, O. [Ecole Polytechnique, Montreal, PQ (Canada). Dept. de Genie Chimique; National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.; Tartakovsky, B. [National Research Council of Canada, Montreal, PQ (Canada). Biotechnology Research Inst.

2008-07-01

Electron transfer reactions in a microbial fuel cell (MFC) were evaluated. The MFC was inoculated with anaerobic mesophilic sludge and operated with carbon felt, carbon cloth, and platinum (Pt) coated carbon cloth. The MFC was then fed with either acetate or glucose as a source of fuel and operated at a temperature of 25 degrees C and a pH of 7. Scanning electron microscopy (SEM) micrographs demonstrated that the micro-organisms colonized the anodes. Cyclic voltammetry and polarization tests were conducted using different fractions of the anodophilic biofilm in order to determine charge transfer routes. The study characterized the electron transfer mechanisms used by the exoelectrogenic micro-organisms to produce electricity. It was concluded that further research is needed to characterize reaction transfer routes. 2 refs., 1 fig.

Layer-dependent surface potential of phosphorene and anisotropic/layer-dependent charge transfer in phosphorene-gold hybrid systems.

Science.gov (United States)

Xu, Renjing; Yang, Jiong; Zhu, Yi; Yan, Han; Pei, Jiajie; Myint, Ye Win; Zhang, Shuang; Lu, Yuerui

2016-01-07

The surface potential and the efficiency of interfacial charge transfer are extremely important for designing future semiconductor devices based on the emerging two-dimensional (2D) phosphorene. Here, we directly measured the strong layer-dependent surface potential of mono- and few-layered phosphorene on gold, which is consistent with the reported theoretical prediction. At the same time, we used an optical way photoluminescence (PL) spectroscopy to probe charge transfer in the phosphorene-gold hybrid system. We firstly observed highly anisotropic and layer-dependent PL quenching in the phosphorene-gold hybrid system, which is attributed to the highly anisotropic/layer-dependent interfacial charge transfer.

CoPc and CoPcF16 on gold: Site-specific charge-transfer processes

Directory of Open Access Journals (Sweden)

Fotini Petraki

2014-04-01

Full Text Available Interface properties of cobalt(II phthalocyanine (CoPc and cobalt(II hexadecafluoro-phthalocyanine (CoPcF16 to gold are investigated by photo-excited electron spectroscopies (X-ray photoemission spectroscopy (XPS, ultraviolet photoemission spectroscopy (UPS and X-ray excited Auger electron spectroscopy (XAES. It is shown that a bidirectional charge transfer determines the interface energetics for CoPc and CoPcF16 on Au. Combined XPS and XAES measurements allow for the separation of chemical shifts based on different local charges at the considered atom caused by polarization effects. This facilitates a detailed discussion of energetic shifts of core level spectra. The data allow the discussion of site-specific charge-transfer processes.

Hydrogen-transfer and charge-transfer in photochemical and radiation induced reactions. Progress report, November 1, 1975--October 31, 1976

International Nuclear Information System (INIS)

Cohen, S.G.

1976-10-01

The relative importance of light absorption, quenching of triplet, and hydrogen transfer repair has been examined in retardation by mercaptans of photoreduction of aromatic ketones by alcohols. In the reduction of benzophenone by 2-propanol, retardation is efficient and, after correction for the first two effects, is due entirely to hydrogen-transfer repair, as indicated by deuterium labeling. In reduction of acetophenone by α-methylbenzyl alcohol, repair by hydrogen transfer is also operative. In reduction of benzophenone by benzhydrol, retardation is less efficient and is due to quenching, as the ketyl radical does not abstract hydrogen from mercaptan rapidly in competition with coupling. Deuterium isotope effects are discussed in terms of competitive reactions. Photoreduction of benzophenone by 2-butylamine and by triethylamine is retarded by aromatic mercaptans and disulfides. Of the retardation not due to light absorption and triplet quenching by the sulfur compounds, half is due to hydrogen-transfer repair, as indicated by racemization and deuterium labeling. The remainder is attributed to quenching by the sulfur compound of the charge-transfer-complex intermediate. Photoreduction by primary and secondary amines, but not by tertiary amines, is accelerated by aliphatic mercaptans. The acceleration is attributed to catalysis of hydrogen transfer by the mercaptan in the charge-transfer complex. The effect is large in hydrocarbon solvent, less in polar organic solvents and absent in water

The influence of charge transfers effects in monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} prepared by sol-gel acrylamide polymerization

Energy Technology Data Exchange (ETDEWEB)

Herrera-Pérez, G., E-mail: guillermo.herrera@cimav.edu.mx [CONACYT Research Fellow. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico); Jiménez-Mier, J. [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, 04510 Mexico D. F (Mexico); Yang, W.-L. [The Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Reyes-Rojas, A.; Fuentes-Cobas, L.E. [Department of Physics of Materials Department. Centro de Investigación en Materiales Avanzados (CIMAV), Miguel de Cervantes 120, Chihuahua 31136, Chihuahua (Mexico)

2016-08-15

Highlights: • We elucidate the electronic structure through the vanadium L{sub 2,3} edge in LaVO{sub 4} by XAS. • The interpretation of XAS spectrum was performed by the multiplet calculation. • Our results suggest that LaVO{sub 4} can be considered in the charge transfer regime. - Abstract: Core-hole spectroscopy such as X-ray absorption spectroscopy (XAS) is useful to determine the electronic structure of strongly correlated and strongly hybridized compounds such as vanadates. Monazite-type LaVO{sub 4} and perovskite-type LaVO{sub 3} are good candidates to elucidate the electronic structure through the vanadium L{sub 2,3} edge. LaVO{sub 4} was prepared by sol-gel acrylamide polymerization and solid-state reaction. LaVO{sub 3} was obtained by reduction of LaVO{sub 4} using Zr as gatherer. Monoclinic crystal phase for LaVO{sub 4} and orthorhombic crystal phase for LaVO{sub 3} were confirmed by the Rietveld refinement of X-ray diffraction patterns. XAS comparison between Vanadium L{sub 2,3} edge confirms the presence of V{sup 5+} for the monazite and V{sup 3+} for the orthorhombic perovskite. Multiplet calculations including crystal field and charge transfer effects (CTM) were performed in order to elucidate the tetragonal (D{sub 4h} symmetry) parameters Dq, Ds and Dt, the charge transfer energy Δ, and d-d Coulomb repulsion energy U parameters. CTM confirms for LaVO{sub 3} the strong V 3d–O 2p hybridization with a significant contribution of covalent character due to the delocalization of 3d electrons. For LaVO{sub 4} this work suggest the reclassification of this band insulator as charge transfer insulator that shows a significant contribution of ionic character.

Identification of the Heat Transfer Coefficient at the Charge Surface Heated on the Chamber Furnace

Directory of Open Access Journals (Sweden)

Gołdasz A.

2017-06-01

Full Text Available The inverse method was applied to determine the heat flux reaching the charge surface. The inverse solution was based upon finding the minimum of the error norm between the measured and calculated temperatures. The charge temperature field was calculated with the finite element method by solving the heat transfer equation for a square charge made of 15HM steel heated on all its surfaces. On the basis of the mean value of heat flux, the value of the heat transfer coefficient at each surface was determined depending on the surface temperature of the material heated.

Study of charge transfer processes in porphyrins- and phthalocyanins-based materials: from the liquid phase to the solid state

International Nuclear Information System (INIS)

Fournier, Thierry

1994-01-01

In order to efficiently conceive and build supramolecular materials for molecular electronics and optoelectronics, one need to have access to a large data base on the interactions between the elementary pieces of the material. Such a data base can be established only through the study of model Systems and model media. Oligomers of porphyrins and phthalocyanines constitute models of choice: due to the chemical versatility of the compounds, their physical and photophysical properties can be adjusted to produce a targeted function. The first part of this thesis is concerned with double- and triple-Decker mixed porphyrin and Phthalocyanines sandwich compounds of cerium. Then we study the photophysical properties of complexes formed by pairing in solution porphyrins and phthalocyanines bearing oppositely charged substituents. The charge transfer reactions and geminated recombinations are investigated by time-resolved absorption spectroscopy (from the femto- to millisecond time scales) for excited complexes either in solution, or confined in sol-gel matrices or in Langmuir-Blodgett films. The results obtained in the various media are compared and analysed by the Marcus theory. They allow to show that, for strongly coupled complexes, the solvent does not play any key role in the forward and backward electron transfer. We conclude this work by introducing a few targeted projects based on of the photophysical properties of these complexes, namely photodynamic therapy of cancers, nonlinear optics and the generation of photovoltage. (author) [fr

129I Moessbauer spectroscopic study of several n-σ charge-transfer complexes of iodine with thioethers

International Nuclear Information System (INIS)

Sakai, Hiroshi; Matsuyama, Tomochika; Maeda, Yutaka

1986-01-01

129 I Moessbauer studies have been made of n-σ charge-transfer complexes of iodine with thioethers, such as thiane, 1,4-oxathiane, and 1,4-dithiane. The spectra of these complexes consist of two sets of quadrupole octets, corresponding to the bridging and terminal iodine atoms. The transferred charges from the thioethers are localized on the terminal iodine atoms, and the bridging iodine atoms have slightly positive charges. This result can be well explained in terms of a covalent bond between the sulfur and bridging iodine atoms or the MO treatment of a delocalized three-center four-electron bonding. The contributions of the dative structure to the ground state are estimated to be 36, 28, and 24 % for thiane-iodine, 1,4-oxathiane-iodine, and 1,4-dithiane-iodine respectively. The nature of the charge-transfer bond is discussed in comparison with amine-iodine complexes. (author)

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

Directory of Open Access Journals (Sweden)

Rohan Isaac

2018-02-01

Full Text Available 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.

Charge-transfer potentials for ionic crystals: Cauchy violation, LO-TO splitting, and the necessity of an ionic reference state.

Science.gov (United States)

Sukhomlinov, Sergey V; Müser, Martin H

2015-12-14

In this work, we study how including charge transfer into force fields affects the predicted elastic and vibrational Γ-point properties of ionic crystals, in particular those of rock salt. In both analytical and numerical calculations, we find that charge transfer generally leads to a negative contribution to the Cauchy pressure, P(C) ≡ C12 - C66, where C12 and C66 are elements of the elastic tensor. This contribution increases in magnitude with pressure for different charge-transfer approaches in agreement with results obtained with density functional theory (DFT). However, details of the charge-transfer models determine the pressure dependence of the longitudinal optical-transverse optical splitting and that for partial charges. These last two quantities increase with density as long as the chemical hardness depends at most weakly on the environment while experiments and DFT find a decrease. In order to reflect the correct trends, the charge-transfer expansion has to be made around ions and the chemical (bond) hardness has to increase roughly exponentially with inverse density or bond lengths. Finally, the adjustable force-field parameters only turn out meaningful, when the expansion is made around ions.

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

Science.gov (United States)

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.

Delocalization Drives Free Charge Generation in Conjugated Polymer Films

Energy Technology Data Exchange (ETDEWEB)

Rumbles, Garry [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Reid, Obadiah G [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Pace, Natalie A [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

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 solid 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.

A Systematic Modelling Framework for Phase Transfer Catalyst Systems

DEFF Research Database (Denmark)

Anantpinijwatna, Amata; Sales-Cruz, Mauricio; Hyung Kim, Sun

2016-01-01

Phase-transfer catalyst systems contain two liquid phases, with a catalyst (PTC) that transfers between the phases, driving product formation in one phase and being regenerated in the other phase. Typically the reaction involves neutral species in an organic phase and regeneration involves ions i....... The application of the framework is made to two cases in order to highlight the performance and issues of activity coefficient models for predicting design and operation and the effects when different organic solvents are employed....

Charge transfer reactions between gas-phase hydrated electrons, molecular oxygen and carbon dioxide at temperatures of 80-300 K.

Science.gov (United States)

Akhgarnusch, Amou; Tang, Wai Kit; Zhang, Han; Siu, Chi-Kit; Beyer, Martin K

2016-09-14

The recombination reactions of gas-phase hydrated electrons (H2O)n˙(-) with CO2 and O2, as well as the charge exchange reaction of CO2˙(-)(H2O)n with O2, were studied by Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry in the temperature range T = 80-300 K. Comparison of the rate constants with collision models shows that CO2 reacts with 50% collision efficiency, while O2 reacts considerably slower. Nanocalorimetry yields internally consistent results for the three reactions. Converted to room temperature condensed phase, this yields hydration enthalpies of CO2˙(-) and O2˙(-), ΔHhyd(CO2˙(-)) = -334 ± 44 kJ mol(-1) and ΔHhyd(O2˙(-)) = -404 ± 28 kJ mol(-1). Quantum chemical calculations show that the charge exchange reaction proceeds via a CO4˙(-) intermediate, which is consistent with a fully ergodic reaction and also with the small efficiency. Ab initio molecular dynamics simulations corroborate this picture and indicate that the CO4˙(-) intermediate has a lifetime significantly above the ps regime.

Charge Transfer Based Colorimetric Detection of Silver Ion

Energy Technology Data Exchange (ETDEWEB)

Han, Seung Choul; Kim, Kwang Seob; Choi, Soon Kyu; Oh, Jinho; Lee, Jae Wook [Dong-A Univ., Busan (Korea, Republic of)

2014-05-15

We have demonstrated the colorimetric chemosensor for detection of Ag{sup +} via formation of nanoparticles which is based on the intramolecular CT interaction between the electron-rich (2,6-dialkoxynaphthalene; Np) moiety and the electron-deficient (methyl viologen; MV{sup 2+}) moiety of a single sensor molecule. Under irradiation of light, Ag{sup +} was reduced to very small silver nanoparticle by CT interaction in the presence of OEGs as flexible recognition moiety of Ag{sup +} and stabilizer for Ag nanoparticles, thus Ag nanoparticles resulted to reddish brown in the color change of sensor solution, gradually. Therefore, the charge-transfer interaction between an electron-deficient and an electron-rich units existing at a sensor molecule can be regarded as a new and efficient method to construct various colorimetric chemosensors. Donor.acceptor interactions or charge transfer (CT) interactions are an important class of non-covalent interactions and have been widely exploited in self-assembling systems. Beyond molecular chemistry, supramolecular chemistry aims at constituting highly complex, functional chemical systems from components held together by intermolecular forces. Chemosensors are the molecules of abiotic origin that bind selectively and reversibly with the analyte with concomitant change in one or more properties of the system. The recognition and signaling of ionic and neutral species of varying complexity is one of the most intensively studied areas of contemporary supramolecular chemistry.

Mechanism and Dynamics of Charge Transfer in Donor-Bridge-Acceptor Systems

NARCIS (Netherlands)

Gorczak-Vos, N.

2016-01-01

Photoinduced charge transfer in organic materials is a fundamental process in various biological and technological areas. Donor-bridge-acceptor (DBA) molecules are used as model systems in numerous theoretical and experimental work to systematically study and unravel the underlying mechanisms of

Charge transfer between hydrogen(deuterium) ions and atoms in metal vapors

International Nuclear Information System (INIS)

Alvarez T, I.; Cisneros G, C.

1981-01-01

The current state of the experiments on charge transfer between hydrogen (deuterium) ions and atoms in metal vapors are given. Emphasis is given to describing different experimental techniques. The results of calculations if available, are compared with existing experimental data. (author)

Humidity independent mass spectrometry for gas phase chemical analysis via ambient proton transfer reaction.

Science.gov (United States)

Zhu, Hongying; Huang, Guangming

2015-03-31

In this work, a humidity independent mass spectrometric method was developed for rapid analysis of gas phase chemicals. This method is based upon ambient proton transfer reaction between gas phase chemicals and charged water droplets, in a reaction chamber with nearly saturate humidity under atmospheric pressure. The humidity independent nature enables direct and rapid analysis of raw gas phase samples, avoiding time- and sample-consuming sample pretreatments in conventional mass spectrometry methods to control sample humidity. Acetone, benzene, toluene, ethylbenzene and meta-xylene were used to evaluate the analytical performance of present method. The limits of detection for benzene, toluene, ethylbenzene and meta-xylene are in the range of ∼0.1 to ∼0.3 ppbV; that of benzene is well below the present European Union permissible exposure limit for benzene vapor (5 μg m(-3), ∼1.44 ppbV), with linear ranges of approximately two orders of magnitude. The majority of the homemade device contains a stainless steel tube as reaction chamber and an ultrasonic humidifier as the source of charged water droplets, which makes this cheap device easy to assemble and facile to operate. In addition, potential application of this method was illustrated by the real time identification of raw gas phase chemicals released from plants at different physiological stages. Copyright © 2015 Elsevier B.V. All rights reserved.

ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

NARCIS (Netherlands)

Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what

Superconductivity and charge transfer excitations in high Tc superconductors

International Nuclear Information System (INIS)

Balseiro, C.A.; Alascio, B.; Gagliano, E.; Rojo, A.

1988-01-01

We present some numerical results to show that in a simple model which includes Cu 3d and O 2p orbitals together with inter and intra atomic correlations pairing between holes can occur due to charge transfer excitations. We present also a simple approximation to derive an effective Hamiltonian containing an interaction between particles which is attractive for some values of the different microscopic parameters

Quantum information transfer between topological and conventional charge qubits

International Nuclear Information System (INIS)

Li Jun; Zou Yan

2016-01-01

We propose a scheme to realize coherent quantum information transfer between topological and conventional charge qubits. We first consider a hybrid system where a quantum dot (QD) is tunnel-coupled to a semiconductor Majorana-hosted nanowire (MNW) via using gated control as a switch, the information encoded in the superposition state of electron empty and occupied state can be transferred to each other through choosing the proper interaction time to make measurements. Then we consider another system including a double QDs and a pair of parallel MNWs, it is shown that the entanglement information transfer can be realized between the two kinds of systems. We also realize long distance quantum information transfer between two quantum dots separated by an MNW, by making use of the nonlocal fermionic level formed with the pared Majorana feimions (MFs) emerging at the two ends of the MNW. Furthermore, we analyze the teleportationlike electron transfer phenomenon predicted by Tewari et al. [Phys. Rev. Lett. 100, 027001 (2008)] in our considered system. Interestingly, we find that this phenomenon exactly corresponds to the case that the information encoded in one QD just returns back to its original place during the dynamical evolution of the combined system from the perspective of quantum state transfer. (paper)

Mixed-mode reversed phase/positively charged repulsion chromatography for intact protein separation.

Science.gov (United States)

Ding, Ling; Guo, Zhimou; Hu, Zhuo; Liang, Xinmiao

2017-05-10

A mixed-mode reversed phase/positively charged repulsion stationary phase C8PN composed of octyl and amino group has been developed for separation of intact protein. Before the separation of proteins, a set of probe compounds were employed to evaluate the chromatographic properties of C8PN, demonstrating typical reversed phase/positively charged repulsion interaction on this stationary phase as estimated. Then the new C8PN stationary phase was used to separate a standard protein mixture on the reversed phase mode. Compared with a commercial C4 stationary phase, it showed different selectivity for some proteins. In order to better understand the properties of C8PN, the effect of acetonitrile content was investigated based on retention equation. Higher values of the equation parameters on C8PN demonstrated that the protein retentions were more sensitive to the change of acetonitrile content. Besides, the influences of buffer salt additives on the protein retentions were also studied. The retention factors of the proteins got larger with the increase of buffer salt concentration, which confirmed the positively charged repulsion interaction on the column. Finally, the C8PN was further applied to separate oxidized- and reduced- forms of Recombinant Human Growth Hormone. Our study indicated the advantages and application potential of mixed-mode reversed phase/positively charged repulsion stationary phase for intact protein separation. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis and photophysical properties of a novel terephthalic PH sensor based on internal charge transfer

International Nuclear Information System (INIS)

Miladinova, Polya M.

2016-01-01

A novel fluorescence sensing derivative of 2-aminodimethylterephthalate configured as a “fluorophore-receptor” system was synthesized and investigated. Due to the internal charge transfer, the designed fluorophore was able to act as a pH-probe via an “off-on” fluorescence sensing mechanism. The sensor activity toward protons as cations and hydroxide as anions in DMF was studied by monitoring the changes of the fluorescence intensity. Keywords: 2-aminoterephthalic derivative, ICT (internal charge transfer), pH sensor.

Charge Transfer Effect on Raman and Surface Enhanced Raman Spectroscopy of Furfural Molecules.

Science.gov (United States)

Wan, Fu; Shi, Haiyang; Chen, Weigen; Gu, Zhaoliang; Du, Lingling; Wang, Pinyi; Wang, Jianxin; Huang, Yingzhou

2017-08-02

The detection of furfural in transformer oil through surface enhanced Raman spectroscopy (SERS) is one of the most promising online monitoring techniques in the process of transformer aging. In this work, the Raman of individual furfural molecules and SERS of furfural-M x (M = Ag, Au, Cu) complexes are investigated through density functional theory (DFT). In the Raman spectrum of individual furfural molecules, the vibration mode of each Raman peak is figured out, and the deviation from experimental data is analyzed by surface charge distribution. In the SERS of furfural-M x complexes, the influence of atom number and species on SERS chemical enhancement factors (EFs) are studied, and are further analyzed by charge transfer effect. Our studies strengthen the understanding of charge transfer effect in the SERS of furfural molecules, which is important in the online monitoring of the transformer aging process through SERS.

Charge transfer to the continuum by heavy ions in atomic hydrogen

International Nuclear Information System (INIS)

Sellin, I.A.

1981-01-01

Design and installation of an atomic hydrogen target for measurements of charge transfer to the continuum by heavy ions are discussed. The design consists of a tungsten gas cell operated at temperatures of 2500 to 2600 0 K. Initial testing is underway

Heat transfer performance of a pulsating heat pipe charged with acetone-based mixtures

Science.gov (United States)

Wang, Wenqing; Cui, Xiaoyu; Zhu, Yue

2017-06-01

Pulsating heat pipes (PHPs) are used as high efficiency heat exchangers, and the selection of working fluids in PHPs has a great impact on the heat transfer performance. This study investigates the thermal resistance characteristics of the PHP charged with acetone-based binary mixtures, where deionized water, methanol and ethanol were added to and mixed with acetone, respectively. The volume mixing ratios were 2:1, 4:1 and 7:1, and the heating power ranged from 10 to 100 W with filling ratios of 45, 55, 62 and 70%. At a low filling ratio (45%), the zeotropic characteristics of the binary mixtures have an influence on the heat transfer performance of the PHP. Adding water, which has a substantially different boiling point compared with that of acetone, can significantly improve the anti-dry-out ability inside the PHP. At a medium filling ratio (55%), the heat transfer performance of the PHP is affected by both phase transition characteristics and physical properties of working fluids. At high heating power, the thermal resistance of the PHP with acetone-water mixture is between that with pure acetone and pure water, whereas the thermal resistance of the PHP with acetone-methanol and acetone-ethanol mixtures at mixing ratios of 2:1 and 4:1 is less than that with the corresponding pure fluids. At high filling ratios (62 and 70%), the heat transfer performance of the PHP is mainly determined by the properties of working fluids that affects the flow resistance. Thus, the PHP with acetone-methanol and acetone-ethanol mixtures that have a lower flow resistance shows better heat transfer performance than that with acetone-water mixture.

Effect of Conjugation Length on Photoinduced Charge-Transfer in π-Conjugated Oligomer-Acceptor Dyads

KAUST Repository

Jiang, Junlin

2017-05-25

A series of -conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge separation (CS) and charge recombination (CR) are strongly exothermic (G0CS ~ -1.1 and G0CR ~ -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE+•) remains approximately constant ( ~ 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1 – 10 ps timescale, with the rates decreasing slightly with increased oligomer length (βCS ~ 0.15 Å-1). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI ~ PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.

Effect of Conjugation Length on Photoinduced Charge-Transfer in π-Conjugated Oligomer-Acceptor Dyads

KAUST Repository

Jiang, Junlin; Alsam, Amani Abdu; Wang, Shanshan; Aly, Shawkat Mohammede; Pan, Zhenxing; Mohammed, Omar F.; Schanze, Kirk S.

2017-01-01

A series of -conjugated oligomer-acceptor dyads were synthesized that feature oligo(phenylene ethynylene) (OPE) conjugated backbones end-capped with a naphthalene diimide (NDI) acceptor. The OPE segments vary in length from 4 to 8 phenylene ethynene units (PEn-NDI, where n = 4, 6 and 8). Fluorescence and transient absorption spectroscopy reveals that intramolecular OPE NDI charge transfer dominates the deactivation of excited states of the PEn-NDI oligomers. Both charge separation (CS) and charge recombination (CR) are strongly exothermic (G0CS ~ -1.1 and G0CR ~ -2.0 eV), and the driving forces do not vary much across the series because the oxidation and reduction potentials and singlet energies of the OPEs do not vary much with their length. Bimolecular photoinduced charge transfer between model OPEs that do not contain the NDI acceptors with methyl viologen was studied, and the results reveal that the absorption of the cation radical state (OPE+•) remains approximately constant ( ~ 575 nm) regardless of oligomer length. This finding suggests that the cation radical (polaron) of the OPE is relatively localized, effectively occupying a confined segment of n 4 repeat units in the longer oligomers. Photoinduced intramolecular electron transfer dynamics in the PEn-NDI series was investigated by UV-visible femtosecond transient absorption spectroscopy with visible and mid-infrared probes. Charge separation occurs on the 1 – 10 ps timescale, with the rates decreasing slightly with increased oligomer length (βCS ~ 0.15 Å-1). The rate for charge-recombination decreases in the sequence PE4-NDI > PE6-NDI ~ PE8-NDI. The discontinuous distance dependence in the rate for charge recombination may be related to the spatial localization of the positive polaron state in the longer oligomers.

Impact of exact exchange in the description of the electronic structure of organic charge-transfer molecular crystals

KAUST Repository

Fonari, Alexandr

2014-10-21

We evaluate the impact that the amount of nonlocal Hartree-Fock (%HF) exchange included in a hybrid density functional has on the microscopic parameters (transfer integrals, band gaps, bandwidths, and effective masses) describing charge transport in high-mobility organic crystals. We consider both crystals based on a single molecule, such as pentacene, and crystals based on mixed-stack charge-transfer systems, such as dibenzo-TTF–TCNQ. In the pentacene crystal, the band gap decreases and the effective masses increase linearly with an increase in the amount of %HF exchange. In contrast, in the charge-transfer crystals, while the band gap increases linearly, the effective masses vary only slightly with an increase in %HF exchange. We show that the superexchange nature of the electronic couplings in charge-transfer systems is responsible for this peculiar evolution of the effective masses. We compare the density functional theory results with results obtained within the G0W0 approximation as a way of benchmarking the optimal amount of %HF exchange needed in a given functional.

Charge transfer and injection barrier at the metal-organic interfaces

Science.gov (United States)

Yan, Li

2002-09-01

The metal-organic interface plays a critical role in determining the functionality and performance of many innovative organic based devices. It has attracted extensive research interests in recent years. This thesis presents investigations of the electronic structures of organic materials, such as tris-(8-hydroxyquinoline) aluminum (Alq3) and copper phthalocyanine (CuPc), during their interface formation with metals. The characterization is accomplished by X-ray and ultraviolet photoelectron spectroscopes (XPS and UPS) and inverse photoelectron spectroscopy (IPES). As discussed herein, both occupied and unoccupied electronic states at the interfaces are carefully examined in different aspects. In Chapter 4, the charge transfer and chemical reaction at various metal/Alq3 interfaces are investigated using XPS and UPS to study the electron injection into the Alga film. Electron transfer from the low work function metal and Al/LiF(CsF) bilayer to the Alga has been observed. The role of the dielectric and possible chemistry at the interface are discussed in comparison of the low work function metals. Further in Chapter 5, the origin of the metal-interface dipole and the estimation of charge injection barrier is explored using several organic materials. A thermodynamic equilibrium model is extended to explain the relation between the charge transfer process ad the interface dipole. Further, in Chapter 6 the combination of XPS, UPS and IPES detailed the evolution of both occupied and unoccupied energy states during the alkali metal doping. The energy gap modification in organic due to metal doping is observed directly for the spectra. Chapter 7 provides stability study of the organic thin films under x-ray and UV light. The results verify the usability of UPS and XPS for the organic materials used in the thesis. Chapter 7 also shows the secondary ion mass spectroscopy results of metal diffusion in organic thin films.

Controlled phase gate for solid-state charge-qubit architectures

International Nuclear Information System (INIS)

Schirmer, S.G.; Oi, D.K.L.; Greentree, Andrew D.

2005-01-01

We describe a mechanism for realizing a controlled phase gate for solid-state charge qubits. By augmenting the positionally defined qubit with an auxiliary state, and changing the charge distribution in the three-dot system, we are able to effectively switch the Coulombic interaction, effecting an entangling gate. We consider two architectures, and numerically investigate their robustness to gate noise

Near thermal charge transfer between Ar+2 and N2

International Nuclear Information System (INIS)

Holzscheiter, H.M.; Church, D.A.

1981-01-01

The near thermal charge transfer reaction of Ar +2 with N 2 has been studied at total pressures below 10 -7 Torr using a stored ion technique. Ar +2 ions produced by electron impact double ionization of Ar gas were selectively stored for times the order of seconds in a split-ring Penning-type ion trap. The decay with time of the initial ion sample number in a mixture of Ar and N 2 gases was fit to the sum of two exponentials, corresponding to different reaction rates for the 3 P and 1 D low-lying Ar +2 levels. The observed Ar +2 number decrease is attributed to the double-charge transfer process Ar +2 +N 2 →Ar+N 2 +2 →Ar+N + +N + in accord with recent flow-tube measurements. A rate constant for the metastable Ar +2 ( 1 D) level reaction with a value k( 1 D)=1.4 x 10 -9 cm 3 /sec is obtained, using the previously measured rate constant for the Ar +2 ( 3 P) state

Charge transfer between acenes and PbS nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Dissanayake, D M N M [Solid State Electronics Laboratory, University of Michigan, Ann Arbor, MI 48109-2122 (United States); Hatton, R A [Department of Chemistry, University of Warwick, Coventry CV4 7AL (United Kingdom); Lutz, T [Departments of Chemistry and Physics, Imperial College, London SW7 2AY (United Kingdom); Curry, R J; Silva, S R P [Advanced Technology Institute, University of Surrey, Guildford GU2 7XH (United Kingdom)], E-mail: ndissa@umich.edu

2009-05-13

Organic-inorganic hybrid heterojunctions have potential as the basis for future photovoltaic devices. Herein, we report the results of investigations exploring the possibility of using pentacene and tetracene as photoelectron donors in conjunction with PbS nanocrystals (PbS-NCs). Photoinduced charge transfer was probed using external quantum efficiency measurements on acene:PbS-NC hybrid photovoltaic devices in conjunction with photoluminescence studies of the corresponding bilayer films. It is shown that photoelectron transfer from pentacene to the PbS-NCs is inefficient as compared to that between tetracene and PbS-NCs. The latter case can be rationalized in terms of the energy level alignment at the heterojunction assuming a common vacuum level. However, in the case of pentacene:PbS-NC junctions an interfacial energy level shift must be considered in order to explain the observations.

A study of vibrational spectra and investigations of charge transfer and chemical bonding features of 2-chloro benzimidazole based on DFT computations

Science.gov (United States)

Muthunatesan, S.; Ragavendran, V.

2015-01-01

Benzimidazoles are bicyclic heteroatomic molecules. Polycyclic heteroatomic molecules have extensive coupling of different modes leading to strong coupling of force constants associated with the various chemical bonds of the molecules. To carry out a detailed vibrational spectroscopic analysis of such a bicyclic heteroatomic molecule, FT-IR and FT-Raman spectra of 2-chloro benzimidazole (CBZ) have been recorded in the condensed phase. Density Functional Theory calculations in the B3LYP/6-31G* level have been carried out to determine the optimized geometry and vibrational frequencies. In order to obtain a close agreement between theoretical and observed frequencies and hence to perform a reliable assignment, the theoretical DFT force field was transformed from Cartesian to local symmetry co-ordinates and then scaled empirically using SQM methodology. The SQM treatment resulted in a RMS deviation of 9.4 cm-1. For visual comparison, the observed and calculated spectra are presented on a common wavenumber scale. From the NBO analysis, the electron density (ED) charge transfers in the σ* and π* antibonding orbitals and second order delocalization energies E(2) confirms the occurrence of intramolecular charge transfer (ICT) within the molecule. The calculated Homo and Lumo energies show that charge transfer occurs within the molecule. The results obtained from the vibrational, NBO and HOMO-LUMO analyses have been properly tabulated.

Charge-Transfer Processes in Warm Dense Matter: Selective Spectral Filtering for Laser-Accelerated Ion Beams

Science.gov (United States)

Braenzel, J.; Barriga-Carrasco, M. D.; Morales, R.; Schnürer, M.

2018-05-01

We investigate, both experimentally and theoretically, how the spectral distribution of laser accelerated carbon ions can be filtered by charge exchange processes in a double foil target setup. Carbon ions at multiple charge states with an initially wide kinetic energy spectrum, from 0.1 to 18 MeV, were detected with a remarkably narrow spectral bandwidth after they had passed through an ultrathin and partially ionized foil. With our theoretical calculations, we demonstrate that this process is a consequence of the evolution of the carbon ion charge states in the second foil. We calculated the resulting spectral distribution separately for each ion species by solving the rate equations for electron loss and capture processes within a collisional radiative model. We determine how the efficiency of charge transfer processes can be manipulated by controlling the ionization degree of the transfer matter.

Synthetic system mimicking the energy transfer and charge separation of natural photosynthesis

Energy Technology Data Exchange (ETDEWEB)

Gust, D.; Moore, T.A.

1985-05-01

A synthetic molecular triad consisting of a porphyrin P linked to both a quinone Q and a carotenoid polyene C has been prepared as a mimic of natural photosynthesis for solar energy conversion purposes. Laser flash excitation of the porphyrin moiety yields a charge-separated state Csup(+.)-P-Qsup(-.) within 100 ps with a quantum yield of more than 0.25. This charge-separated state has a lifetime on the microsecond time scale in suitable solvents. The triad also models photosynthetic antenna function and photoprotection from singlet oxygen damge. The successful biomimicry of photosynthetic charge separation is in part the result of multistep electron transfers which rapidly separate the charges and leave the system at high potential, but with a considerable barrier to recombination.

Experimental determination of the heat transfer and cold storage characteristics of a microencapsulated phase change material in a horizontal tank

International Nuclear Information System (INIS)

Allouche, Yosr; Varga, Szabolcs; Bouden, Chiheb; Oliveira, Armando C.

2015-01-01

Highlights: • Cold storage characteristics in latent and sensible heat storage mediums were studied. • Thermo-physical characterization of the phase change material was carried out. • A non-Newtonian shear thickening behavior of the phase change material was observed. • An energy storage enhancement (53%) was observed in the latent heat storage medium. - Abstract: In the present paper, the performance of a microencapsulated phase change material (in 45% w/w concentration) for low temperature thermal energy storage, suitable for air conditioning applications is studied. The results are compared to a sensible heat storage unit using water. Thermo-physical properties such as the specific heat, enthalpy variation, thermal conductivity and density are also experimentally determined. The non-Newtonian shear-thickening behavior of the phase change material slurry is quantified. Thermal energy performance is experimentally determined for a 100 l horizontal tank. The heat transfer between the heat transfer fluid and the phase change material was provided by a tube-bundle heat exchanger inside the tank. The results show that the amount of energy stored using the phase change material is 53% higher than for water after 10 h of charging, for the same storage tank volume. It was found that the heat transfer coefficient between the phase change material and the tube wall increases during the phase change temperature range, however it remains smaller than the values obtained for water

Charge and energy transfer interplay in hybrid sensitized solar cells mediated by graphene quantum dots

International Nuclear Information System (INIS)

Mihalache, Iuliana; Radoi, Antonio; Mihaila, Mihai; Munteanu, Cornel; Marin, Alexandru; Danila, Mihai; Kusko, Mihaela; Kusko, Cristian

2015-01-01

Highlights: • We report a one pot synthesis metod of GQD with controlled size and optoelectronic properties. • An improvement of common N3-DSSC characteristics is achieved when GQDs are used as co-sensitiser. • The role of GQD as cosensitisers in hybrid DSSC was investigated and the interplay between charge and energy transfer phenomena mediated by GQDs was demonstrated. • The GQDs presence determines an inhibition of the recombination processes at the TiO 2 /electrolyte interface. - Abstract: We explored the role of graphene quantum dots (GQDs) as co-sensitizers in hybrid dye sensitized solar cell (DSSC) architectures, focusing on various concurring mechanisms, such as: charge transfer, energy transfer and recombination rate, towards light harvesting improvement. GQDs were prepared by the hydrothermal method that allows the tuning of electronic levels and optical properties by employing appropriate precursors and synthesis conditions. The aim was to realize a type II alignment for TiO 2 /GQD/dye hybrid configuration, using standard N3 Ru-dye in order to improve charge transfer. When GQDs were used as co-sensitizers together with N3 Ru-dye, an improvement in power conversion efficiency was achieved, as shown by electrical measurements. The experimental analysis indicates that this improvement arises from the interplay of various mechanisms mediated by GQDs: (i) enhancement of charge separation and collection due to the cascaded alignment of the energy levels; (ii) energy transfer from GQDs to N3 Ru-dye due to the overlap between GQD photoluminescence and N3 Ru-dye absorption spectra; and (iii) reduction of the electron recombination to the redox couple due to the inhibition of the back electron transfer to the electrolyte by the GQDs

Effect of net surface charge on particle sizing and material recognition by using phase Doppler anemometry

International Nuclear Information System (INIS)

Zhou Jun; Xie Li

2011-01-01

By taking net surface charge into consideration, the scattering field of particles illuminated by dual laser beams of phase Doppler anemometry (PDA) is computed based on Mie's theory, and the effect of net surface charge on the phase-diameter relationship and the phase ratio is studied. It is found that the phase-diameter relationship and the relationship between the phase ratio and the refractive index of charged particles could be significantly different from those of uncharged particles, which would lead to errors in particle sizing and the measurement of refractive indices. A method of recognizing charged particles and determining the value of their surface conductivity, which is related to net surface charge, is proposed by utilizing the effect of net surface charge on the measurement of refractive indices using PDA.

Effect of net surface charge on particle sizing and material recognition by using phase Doppler anemometry

Energy Technology Data Exchange (ETDEWEB)

Zhou Jun; Xie Li

2011-01-20

By taking net surface charge into consideration, the scattering field of particles illuminated by dual laser beams of phase Doppler anemometry (PDA) is computed based on Mie's theory, and the effect of net surface charge on the phase-diameter relationship and the phase ratio is studied. It is found that the phase-diameter relationship and the relationship between the phase ratio and the refractive index of charged particles could be significantly different from those of uncharged particles, which would lead to errors in particle sizing and the measurement of refractive indices. A method of recognizing charged particles and determining the value of their surface conductivity, which is related to net surface charge, is proposed by utilizing the effect of net surface charge on the measurement of refractive indices using PDA.

Charge transfer collisions of Si^3+ with H at low energies

Science.gov (United States)

Joseph, D. C.; Gu, J. P.; Saha, B. C.

2009-11-01

Charge transfer of positively charged ions with atomic hydrogen is important not only in magnetically confined plasmas between impurity ions and H atoms from the chamber walls influences the overall ionization balance and effects the plasma cooling but also in astrophysics, where it plays a key role in determining the properties of the observed gas. It also provides a recombination mechanism for multiply charged ions in X-ray ionized astronomical environments. We report an investigation using the molecular-orbital close-coupling (MOCC) method, both quantum mechanically and semi-classically, in the adiabatic representation. Ab initio adiabatic potentials and coupling matrix elements--radial and angular--are calculated using the MRD-CI method. Comparison of our results with other theoretical as well as experimental findings will be discussed.

Theoretical Study of the Charge-Transfer State Separation within Marcus Theory

DEFF Research Database (Denmark)

Volpi, Riccardo; Nassau, Racine; Nørby, Morten Steen

2016-01-01

We study, within Marcus theory, the possibility of the charge-transfer (CT) state splitting at organic interfaces and a subsequent transport of the free charge carriers to the electrodes. As a case study we analyze model anthracene-C60 interfaces. Kinetic Monte Carlo (KMC) simulations on the cold...... CT state were performed at a range of applied electric fields, and with the fields applied at a range of angles to the interface to simulate the action of the electric field in a bulk heterojunction (BHJ) interface. The results show that the inclusion of polarization in our model increases CT state...... dissociation and charge collection. The effect of the electric field on CT state splitting and free charge carrier conduction is analyzed in detail with and without polarization. Also, depending on the relative orientation of the anthracene and C60 molecules at the interface, CT state splitting shows different...

Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses

Directory of Open Access Journals (Sweden)

Rebecca Boll

2016-07-01

Full Text Available Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I21+. The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse.

Structure and charge transfer correlated with oxygen content for a Y0.8Ca0.2Ba2Cu3Oy (y = 6.84 6.32) system: a positron study

Science.gov (United States)

Cao, Shixun; Li, Lingwei; Liu, Fen; Li, Wenfeng; Chi, Changyun; Jing, Chao; Zhang, Jincang

2005-05-01

The structure and charge transfer correlated with oxygen content are studied by measuring the positron lifetime parameters of the Y0.8Ca0.2Ba2Cu3Oy system with a large range of oxygen content (y = 6.84-6.32). The local electron density ne is evaluated from the positron lifetime data. The positron lifetime parameters show a clear change around y = 6.50 where the compounds undergo the orthorhombic-tetragonal phase transition. The effect of ne and oxygen content on the structure, charge transfer and superconductivity are discussed. With the decrease of oxygen content y, O(4) tends to the Cu(1) site, causing carrier localization, and accordingly, the decrease of ne. This would prove that the localized carriers (electrons and holes) in the Cu-O chain region have great influence on the superconductivity by affecting the charge transfer between the reservoir layers and the conducting layers. The positron annihilation mechanism and its relation with superconductivity are also discussed.

Single-crystal charge transfer interfaces for efficient photonic devices (Conference Presentation)

Science.gov (United States)

Alves, Helena; Pinto, Rui M.; Maçôas, Ermelinda M. S.; Baleizão, Carlos; Santos, Isabel C.

2016-09-01

Organic semiconductors have unique optical, mechanical and electronic properties that can be combined with customized chemical functionality. In the crystalline form, determinant features for electronic applications such as molecular purity, the charge mobility or the exciton diffusion length, reveal a superior performance when compared with materials in a more disordered form. Combining crystals of two different conjugated materials as even enable a new 2D electronic system. However, the use of organic single crystals in devices is still limited to a few applications, such as field-effect transistors. In 2013, we presented the first system composed of single-crystal charge transfer interfaces presenting photoconductivity behaviour. The system composed of rubrene and TCNQ has a responsivity reaching 1 A/W, corresponding to an external quantum efficiency of nearly 100%. A similar approach, with a hybrid structure of a PCBM film and rubrene single crystal also presents high responsivity and the possibility to extract excitons generated in acceptor materials. This strategy led to an extended action towards the near IR. By adequate material design and structural organisation of perylediimides, we demonstrate that is possible to improve exciton diffusion efficiency. More recently, we have successfully used the concept of charge transfer interfaces in phototransistors. These results open the possibility of using organic single-crystal interfaces in photonic applications.

Charge transfer luminescence of Yb3+ ions in LiY1-xYbxP4O12 phosphates

International Nuclear Information System (INIS)

Stryganyuk, G; Zazubovich, S; Voloshinovskii, A; Pidzyrailo, M; Zimmerer, G; Peters, R; Petermann, K

2007-01-01

Spectral-kinetic studies have been performed for LiY 1-x Yb x P 4 O 12 (x = 0; 0.1; 0.9) phosphates at T = 8-320 K using synchrotron radiation for excitation within the 5-17 eV energy range. Mechanisms for the excitation of Yb 3+ charge transfer and f-f luminescence are discussed. The quasimolecular character of Yb 3+ charge transfer luminescence (CTL) is pointed out. The central Yb 2+ ion and hole delocalized over the surrounding ligands are proposed for consideration as a 'charge transfer cluster' (Yb 2+ CT cluster). Possible mechanisms of Yb 3+ CTL quenching are presumed

Ultrafast spin exchange-coupling torque via photo-excited charge-transfer processes

Science.gov (United States)

Ma, X.; Fang, F.; Li, Q.; Zhu, J.; Yang, Y.; Wu, Y. Z.; Zhao, H. B.; Lüpke, G.

2015-10-01

Optical control of spin is of central importance in the research of ultrafast spintronic devices utilizing spin dynamics at short time scales. Recently developed optical approaches such as ultrafast demagnetization, spin-transfer and spin-orbit torques open new pathways to manipulate spin through its interaction with photon, orbit, charge or phonon. However, these processes are limited by either the long thermal recovery time or the low-temperature requirement. Here we experimentally demonstrate ultrafast coherent spin precession via optical charge-transfer processes in the exchange-coupled Fe/CoO system at room temperature. The efficiency of spin precession excitation is significantly higher and the recovery time of the exchange-coupling torque is much shorter than for the demagnetization procedure, which is desirable for fast switching. The exchange coupling is a key issue in spin valves and tunnelling junctions, and hence our findings will help promote the development of exchange-coupled device concepts for ultrafast coherent spin manipulation.

Evidence for charge-trapping inducing polymorphic structural-phase transition in pentacene.

Science.gov (United States)

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.

Development of highly accurate approximate scheme for computing the charge transfer integral

Energy Technology Data Exchange (ETDEWEB)

Pershin, Anton; Szalay, Péter G. [Laboratory for Theoretical Chemistry, Institute of Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest (Hungary)

2015-08-21

The charge transfer integral is a key parameter required by various theoretical models to describe charge transport properties, e.g., in organic semiconductors. The accuracy of this important property depends on several factors, which include the level of electronic structure theory and internal simplifications of the applied formalism. The goal of this paper is to identify the performance of various approximate approaches of the latter category, while using the high level equation-of-motion coupled cluster theory for the electronic structure. The calculations have been performed on the ethylene dimer as one of the simplest model systems. By studying different spatial perturbations, it was shown that while both energy split in dimer and fragment charge difference methods are equivalent with the exact formulation for symmetrical displacements, they are less efficient when describing transfer integral along the asymmetric alteration coordinate. Since the “exact” scheme was found computationally expensive, we examine the possibility to obtain the asymmetric fluctuation of the transfer integral by a Taylor expansion along the coordinate space. By exploring the efficiency of this novel approach, we show that the Taylor expansion scheme represents an attractive alternative to the “exact” calculations due to a substantial reduction of computational costs, when a considerably large region of the potential energy surface is of interest. Moreover, we show that the Taylor expansion scheme, irrespective of the dimer symmetry, is very accurate for the entire range of geometry fluctuations that cover the space the molecule accesses at room temperature.

Strategies to enhance the excitation energy-transfer efficiency in a light-harvesting system using the intra-molecular charge transfer character of carotenoids

Energy Technology Data Exchange (ETDEWEB)

Yukihira, Nao [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Sugai, Yuko [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Fujiwara, Masazumi [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan; Kosumi, Daisuke [Institute of Pulsed Power Science; Kumamoto University; Kumamoto; Japan; Iha, Masahiko [South Product Co. Ltd.; Uruma-shi; Japan; Sakaguchi, Kazuhiko [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Katsumura, Shigeo [Department of Chemistry; Graduate School of Science; Osaka City University; Osaka 558-8585; Japan; Gardiner, Alastair T. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Cogdell, Richard J. [Glasgow Biomedical Research Centre; University of Glasgow; 126 University Place; Glasgow, G12 8QQ; UK; Hashimoto, Hideki [Department of Applied Chemistry for Environment; School of Science and Technology; Kwansei Gakuin University; Sanda; Japan

2017-01-01

Fucoxanthin is a carotenoid that is mainly found in light-harvesting complexes from brown algae and diatoms. Due to the presence of a carbonyl group attached to polyene chains in polar environments, excitation produces an excited intra-molecular charge transfer. This intra-molecular charge transfer state plays a key role in the highly efficient (~95%) energy-transfer from fucoxanthin to chlorophyllain the light-harvesting complexes from brown algae. In purple bacterial light-harvesting systems the efficiency of excitation energy-transfer from carotenoids to bacteriochlorophylls depends on the extent of conjugation of the carotenoids. In this study we were successful, for the first time, in incorporating fucoxanthin into a light-harvesting complex 1 from the purple photosynthetic bacterium,Rhodospirillum rubrumG9+ (a carotenoidless strain). Femtosecond pump-probe spectroscopy was applied to this reconstituted light-harvesting complex in order to determine the efficiency of excitation energy-transfer from fucoxanthin to bacteriochlorophyllawhen they are bound to the light-harvesting 1 apo-proteins.

Polarization and charge transfer in the hydration of chloride ions

International Nuclear Information System (INIS)

Zhao Zhen; Rogers, David M.; Beck, Thomas L.

2010-01-01

A theoretical study of the structural and electronic properties of the chloride ion and water molecules in the first hydration shell is presented. The calculations are performed on an ensemble of configurations obtained from molecular dynamics simulations of a single chloride ion in bulk water. The simulations utilize the polarizable AMOEBA force field for trajectory generation and MP2-level calculations are performed to examine the electronic structure properties of the ions and surrounding waters in the external field of more distant waters. The ChelpG method is employed to explore the effective charges and dipoles on the chloride ions and first-shell waters. The quantum theory of atoms in molecules (QTAIM) is further utilized to examine charge transfer from the anion to surrounding water molecules. The clusters extracted from the AMOEBA simulations exhibit high probabilities of anisotropic solvation for chloride ions in bulk water. From the QTAIM analysis, 0.2 elementary charges are transferred from the ion to the first-shell water molecules. The default AMOEBA model overestimates the average dipole moment magnitude of the ion compared to the quantum mechanical value. The average magnitude of the dipole moment of the water molecules in the first shell treated at the MP2-level, with the more distant waters handled with an AMOEBA effective charge model, is 2.67 D. This value is close to the AMOEBA result for first-shell waters (2.72 D) and is slightly reduced from the bulk AMOEBA value (2.78 D). The magnitude of the dipole moment of the water molecules in the first solvation shell is most strongly affected by the local water-water interactions and hydrogen bonds with the second solvation shell, rather than by interactions with the ion.

Phase-Transfer Energetics of Small-Molecule Alcohols Across the Water-Hexane Interface: Molecular Dynamics Simulation Using Charge Equilibration Models

Science.gov (United States)

Bauer, Brad A.; Zhong, Yang; Meninger, David J.; Davis, Joseph E.; Patel, Sandeep

2010-01-01

We study the water-hexane interface using molecular dynamics (MD) and polarizable charge equilibration (CHEQ) force fields. Bulk densities for TIP4P-FQ water and hexane, 1.0086±0.0002 g/cm3 and 0.6378±0.0001 g/cm3, demonstrate excellent agreement with experiment. Interfacial width and interfacial tension are consistent with previously reported values. The in-plane component of the dielectric permittivity (ε∥) for water is shown to decrease from 81.7±0.04 to unity, transitioning longitudinally from bulk water to bulk hexane. ε∥ for hexane reaches a maximum in the interface, but this term represents only a small contribution to the total dielectric constant (as expected for a non-polar species). Structurally, net orientations of the molecules arise in the interfacial region such that hexane lies slightly parallel to the interface and water reorients to maximize hydrogen bonding. Interfacial potentials due to contributions of the water and hexane are calculated to be -567.9±0.13mV and 198.7±0.01mV, respectively, giving rise to a total potential in agreement with the range of values reported from previous simulations of similar systems. Potentials of mean force (PMF) calculated for methanol, ethanol, and 1-propanol for the transfer from water to hexane indicate an interfacial free energy minimum, corresponding to the amphiphilic nature of the molecules. The magnitudes of transfer free energies were further characterized from the solvation free energies of alcohols in water and hexane using thermodynamic integration. This analysis shows that solvation free energies for alcohols in hexane are 0.2-0.3 kcal/mol too unfavorable, whereas solvation of alcohols in water is approximately 1 kcal/mol too favorable. For the pure hexane-water interfacial simulations, we observe a monotonic decrease of the water dipole moment to near-vacuum values. This suggests that the electrostatic component of the desolvation free energy is not as severe for polarizable models than

Spectroscopic study of the charge-transfer complexes TiCl4/styrene and TiCl4/polystyrene

Science.gov (United States)

Gonçalves, Norberto S.; Noda, Lúcia. K.

2017-10-01

In this work, solutions of TiCl4/styrene and TiCl4/polystyrene charge-transfer complexes in CHCl3 or CDCl3 were investigated by UV-vis, resonance Raman and 1H NMR spectroscopies in order to study their molecular and electronic structures. Both show a yellow colour due to absorption in the 400 nm region, related to a charge-transfer transition. In Raman spectra, as the excitation approaches the resonance region, the primary enhancement of aromatic ring modes was mainly observed, rather than intensification of the vinylic double-bond stretch. Under the experimental conditions it was observed that formation of polystyrene takes place, as showed by 1H NMR spectra, and the most significant interaction occurs at the aromatic ring, as supported by the results from interaction of TiCl4 with polystyrene, as indicated by the charge-transfer band and resonant intensification of the aromatic ring modes.

Communication: Modeling of concentration dependent water diffusivity in ionic solutions: Role of intermolecular charge transfer

Energy Technology Data Exchange (ETDEWEB)

Yao, Yi; Berkowitz, Max L., E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu; Kanai, Yosuke, E-mail: maxb@unc.edu, E-mail: ykanai@unc.edu [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599 (United States)

2015-12-28

The translational diffusivity of water in solutions of alkali halide salts depends on the identity of ions, exhibiting dramatically different behavior even in solutions of similar salts of NaCl and KCl. The water diffusion coefficient decreases as the salt concentration increases in NaCl. Yet, in KCl solution, it slightly increases and remains above bulk value as salt concentration increases. Previous classical molecular dynamics simulations have failed to describe this important behavior even when polarizable models were used. Here, we show that inclusion of dynamical charge transfer among water molecules produces results in a quantitative agreement with experiments. Our results indicate that the concentration-dependent diffusivity reflects the importance of many-body effects among the water molecules in aqueous ionic solutions. Comparison with quantum mechanical calculations shows that a heterogeneous and extended distribution of charges on water molecules around the ions due to ion-water and also water-water charge transfer plays a very important role in controlling water diffusivity. Explicit inclusion of the charge transfer allows us to model accurately the difference in the concentration-dependent water diffusivity between Na{sup +} and K{sup +} ions in simulations, and it is likely to impact modeling of a wide range of systems for medical and technological applications.

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Gross, Dieter Konrad Michael

2013-11-08

Closely packed nanocrystal systems have been investigated in this thesis with respect to charge separation by charge carrier tunneling. Clustered and layered samples have been analyzed using PL-measurements and SPV-methods. The most important findings are reviewed in the following. A short outlook is also provided for potential further aspects and application of the presented results. The main purpose of this thesis was to find and quantify electronic tunneling transfer in closely packed self-assembled nanocrystal structures presenting quantum mechanical barriers of about 1 nm width. We successfully used hybrid assemblies of CdTe and CdSe nanocrystals where the expected type II alignment between CdTe and CdSe typically leads to a concentration of electrons in CdSe and holes in CdTe nanocrystals. We were able to prove the charge selectivity of the CdTe-CdSe nanocrystal interface which induces charge separation. We mainly investigated the effects related to the electron transfer from CdTe to CdSe nanocrystals. Closely packing was achieved by two independent methods: the disordered colloidal clustering in solution and the layered assembly on dry glass substrates. Both methods lead to an inter-particle distance of about 1 nm of mainly organic material which acts as a tunneling barrier. PL-spectroscopy was applied. The PL-quenching of the CdTe nanocrystals in hybrid assemblies indicates charge separation by electron transfer from CdTe to CdSe nanocrystals. A maximum quenching rate of up to 1/100 ps was measured leading to a significant global PL-quenching of up to about 70 % for the CdTe nanocrystals. It was shown that charge separation dynamics compete with energy transfer dynamics and that charge separation typically dominates. The quantum confinement effect was used to tune the energetic offset between the CdTe and CdSe nanocrystals. We thus observe a correlation of PL-quenching and offset of the energy states for the electron transfer. The investigated PL

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

International Nuclear Information System (INIS)

Gross, Dieter Konrad Michael

2013-01-01

Closely packed nanocrystal systems have been investigated in this thesis with respect to charge separation by charge carrier tunneling. Clustered and layered samples have been analyzed using PL-measurements and SPV-methods. The most important findings are reviewed in the following. A short outlook is also provided for potential further aspects and application of the presented results. The main purpose of this thesis was to find and quantify electronic tunneling transfer in closely packed self-assembled nanocrystal structures presenting quantum mechanical barriers of about 1 nm width. We successfully used hybrid assemblies of CdTe and CdSe nanocrystals where the expected type II alignment between CdTe and CdSe typically leads to a concentration of electrons in CdSe and holes in CdTe nanocrystals. We were able to prove the charge selectivity of the CdTe-CdSe nanocrystal interface which induces charge separation. We mainly investigated the effects related to the electron transfer from CdTe to CdSe nanocrystals. Closely packing was achieved by two independent methods: the disordered colloidal clustering in solution and the layered assembly on dry glass substrates. Both methods lead to an inter-particle distance of about 1 nm of mainly organic material which acts as a tunneling barrier. PL-spectroscopy was applied. The PL-quenching of the CdTe nanocrystals in hybrid assemblies indicates charge separation by electron transfer from CdTe to CdSe nanocrystals. A maximum quenching rate of up to 1/100 ps was measured leading to a significant global PL-quenching of up to about 70 % for the CdTe nanocrystals. It was shown that charge separation dynamics compete with energy transfer dynamics and that charge separation typically dominates. The quantum confinement effect was used to tune the energetic offset between the CdTe and CdSe nanocrystals. We thus observe a correlation of PL-quenching and offset of the energy states for the electron transfer. The investigated PL

Charge separation and transfer in hybrid type II tunneling structures of CdTe and CdSe nanocrystals

Energy Technology Data Exchange (ETDEWEB)

Gross, Dieter Konrad Michael

2013-11-08

Closely packed nanocrystal systems have been investigated in this thesis with respect to charge separation by charge carrier tunneling. Clustered and layered samples have been analyzed using PL-measurements and SPV-methods. The most important findings are reviewed in the following. A short outlook is also provided for potential further aspects and application of the presented results. The main purpose of this thesis was to find and quantify electronic tunneling transfer in closely packed self-assembled nanocrystal structures presenting quantum mechanical barriers of about 1 nm width. We successfully used hybrid assemblies of CdTe and CdSe nanocrystals where the expected type II alignment between CdTe and CdSe typically leads to a concentration of electrons in CdSe and holes in CdTe nanocrystals. We were able to prove the charge selectivity of the CdTe-CdSe nanocrystal interface which induces charge separation. We mainly investigated the effects related to the electron transfer from CdTe to CdSe nanocrystals. Closely packing was achieved by two independent methods: the disordered colloidal clustering in solution and the layered assembly on dry glass substrates. Both methods lead to an inter-particle distance of about 1 nm of mainly organic material which acts as a tunneling barrier. PL-spectroscopy was applied. The PL-quenching of the CdTe nanocrystals in hybrid assemblies indicates charge separation by electron transfer from CdTe to CdSe nanocrystals. A maximum quenching rate of up to 1/100 ps was measured leading to a significant global PL-quenching of up to about 70 % for the CdTe nanocrystals. It was shown that charge separation dynamics compete with energy transfer dynamics and that charge separation typically dominates. The quantum confinement effect was used to tune the energetic offset between the CdTe and CdSe nanocrystals. We thus observe a correlation of PL-quenching and offset of the energy states for the electron transfer. The investigated PL

Momentum transfer in relativistic heavy ion charge-exchange reactions

Science.gov (United States)

Townsend, L. W.; Wilson, J. W.; Khan, F.; Khandelwal, G. S.

1991-01-01

Relativistic heavy ion charge-exchange reactions yield fragments (Delta-Z = + 1) whose longitudinal momentum distributions are downshifted by larger values than those associated with the remaining fragments (Delta-Z = 1, -2,...). Kinematics alone cannot account for the observed downshifts; therefore, an additional contribution from collision dynamics must be included. In this work, an optical model description of collision momentum transfer is used to estimate the additional dynamical momentum downshift. Good agreement between theoretical estimates and experimental data is obtained.

Observation of excited state charge transfer with fs/ps-CARS

International Nuclear Information System (INIS)

Blom, Alex Jason

2009-01-01

Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4(prime)-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4(prime)-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles

Observation of excited state charge transfer with fs/ps-CARS

Energy Technology Data Exchange (ETDEWEB)

Blom, Alex Jason [Iowa State Univ., Ames, IA (United States)

2009-01-01

Excited state charge transfer processes are studied using the fs/ps-CARS probe technique. This probe allows for multiplexed detection of Raman active vibrational modes. Systems studied include Michler's Ketone, Coumarin 120, 4-dimethylamino-4'-nitrostilbene, and several others. The vibrational spectrum of the para di-substituted benzophenone Michler's Ketone in the first excited singlet state is studied for the first time. It is found that there are several vibrational modes indicative of structural changes of the excited molecule. A combined experimental and theoretical approach is used to study the simplest 7-amino-4-methylcoumarin, Coumarin 120. Vibrations observed in FTIR and spontaneous Raman spectra are assigned using density functional calculations and a continuum solvation model is used to predict how observed modes are affected upon inclusion of a solvent. The low frequency modes of the excited state charge transfer species 4-dimethylamino-4{prime}-nitrostilbene are studied in acetonitrile. Results are compared to previous work on this molecule in the fingerprint region. Finally, several partially completed projects and their implications are discussed. These include the two photon absorption of Coumarin 120, nanoconfinement in cyclodextrin cavities and sensitization of titania nanoparticles.

The description of charge transfer in fast negative ions scattering on water covered Si(100) surfaces

Energy Technology Data Exchange (ETDEWEB)

Chen, Lin; Qiu, Shunli; Liu, Pinyang; Xiong, Feifei; Lu, Jianjie; Liu, Yuefeng; Li, Guopeng; Liu, Yiran; Ren, Fei; Xiao, Yunqing; Gao, Lei; Zhao, Qiushuang; Ding, Bin; Li, Yuan [School of Nuclear Science and Technology, Lanzhou University, 730000 (China); Key Laboratory of Special Function Materials and Structure Design, Ministry of Education, Lanzhou University, 730000 (China); Guo, Yanling, E-mail: guoyanling@lzu.edu.cn [School of Nuclear Science and Technology, Lanzhou University, 730000 (China); Key Laboratory of Special Function Materials and Structure Design, Ministry of Education, Lanzhou University, 730000 (China); Chen, Ximeng, E-mail: chenxm@lzu.edu.cn [School of Nuclear Science and Technology, Lanzhou University, 730000 (China); Key Laboratory of Special Function Materials and Structure Design, Ministry of Education, Lanzhou University, 730000 (China)

2016-11-30

Highlights: • We first observe that negative-ion fractions present no variation with the doping concentration, which is very different from the results of low energy Li neutralization from doped Si samples. • Our work shows that the affinity levels and collision time significantly counteract the band gap effect on negative ion formation. The work will improve our understanding on electron transfer on semiconductor surfaces associated with doping. • In addition, we build a complete theoretical framework to quantitatively calculate the negative-ion fractions. • Our work is related to charge transfer on semiconductor surfaces, which will be of interest to a broad audience due to the wide necessity of the knowledge of charge exchange on semiconductor surfaces in different fields. - Abstract: Doping has significantly affected the characteristics and performance of semiconductor electronic devices. In this work, we study the charge transfer processes for 8.5–22.5 keV C{sup −} and F{sup −} ions scattering on H{sub 2}O-terminated p-type Si(100) surfaces with two different doping concentrations. We find that doping has no influence on negative-ion formation for fast collisions in this relatively high energy range. Moreover, we build a model to calculate negative ion fractions including the contribution from positive ions. The calculations support the nonadiabatic feature of charge transfer.

Thermodynamic geometry and phase transitions of dyonic charged AdS black holes

Energy Technology Data Exchange (ETDEWEB)

Chaturvedi, Pankaj; Sengupta, Gautam [Indian Institute of Technology Kanpur, Department of Physics, Kanpur (India); Das, Anirban [Tata Institute of Fundamental Research, Department of Theoretical Physics, Mumbai (India)

2017-02-15

We investigate phase transitions and critical phenomena of four dimensional dyonic charged AdS black holes in the framework of thermodynamic geometry. In a mixed canonical-grand canonical ensemble with a fixed electric charge and varying magnetic charge these black holes exhibit a liquid-gas like first order phase transition culminating in a second order critical point similar to the van der Waals gas. We show that the thermodynamic scalar curvature R for these black holes follow our proposed geometrical characterization of the R-crossing Method for the first order liquid-gas like phase transition and exhibits a divergence at the second order critical point. The pattern of R crossing and divergence exactly corresponds to those of a van der Waals gas described by us in an earlier work. (orig.)

Heat transfer modelling of two-phase bubbles swarm condensing in three - phase direct - contact condenser

Directory of Open Access Journals (Sweden)

Mahood Hameed B.

2016-01-01

Full Text Available An analytical model for the convective heat transfer coefficient and the two-phase bubble size of a three-phase direct contact heat exchanger was developed. Until the present, there has only been a theoretical model available that deals with a single two-phase bubble and a bubble train condensation in an immiscible liquid. However, to understand the actual heat transfer process within the three-phase direct contact condenser, characteristic models are required. A quasi - steady energy equation in a spherical coordinate system with a potential flow assumption and a cell model configuration has been simplified and solved analytically. The convective heat transfer in terms of Nu number has been derived, and it was found to be a function to Pe number and a system void fraction. In addition, the two-phase bubble size relates to the system void fraction and has been developed by solving a simple energy balance equation and using the derived convective heat transfer coefficient expression. Furthermore, the model correlates well with previous experimental data and theoretical results.

Charge Transfer in Collisions of S^4+ with H.

Science.gov (United States)

Stancil, P. C.; Turner, A. R.; Cooper, D. L.; Schultz, D. R.; Rakovic, M. J.; Fritsch, W.; Zygelman, B.

2001-05-01

Charge transfer processes due to collisions of ground state S^4+ ions with atomic hydrogen were investigated for energies between 1 meV/u and 10 MeV/u using the quantum-mechanical molecular-orbital close-coupling (MOCC), atomic-orbital close-coupling, classical trajectory Monte Carlo (CTMC), and continuum distorted wave methods. The MOCC calculations utilized ab initio adiabatic potentials and nonadiabatic radial coupling matrix elements obtained with the spin-coupled valence-bond approach. A number of variants of the CTMC approach were explored, including different momentum and radial distributions for the initial state, as well as effective charge and quantum-defect models to determine the corresponding quantum state after capture into final partially-stripped S^3+ excited classical states. Hydrogen target isotope effects were explored and rate coefficients for temperatures between 100 and 10^6 K will be presented

Charge transfer in proton-hydrogen collisions under Debye plasma

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Arka [Department of Mathematics, Burdwan University, Golapbag, Burdwan 713 104, West Bengal (India); Kamali, M. Z. M. [Centre for Foundation Studies in Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Ghoshal, Arijit, E-mail: arijit98@yahoo.com [Department of Mathematics, Burdwan University, Golapbag, Burdwan 713 104, West Bengal (India); Department of Mathematics, Kazi Nazrul University, B.C.W. Campus, Asansol 713 304, West Bengal (India); Institute of Mathematical Sciences, Faculty of Science, University of Malaya, 50603 Kuala Lumpur (Malaysia); Ratnavelu, K. [Department of Mathematics, Kazi Nazrul University, B.C.W. Campus, Asansol 713 304, West Bengal (India)

2015-02-15

The effect of plasma environment on the 1s → nlm charge transfer, for arbitrary n, l, and m, in proton-hydrogen collisions has been investigated within the framework of a distorted wave approximation. The effect of external plasma has been incorporated using Debye screening model of the interacting charge particles. Making use of a simple variationally determined hydrogenic wave function, it has been possible to obtain the scattering amplitude in closed form. A detailed study has been made to investigate the effect of external plasma environment on the differential and total cross sections for electron capture into different angular momentum states for the incident energy in the range of 20–1000 keV. For the unscreened case, our results are in close agreement with some of the most accurate results available in the literature.

Microchip-calorimetry of organic charge transfer complex which shows superconductivity at low temperatures

Energy Technology Data Exchange (ETDEWEB)

Muraoka, Yuki [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Yamashita, Satoshi [RIKEN, Hirosawa 2-1, Wako, Saitama 351-0198 (Japan); Yamamoto, Takashi [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Nakazawa, Yasuhiro, E-mail: nakazawa@chem.sci.osaka-u.ac.jp [Department of Chemistry, Graduate School of Science, Osaka University, Machikaneyama 1-1, Toyonaka, Osaka 560-0043 (Japan); Institute for Molecular Science, Nishigonaka 38, Myodaiji, Okazaki 444-8585 (Japan)

2012-03-20

Highlights: Black-Right-Pointing-Pointer Organic charge transfer salt of {kappa}-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br shows superconductivity. Black-Right-Pointing-Pointer We succeeded to detect thermal anomaly microchip device TCG3880. Black-Right-Pointing-Pointer Development details of the calorimeter and the detection system is presented. Black-Right-Pointing-Pointer The magnetic fields dependence shows typical character of layered superconductor. - Abstract: We carried out thermodynamic measurements of organic charge transfer complex of {kappa}-(BEDT-TTF){sub 2}Cu[N(CN){sub 2}]Br, where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene by TCG3880 chip device in order to examine capability of the chip calorimeter at low temperature region and under magnetic fields. TCG3880 chip is mounted on a {sup 3}He cryostat available in combination with a superconductive magnet up to 7 T. Thermal anomalies related to the glass-like freezing of ethylene groups of BEDT-TTF molecules and the superconductive transition were observed. A frequency dependence of the thermal anomaly of the glass formation and a magnetic fields dependence of the thermal anomaly of the superconductive transition are reported. The results presented in this work demonstrate that the TCG3880 is quite useful for thermodynamic investigations of the organic charge transfer complex with much reduced sample quantity as compared with those of relaxation and adiabatic calorimetry.

Doping graphene films via chemically mediated charge transfer

Directory of Open Access Journals (Sweden)

Ishikawa Ryousuke

2011-01-01

Full Text Available Abstract Transparent conductive films (TCFs are critical components of a myriad of technologies including flat panel displays, light-emitting diodes, and solar cells. Graphene-based TCFs have attracted a lot of attention because of their high electrical conductivity, transparency, and low cost. Carrier doping of graphene would potentially improve the properties of graphene-based TCFs for practical industrial applications. However, controlling the carrier type and concentration of dopants in graphene films is challenging, especially for the synthesis of p-type films. In this article, a new method for doping graphene using the conjugated organic molecule, tetracyanoquinodimethane (TCNQ, is described. Notably, TCNQ is well known as a powerful electron accepter and is expected to favor electron transfer from graphene into TCNQ molecules, thereby leading to p-type doping of graphene films. Small amounts of TCNQ drastically improved the resistivity without degradation of optical transparency. Our carrier doping method based on charge transfer has a huge potential for graphene-based TCFs.

Phase change heat transfer device for process heat applications

International Nuclear Information System (INIS)

Sabharwall, Piyush; Patterson, Mike; Utgikar, Vivek; Gunnerson, Fred

2010-01-01

The next generation nuclear plant (NGNP) will most likely produce electricity and process heat, with both being considered for hydrogen production. To capture nuclear process heat, and transport it to a distant industrial facility requires a high temperature system of heat exchangers, pumps and/or compressors. The heat transfer system is particularly challenging not only due to the elevated temperatures (up to ∼1300 K) and industrial scale power transport (≥50 MW), but also due to a potentially large separation distance between the nuclear and industrial plants (100+ m) dictated by safety and licensing mandates. The work reported here is the preliminary analysis of two-phase thermosyphon heat transfer performance with alkali metals. A thermosyphon is a thermal device for transporting heat from one point to another with quite extraordinary properties. In contrast to single-phased forced convective heat transfer via 'pumping a fluid', a thermosyphon (also called a wickless heat pipe) transfers heat through the vaporization/condensing process. The condensate is further returned to the hot source by gravity, i.e., without any requirement of pumps or compressors. With this mode of heat transfer, the thermosyphon has the capability to transport heat at high rates over appreciable distances, virtually isothermally and without any requirement for external pumping devices. Two-phase heat transfer by a thermosyphon has the advantage of high enthalpy transport that includes the sensible heat of the liquid, the latent heat of vaporization, and vapor superheat. In contrast, single-phase forced convection transports only the sensible heat of the fluid. Additionally, vapor-phase velocities within a thermosyphon are much greater than single-phase liquid velocities within a forced convective loop. Thermosyphon performance can be limited by the sonic limit (choking) of vapor flow and/or by condensate entrainment. Proper thermosyphon requires analysis of both.

Charge-transfer mobility and electrical conductivity of PANI as conjugated organic semiconductors.

Science.gov (United States)

Zhang, Yahong; Duan, Yuping; Song, Lulu; Zheng, Daoyuan; Zhang, Mingxing; Zhao, Guangjiu

2017-09-21

The intramolecular charge transfer properties of a phenyl-end-capped aniline tetramer (ANIH) and a chloro-substituted derivative (ANICl) as organic semiconductors were theoretically studied through the first-principles calculation based on the Marcus-Hush theory. The reorganization energies, intermolecular electronic couplings, angular resolution anisotropic mobilities, and density of states of the two crystals were evaluated. The calculated results demonstrate that both ANIH and ANICl crystals show the higher electron transfer mobilities than the hole-transfer mobilities, which means that the two crystals should prefer to function as n-type organic semiconductors. Furthermore, the angle dependence mobilities of the two crystals show remarkable anisotropic character. The maximum mobility μ max of ANIH and ANICl crystals is 1.3893 and 0.0272 cm 2 V -1 s -1 , which appear at the orientation angles near 176°/356° and 119°/299° of a conducting channel on the a-b reference plane. It is synthetically evaluated that the ANIH crystal possesses relatively lower reorganization energy, higher electronic coupling, and electron transfer mobility, which means that the ANIH crystal may be the more ideal candidate as a high performance n-type organic semiconductor material. The systematic theoretical studies on organic crystals should be conducive to evaluating the charge-transport properties and designing higher performance organic semiconductor materials.

Reduced Charge Transfer Exciton Recombination in Organic Semiconductor Heterojunctions by Molecular Doping

NARCIS (Netherlands)

Deschler, Felix; Da Como, Enrico; Limmer, Thomas; Tautz, Raphael; Godde, Tillmann; Bayer, Manfred; von Hauff, Elizabeth; Yilmaz, Seyfullah; Allard, Sybille; Scherf, Ullrich; Feldmann, Jochen

2011-01-01

We investigate the effect of molecular doping on the recombination of electrons and holes localized at conjugated-polymer–fullerene interfaces. We demonstrate that a low concentration of p-type dopant molecules (<4% weight) reduces the interfacial recombination via charge transfer excitons and

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals

Directory of Open Access Journals (Sweden)

Parul Chawla

2014-08-01

Full Text Available In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO and tri-n-octylphosphine (TOP and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern–Volmer quenching constant (KSV and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor–acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe. Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

An insight into the mechanism of charge-transfer of hybrid polymer:ternary/quaternary chalcopyrite colloidal nanocrystals.

Science.gov (United States)

Chawla, Parul; Singh, Son; Sharma, Shailesh Narain

2014-01-01

In this work, we have demonstrated the structural and optoelectronic properties of the surface of ternary/quaternary (CISe/CIGSe/CZTSe) chalcopyrite nanocrystallites passivated by tri-n-octylphosphine-oxide (TOPO) and tri-n-octylphosphine (TOP) and compared their charge transfer characteristics in the respective polymer: chalcopyrite nanocomposites by dispersing them in poly(3-hexylthiophene) polymer. It has been found that CZTSe nanocrystallites due to their high crystallinity and well-ordered 3-dimensional network in its pristine form exhibit a higher steric- and photo-stability, resistance against coagulation and homogeneity compared to the CISe and CIGSe counterparts. Moreover, CZTSe nanocrystallites display efficient photoluminescence quenching as evident from the high value of the Stern-Volmer quenching constant (K SV) and eventually higher charge transfer efficiency in their respective polymer P3HT:CZTSe composites. We modelled the dependency of the charge transfer from the donor and the charge separation mechanism across the donor-acceptor interface from the extent of crystallinity of the chalcopyrite semiconductors (CISe/CIGSe/CZTSe). Quaternary CZTSe chalcopyrites with their high crystallinity and controlled morphology in conjunction with regioregular P3HT polymer is an attractive candidate for hybrid solar cells applications.

Collective charge and mass transfer in heavy ion reactions

International Nuclear Information System (INIS)

Hahn, J.

1982-01-01

In this thesis the dynamics of the charge and mass asymmetry degree of freedom was studied in the framework of the fragmentation theory by means of a time-dependent Schroedinger equation. New is the introduction of a friction potential which describes the coupling of these collective degrees of freedom to the not explicitely treated other collective respectively internal degrees of freedom. Thereby it was shown that the measured widths of the isobaric charge distributions in the 86 Kr+sup(92,98)Mo reaction can be explained mainly by the quantum mechanical uncertainty in the charge asymmetry degree of freedom. The charge equilibration occurring at the begin of a deep inelastic collision can therefore by considered as a quantum mechanical, collective, damped motion which is connected with the excitation of the isovector giant dipole resonance of the nucleus-nucleus system. The study of the mass transfer in the reactions 132 Xe+ 120 Sn and 86 Kr+ 166 Er shows, how important at the begin of a deep inelastic collision shell structures and their conservation are for a large part of the reaction, even if the elemental distribution show no maxima in the region of magic shell closures. The experimental width are up to 10 MeV/A well described under conservation of the shell structure. (orig./HSI) [de

Coil Design for High Misalignment Tolerant Inductive Power Transfer System for EV Charging

Directory of Open Access Journals (Sweden)

Kafeel Ahmed Kalwar

2016-11-01

Full Text Available The inductive power transfer (IPT system for electric vehicle (EV charging has acquired more research interest in its different facets. However, the misalignment tolerance between the charging coil (installed in the ground and pick-up coil (mounted on the car chassis, has been a challenge and fundamental interest in the future market of EVs. This paper proposes a new coil design QDQ (Quad D Quadrature that maintains the high coupling coefficient and efficient power transfer during reasonable misalignment. The QDQ design makes the use of four adjacent circular coils and one square coil, for both charging and pick-up side, to capture the maximum flux at any position. The coil design has been modeled in JMAG software for calculation of inductive parameters using the finite element method (FEM, and its hardware has been tested experimentally at various misaligned positions. The QDQ coils are shown to be capable of achieving good coupling coefficient and high efficiency of the system until the misalignment displacement reaches 50% of the employed coil size.

A model for the chain-to-plane charge transfer in YBa2Cu3O6+x

International Nuclear Information System (INIS)

Matic, V. M.; Lazarov, N. Dj.; Milic, M.

2012-01-01

A model for the chain-to-plane charge transfer is proposed to account for the two plateaus, at 60 K and at 90 K, of the T c (x) characteristics of the YBa 2 Cu 3 O 6+x high-T c superconductor. It is assumed that the number of holes transferred from a CuO chain of length l to two nearby CuO 2 sheets is proportional to l (that is, to the number of oxygen atoms in the chain), if the chain length is greater than, or equal to, a certain critical chain length, l cr , that is required to trigger the charge transfer process. No holes are assumed to have been transferred from chains of length l cr . The calculated T c (x) dependence is found to be in excellent agreement with the experimentally reported T c (x). The critical chain length parameter is estimated to be equal to l cr = 11 (eleven oxygen atoms in a chain), which is a greater value than that obtained in the previously proposed model for the chain-to-plane charge transfer (l cr = 4). The results obtained out of the proposed model are briefly discussed

Heat transfer in two-phase flow of helium

International Nuclear Information System (INIS)

Subbotin, V.I.; Deev, V.I.; Solodovnikov, V.V.; Arkhipov, V.V.

1986-01-01

The results of experimental study of heat transfer in two-phase helium flow are presented. The effect of operating parameters (pressure, mass velocity, heat flux and quality) on boiling heat transfer intensity was investigated. A significant influence of boiling process prehistory on heat transfer coefficients was demonstrated. On the basis of experimental data obtained three typical regimes of flow boiling heat transfer were found. Analogy of heat transfer in flow boiling and pool boiling of helium and noncryogenic liquids was established. Correlations were developed which are in close agreement with available heat transfer data

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics

Directory of Open Access Journals (Sweden)

Shutthanandan V

2008-06-01

Full Text Available Abstract Molybdenum disulfide (MoS2, a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia. The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM, scanning electron microscopy (SEM, transmission electron microscopy (TEM, Rutherford backscattering spectrometry (RBS, and nuclear reaction analysis (NRA. Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400°C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and

Oxidation and metal-insertion in molybdenite surfaces: evaluation of charge-transfer mechanisms and dynamics.

Science.gov (United States)

Ramana, C V; Becker, U; Shutthanandan, V; Julien, C M

2008-06-05

Molybdenum disulfide (MoS2), a layered transition-metal dichalcogenide, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and geotechnical engineering. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. In addition, understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is important to utilize these minerals in technological applications. Furthermore, a detailed investigation of thermal oxidation behavior and metal-insertion will provide a basis to further explore and model the mechanism of adsorption of metal ions onto geomedia.The present work was performed to understand thermal oxidation and metal-insertion processes of molybdenite surfaces. The analysis was performed using atomic force microscopy (AFM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and nuclear reaction analysis (NRA).Structural studies using SEM and TEM indicate the local-disordering of the structure as a result of charge-transfer process between the inserted lithium and the molybdenite layer. Selected area electron diffraction measurements indicate the large variations in the diffusivity of lithium confirming that the charge-transfer is different along and perpendicular to the layers in molybdenite. Thermal heating of molybenite surface in air at 400 degrees C induces surface oxidation, which is slow during the first hour of heating and then increases significantly. The SEM results indicate that the crystals formed on the molybdenite surface as a result of thermal oxidation exhibit regular thin-elongated shape. The average size and density of the crystals on the surface is dependent on the time of annealing; smaller size and high density during the first one-hour and significant

Chaos in charged AdS black hole extended phase space

Science.gov (United States)

Chabab, M.; El Moumni, H.; Iraoui, S.; Masmar, K.; Zhizeh, S.

2018-06-01

We present an analytical study of chaos in a charged black hole in the extended phase space in the context of the Poincare-Melnikov theory. Along with some background on dynamical systems, we compute the relevant Melnikov function and find its zeros. Then we analyse these zeros either to identify the temporal chaos in the spinodal region, or to observe spatial chaos in the small/large black hole equilibrium configuration. As a byproduct, we derive a constraint on the Black hole' charge required to produce chaotic behaviour. To the best of our knowledge, this is the first endeavour to understand the correlation between chaos and phase picture in black holes.

Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

Science.gov (United States)

Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

2015-08-11

The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

Charge Transfer Effects in Naturally Occurring van der Waals Heterostructures (PbSe )1.16(TiSe2 )m (m =1 , 2)

Science.gov (United States)

Yao, Q.; Shen, D. W.; Wen, C. H. P.; Hua, C. Q.; Zhang, L. Q.; Wang, N. Z.; Niu, X. H.; Chen, Q. Y.; Dudin, P.; Lu, Y. H.; Zheng, Y.; Chen, X. H.; Wan, X. G.; Feng, D. L.

2018-03-01

van der Waals heterostructures (VDWHs) exhibit rich properties and thus has potential for applications, and charge transfer between different layers in a heterostructure often dominates its properties and device performance. It is thus critical to reveal and understand the charge transfer effects in VDWHs, for which electronic structure measurements have proven to be effective. Using angle-resolved photoemission spectroscopy, we studied the electronic structures of (PbSe )1.16(TiSe2 )m (m =1 , 2), which are naturally occurring VDWHs, and discovered several striking charge transfer effects. When the thickness of the TiSe2 layers is halved from m =2 to m =1 , the amount of charge transferred increases unexpectedly by more than 250%. This is accompanied by a dramatic drop in the electron-phonon interaction strength far beyond the prediction by first-principles calculations and, consequently, superconductivity only exists in the m =2 compound with strong electron-phonon interaction, albeit with lower carrier density. Furthermore, we found that the amount of charge transferred in both compounds is nearly halved when warmed from below 10 K to room temperature, due to the different thermal expansion coefficients of the constituent layers of these misfit compounds. These unprecedentedly large charge transfer effects might widely exist in VDWHs composed of metal-semiconductor contacts; thus, our results provide important insights for further understanding and applications of VDWHs.

Phase-transfer and film formation of silver nanoparticles.

Science.gov (United States)

Sarkar, Anjana; Chadha, Ridhima; Biswas, Nandita; Mukherjee, Tulsi; Kapoor, Sudhir

2009-04-01

In this article, a simple method for either transfer of silver nanoparticles from formamide to chloroform or to form a film at their interface is demonstrated. The transfer of the particles is a two-step size-dependent process. The size distribution of the colloidal hydrophobic silver particles in chloroform was almost the same as that before its transfer. Particles can be isolated by evaporation of chloroform. During evaporation, the hydrophobic particles become hydrophilic (charged) due to the formation of bilayer of CTAB over their surface. The isolated particles can be re-dispersed easily in polar solvents such as water and methanol. Nanocrystalline film of Ag is also prepared at the formamide-chloroform interface using suitable stabilizers in two immiscible layers. The nanocrystals have been characterized by various microscopic and spectroscopic techniques. The free standing film could be easily transferred on solid support.

Interface charge transfer process in ZnO:Mn/ZnS nanocomposites

Energy Technology Data Exchange (ETDEWEB)

Stefan, M.; Toloman, D., E-mail: dana.toloman@itim-cj.ro; Popa, A. [National Institute for R & D of Isotopic and Molecular Technology (Romania); Mesaros, A. [Technical University of Cluj-Napoca, Superconductivity, Spintronics and Surface Science Center – C4S (Romania); Vasile, O. R. [University “Politehnica” from Bucharest, Faculty of Applied Chemistry and Material Science (Romania); Leostean, C.; Pana, O. [National Institute for R & D of Isotopic and Molecular Technology (Romania)

2016-03-15

ZnO:Mn/ZnS nanocomposites were prepared by seed-mediated growth of ZnS QDs onto the preformed ZnO:Mn nanoparticles. The formation of the nanocomposite structure has been evidenced by XRD, HRTEM, and XPS. The architecture of the nanocomposite with outer ZnS QDs around ZnO:Mn cores is sustained by the sulfur and oxygen depth profiles resulted from XPS. When the two components are brought together, the band gap of ZnS component decreases while that of ZnO:Mn increases. It is the result of interface charge transfer from ZnO:Mn to ZnS QDs. Here ZnO:Mn valence states are extended through the interface into unoccupied gap states of ZnS. The energy band setup is modified from a type II into a type I band alignment. The process is accompanied by enhancement of composite UV emission of PL spectra as compared to its counterparts. The charge transfer from valence band also determines the increase of the core-polarization effect of sshell electrons at Mn{sup 2+} nucleus, thus determining the increase of the hyperfine field through the reduction of the covalency degree of Zn(Mn)–O bonds. The quantum confinement in ZnS QDs promotes the ferromagnetic coupling of singly occupied states due to Zn vacancies determining a superparamagnetic behavior of the ensemble. When the nanocomposites are formed, due to interface charge transfer effects, an increased number of filled cation vacancies in ZnS QDs develop, thus disrupting the pre-existing ferromagnetic coupling between spins resulting in a significant reduction of the overall saturation magnetization. The possibility to modulate nanocomposite properties by controlling the interface interactions may be foreseen in these types of materials.

Total and differential charge transfer cross sections in He{sup 2+}+N{sup 4+} collisions

Energy Technology Data Exchange (ETDEWEB)

Diemar, K. von; Melchert, F.; Huber, K.; Salzborn, E. [Institut fuer Kernphysik, Universitaet Giessen, Giessen (Germany); Trassl, R. [Institut fuer Kernphysik, Universitaet Giessen, Giessen (Germany)]. E-mail: Roland.H.Trassl@strz.uni-giessen.de; Opradolce, L. [Instituto de Astronomia y Fisica del Espacio (CONICET-UBA), Buenos Aires (Argentina); Piacentini, R.D. [Instituto de Fisica Rosario (CONICET-UNR), 2000 Rosario (Argentina)

2001-02-28

Charge transfer in the collision system He{sup 2+}+N{sup 4+} has been investigated both theoretically and experimentally for centre-of-mass energies between 8 and 200 keV. The theoretical calculations of the collision process have been carried out in the semi-classical impact parameter eikonal approach expanding the electronic wavefunction in a multi-state molecular-orbital basis with translation factors. The measurements of the charge-transfer cross sections were performed at an ion-ion crossed-beams experiment. Good agreement between the calculations and the experimental results for both total and differential cross sections is obtained. (author). Letter-to-the-editor.

Electrostatic sensors applied to the measurement of electric charge transfer in gas-solids pipelines

International Nuclear Information System (INIS)

Woodhead, S R; Denham, J C; Armour-Chelu, D I

2005-01-01

This paper describes the development of a number of electric charge sensors. The sensors have been developed specifically to investigate triboelectric charge transfer which takes place between particles and the pipeline wall, when powdered materials are conveyed through a pipeline using air. A number of industrial applications exist for such gas-solids pipelines, including pneumatic conveyors, vacuum cleaners and dust extraction systems. The build-up of electric charge on pipelines and powdered materials can lead to electrostatic discharge and so is of interest from a safety viewpoint. The charging of powders can also adversely affect their mechanical handling characteristics and so is of interest to handling equipment engineers. The paper presents the design of the sensors, the design of the electric charge test rig and electric charge measurement test results

K-shell-hole production, multiple-hole production, charge transfer, and antisymmetry

International Nuclear Information System (INIS)

Reading, J.F.; Ford, A.L.

1980-01-01

In calculating K-shell-hole production when an ion collides with an atom, account must be taken of the fact that processes involving electrons other than the K-shell electron can occur. For example, after making a K-shell hole an L-shell electron may be knocked into it, or an L-shell vacancy may be produced and the K-shell electron promoted to that vacancy in the ''Fermi sea'' of the target-atom orbitals. In 1973 a theorem was proved by one of the present authors demonstrating that all these multielectron processes cancel in an independent-particle model for the target atom. In this paper it is shown that the same thing occurs for hole production by charge transfer to the ion. The authors demonstrate that multihole production does not obey this simple rule and that the probability for multihole production is not the product of independent single-electron probabilities. The correct expressions that should be used for these processes are given, together with new results for charge-transfer processes accompanied by hole production

Charge transfer in low-energy collisions of H with He+ and H+ with He in excited states

Science.gov (United States)

Loreau, J.; Ryabchenko, S.; Muñoz Burgos, J. M.; Vaeck, N.

2018-04-01

The charge transfer process in collisions of excited (n = 2, 3) hydrogen atoms with He+ and in collisions of excited helium atoms with H+ is studied theoretically. A combination of a fully quantum-mechanical method and a semi-classical approach is employed to calculate the charge-exchange cross sections at collision energies from 0.1 eV u‑1 up to 1 keV u‑1. These methods are based on accurate ab initio potential energy curves and non-adiabatic couplings for the molecular ion HeH+. Charge transfer can occur either in singlet or in triplet states, and the differences between the singlet and triplet spin manifolds are discussed. The dependence of the cross section on the quantum numbers n and l of the initial state is demonstrated. The isotope effect on the charge transfer cross sections, arising at low collision energy when H is substituted by D or T, is investigated. Rate coefficients are calculated for all isotopes up to 106 K. Finally, the impact of the present calculations on models of laboratory plasmas is discussed.

Charge distribution effects in polyatomic reactants involved in simple electron transfer reactions

Czech Academy of Sciences Publication Activity Database

Fawcett, W. R.; Chavis, G. J.; Hromadová, Magdaléna

2008-01-01

Roč. 53, č. 23 (2008), s. 6787-6792 ISSN 0013-4686 Institutional research plan: CEZ:AV0Z40400503 Keywords : electron transfer kinetics * charge distribution effects * double - layer effects in electrode kinetics Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.078, year: 2008

Fabrication of Tiron-TiO{sub 2} charge-transfer complex with excellent visible-light photocatalytic performance

Energy Technology Data Exchange (ETDEWEB)

Yao, Binghua, E-mail: bhyao@xaut.edu.cn [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); The Key Laboratory of Northwest Water Resources and Environmental Ecology of Ministry of Education, Xi' an University of Technology, Xi' an 710048 (China); Peng, Chao; Lu, Pan; He, Yangqing [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); Zhang, Wen, E-mail: wenzhang@uark.edu [Department of Civil Engineering, University of Arkansas, Fayetteville 72701 (United States); Zhang, Qinku [Department of Applied Chemistry, Xi' an University of Technology, Xi' an 710048 (China); The Key Laboratory of Northwest Water Resources and Environmental Ecology of Ministry of Education, Xi' an University of Technology, Xi' an 710048 (China)

2016-12-01

A new charge-transfer(CT) complex (Tiron-TiO{sub 2}) was prepared via the 1,2-dihydroxy-3,5-benzenedisulfonic acid disodium salt (Tiron) as chelate sensitizer. The phase structures and morphologies were measured by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results demonstrated that the as-prepared Tiron-TiO{sub 2} is of anatase microspheres with size range between 300 and 350 nm. The analysis of FT-IR and XPS revealed that the binding structure of the Tiron-TiO{sub 2} CT complex is of the characteristic of bidentate binuclear binding-bridging. UV–vis analysis showed that the formation of CT complex on the surface of TiO{sub 2} through Tiron significantly extends the photoresponse of Tiron-TiO{sub 2} nanoparticles to visible light range (400–600 nm). Compared with unmodified TiO{sub 2}, Tiron-modified TiO{sub 2}(Tiron-TiO{sub 2}) exhibited excellent photocatalytic activity for the photocatalytic degradation of methylene blue(MB) and three kind of antibiotics under visible light irradiation (λ > 400 nm). - Highlights: • The Tiron-TiO{sub 2} charge transfer complex was synthesized. • The incorporation of Tiron with TiO{sub 2} extended TiO{sub 2} response to visible light region. • Tiron-TiO{sub 2} exhibited significant photocatalytic degradation for antibiotics. • Tiron-TiO{sub 2} showed the long-term stability and reusability.

The model of metal-insulator phase transition in vanadium oxide

International Nuclear Information System (INIS)

Vikhnin, V.S.; Lysenko, S.; Rua, A.; Fernandez, F.; Liu, H.

2005-01-01

Thermally induced metal-insulator phase transitions (PT) in VO 2 thin films are studied theoretically and experimentally. The hysteresis phenomena in the region of the transition for different type thin films were investigated. The phenomenological model of the PT is suggested. The charge transfer-lattice instability in VO 2 metallic phase is considered as basis of the first order metal-insulator PT in VO 2 . The charge transfer is treated as an order parameter

Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

KAUST Repository

Van Regemorter, Tanguy; Guillaume, Maxime; Sini, Gjergji; Sears, John S.; Geskin, Victor; Bré das, Jean-Luc; Beljonne, David; Cornil, Jé rô me

2012-01-01

In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

Overcoming the Cut-Off Charge Transfer Bandgaps at the PbS Quantum Dot Interface

KAUST Repository

El-Ballouli, Ala'a O.

2015-11-17

Light harvesting from large size of semiconductor PbS quantum dots (QDs) with a bandgap of less than 1 eV is one of the greatest challenges precluding the development of PbS QD-based solar cells because the interfacial charge transfer (CT) from such QDs to the most commonly used electron acceptor materials is very inefficient, if it occurs at all. Thus, an alternative electron-accepting unit with a new driving force for CT is urgently needed to harvest the light from large-sized PbS QDs. Here, a cationic porphyrin is utilized as a new electron acceptor unit with unique features that bring the donor–acceptor components into close molecular proximity, allowing ultrafast and efficient electron transfer for QDs of all sizes, as inferred from the drastic photoluminescence quenching and the ultrafast formation of the porphyrin anionic species. The time-resolved results clearly demonstrate the possibility of modulating the electron transfer process between PbS QDs and porphyrin moieties not only by the size quantization effect but also by the interfacial electrostatic interaction between the positively charged porphyrin and the negatively charged QDs. This approach provides a new pathway for engineering QD-based solar cells that make the best use of the diverse photons making up the Sun\\'s broad irradiance spectrum.

Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

KAUST Repository

Van Regemorter, Tanguy

2012-09-15

In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

Overcoming the Cut-Off Charge Transfer Bandgaps at the PbS Quantum Dot Interface

KAUST Repository

El-Ballouli, Ala'a O.; Alarousu, Erkki; Kirmani, Ahmad R.; Amassian, Aram; Bakr, Osman; Mohammed, Omar F.

2015-01-01

Light harvesting from large size of semiconductor PbS quantum dots (QDs) with a bandgap of less than 1 eV is one of the greatest challenges precluding the development of PbS QD-based solar cells because the interfacial charge transfer (CT) from such QDs to the most commonly used electron acceptor materials is very inefficient, if it occurs at all. Thus, an alternative electron-accepting unit with a new driving force for CT is urgently needed to harvest the light from large-sized PbS QDs. Here, a cationic porphyrin is utilized as a new electron acceptor unit with unique features that bring the donor–acceptor components into close molecular proximity, allowing ultrafast and efficient electron transfer for QDs of all sizes, as inferred from the drastic photoluminescence quenching and the ultrafast formation of the porphyrin anionic species. The time-resolved results clearly demonstrate the possibility of modulating the electron transfer process between PbS QDs and porphyrin moieties not only by the size quantization effect but also by the interfacial electrostatic interaction between the positively charged porphyrin and the negatively charged QDs. This approach provides a new pathway for engineering QD-based solar cells that make the best use of the diverse photons making up the Sun's broad irradiance spectrum.

"Inverted" Solvent Effect on Charge Transfer in the Excited State.

Science.gov (United States)

Nau; Pischel

1999-10-04

Faster in cyclohexane than in acetonitrile is the fluorescence quenching of the azoalkane 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by amines and sulfides. Although this photoreaction is induced by charge transfer (CT; see picture) and exciplexes are formed, the increase in the dipole moment of the exciplex is not large enough to offset the solvent stabilization of the excited reactants, and an "inverted" solvent effect results.

Charge Transfer and Support Effects in Heterogeneous Catalysis

Energy Technology Data Exchange (ETDEWEB)

Hervier, Antoine [Univ. of California, Berkeley, CA (United States)

2011-12-21

The kinetic, electronic and spectroscopic properties of two-dimensional oxide-supported catalysts were investigated in order to understand the role of charge transfer in catalysis. Pt/TiO₂ nanodiodes were fabricated and used as catalysts for hydrogen oxidation. During the reaction, the current through the diode, as well as its I-V curve, were monitored, while gas chromatography was used to measure the reaction rate. The current and the turnover rate were found to have the same temperature dependence, indicating that hydrogen oxidation leads to the non-adiabatic excitation of electrons in Pt. A fraction of these electrons have enough energy to ballistically transport through Pt and overcome the Schottky barrier at the interface with TiO₂. The yield for this phenomenon is on the order of 10^-4 electrons per product molecule formed, similar to what has been observed for CO oxidation and for the adsorption of many different molecules. The same Pt/TiO₂ system was used to compare currents in hydrogen oxidation and deuterium oxidation. The current through the diode under deuterium oxidation was found to be greater than under hydrogen oxidation by a factor of three. Weighted by the difference in turnover frequencies for the two isotopes, this would imply a chemicurrent yield 5 times greater for D₂ compared to H₂, contrary to what is expected given the higher mass of D₂. Reversible changes in the rectification factor of the diode are observed when switching between D₂ and H₂. These changes are a likely cause for the differences in current between the two isotopes. In the nanodiode experiments, surface chemistry leads to charge flow, suggesting the possibility of creating charge flow to tune surface chemistry. This was done first by exposing a Pt/Si diode to visible light while using it as a catalyst for H₂ oxidation. Absorption of the light in the Si, combined with

Interfacial charge distributions in carbon-supported palladium catalysts

DEFF Research Database (Denmark)

Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

2017-01-01

Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

Amino-Acid-Induced Preferential Orientation of Perovskite Crystals for Enhancing Interfacial Charge Transfer and Photovoltaic Performance.

Science.gov (United States)

Shih, Yen-Chen; Lan, Yu-Bing; Li, Chia-Shuo; Hsieh, Hsiao-Chi; Wang, Leeyih; Wu, Chih-I; Lin, King-Fu

2017-06-01

Interfacial engineering of perovskite solar cells (PSCs) is attracting intensive attention owing to the charge transfer efficiency at an interface, which greatly influences the photovoltaic performance. This study demonstrates the modification of a TiO 2 electron-transporting layer with various amino acids, which affects charge transfer efficiency at the TiO 2 /CH 3 NH 3 PbI 3 interface in PSC, among which the l-alanine-modified cell exhibits the best power conversion efficiency with 30% enhancement. This study also shows that the (110) plane of perovskite crystallites tends to align in the direction perpendicular to the amino-acid-modified TiO 2 as observed in grazing-incidence wide-angle X-ray scattering of thin CH 3 NH 3 PbI 3 perovskite film. Electrochemical impedance spectroscopy reveals less charge transfer resistance at the TiO 2 /CH 3 NH 3 PbI 3 interface after being modified with amino acids, which is also supported by the lower intensity of steady-state photoluminescence (PL) and the reduced PL lifetime of perovskite. In addition, based on the PL measurement with excitation from different side of the sample, amino-acid-modified samples show less surface trapping effect compared to the sample without modification, which may also facilitate charge transfer efficiency at the interface. The results suggest that appropriate orientation of perovskite crystallites at the interface and trap-passivation are the niche for better photovoltaic performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Neutralized ion beam modification of cellulose membranes for study of ion charge effect on ion-beam-induced DNA transfer

Science.gov (United States)

Prakrajang, K.; Sangwijit, K.; Anuntalabhochai, S.; Wanichapichart, P.; Yu, L. D.

2012-02-01

Low-energy ion beam biotechnology (IBBT) has recently been rapidly developed worldwide. Ion-beam-induced DNA transfer is one of the important applications of IBBT. However, mechanisms involved in this application are not yet well understood. In this study plasma-neutralized ion beam was applied to investigate ion charge effect on induction of DNA transfer. Argon ion beam at 7.5 keV was neutralized by RF-driven plasma in the beam path and then bombarded cellulose membranes which were used as the mimetic plant cell envelope. Electrical properties such as impedance and capacitance of the membranes were measured after the bombardment. An in vitro experiment on plasmid DNA transfer through the cellulose membrane was followed up. The results showed that the ion charge input played an important role in the impedance and capacitance changes which would affect DNA transfer. Generally speaking, neutral particle beam bombardment of biologic cells was more effective in inducing DNA transfer than charged ion beam bombardment.

Scientific Computation Application Partnerships in Materials and Chemical Sciences, Charge Transfer and Charge Transport in Photoactivated Systems, Developing Electron-Correlated Methods for Excited State Structure and Dynamics in the NWChem Software Suite

Energy Technology Data Exchange (ETDEWEB)

Cramer, Christopher J. [Univ. of Minnesota, Minneapolis, MN (United States)

2017-11-12

Charge transfer and charge transport in photoactivated systems are fundamental processes that underlie solar energy capture, solar energy conversion, and photoactivated catalysis, both organometallic and enzymatic. We developed methods, algorithms, and software tools needed for reliable treatment of the underlying physics for charge transfer and charge transport, an undertaking with broad applicability to the goals of the fundamental-interaction component of the Department of Energy Office of Basic Energy Sciences and the exascale initiative of the Office of Advanced Scientific Computing Research.

Through space and through bridge channels of charge transfer at p-n nano-junctions: A DFT study

Energy Technology Data Exchange (ETDEWEB)

Dandu, Naveen [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States); Tretiak, Sergei [Theoretical Division, Center for Nonlinear Studies (CNLS) and Center for Integrated Nanotechnologies (CINT), Los Alamos National Laboratory, Los Alamos, 57069, NM 87454 (United States); Kilina, Svetlana [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States); Kilin, Dmitri, E-mail: Dmitri.Kilin@ndsu.edu [Department of Chemistry and Biochemistry, NDSU, Fargo, ND 58108 (United States)

2016-12-20

Highlights: • Properties of interacting QDs depend on the fashion of interaction: through-bond or through-space. • The disconnected and undoped dimer models shows FÓ§rster band formation. • Dimer models with some doping exhibit degenerate charge-transfer excitons. • p- and n-doped qds shows polarization at the interface. • A photoexcitation polarizes p-n interface, in relation to phototovoltaic effect. - Abstract: Details of charge density distribution at p-n nano interface are analyzed with density functional theory techniques using model system of dimers of doped silicon quantum dots interacting through bond and through space. Spatial distributions of transition densities between the ground and excited states suggest the character of essential electronic excitations, which have a FÓ§rster, bound, unbound, or charge transfer character. A redistribution of electronic density from n-impurities to p-impurities results in a ground state polarization and creates an offset of energies of the bands localized on p-doped quantum dot and the bands localized on n-doped quantum dot. Although impurities contribute very few orbitals to the total density, a ground state charge redistribution and polarization are both responsible for the presence of a large number of charge transfer excitations involving solely silicon orbitals.

Ultrafast dynamics of solvation and charge transfer in a DNA-based biomaterial.

Science.gov (United States)

Choudhury, Susobhan; Batabyal, Subrata; Mondol, Tanumoy; Sao, Dilip; Lemmens, Peter; Pal, Samir Kumar

2014-05-01

Charge migration along DNA molecules is a key factor for DNA-based devices in optoelectronics and biotechnology. The association of a significant amount of water molecules in DNA-based materials for the intactness of the DNA structure and their dynamic role in the charge-transfer (CT) dynamics is less documented in contemporary literature. In the present study, we have used a genomic DNA-cetyltrimethyl ammonium chloride (CTMA) complex, a technological important biomaterial, and Hoechest 33258 (H258), a well-known DNA minor groove binder, as fluorogenic probe for the dynamic solvation studies. The CT dynamics of CdSe/ZnS quantum dots (QDs; 5.2 nm) embedded in the as-prepared and swollen biomaterial have also been studied and correlated with that of the timescale of solvation. We have extended our studies on the temperature-dependent CT dynamics of QDs in a nanoenvironment of an anionic, sodium bis(2-ethylhexyl)sulfosuccinate reverse micelle (AOT RMs), whereby the number of water molecules and their dynamics can be tuned in a controlled manner. A direct correlation of the dynamics of solvation and that of the CT in the nanoenvironments clearly suggests that the hydration barrier within the Arrhenius framework essentially dictates the charge-transfer dynamics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Refrigerant charge, pressure drop, and condensation heat transfer in flattened tubes

Energy Technology Data Exchange (ETDEWEB)

Wilson, M J; Newell, T A; Chato, J C [University of Illinois, Urbana, IL (United States). Dept. of Mechanical and Industrial Engineering; Infante Ferreira, C A [Delft University of Technology (Netherlands). Laboratory for Refrigeration and Indoor Climate Control

2003-06-01

Horizontal smooth and microfinned copper tubes with an approximate diameter of 9 mm were successively flattened in order to determine changes in flow field characteristics as a round tube is altered into a flattened tube profile. Refrigerants R134a and R410A were investigated over a mass flux range from 75 to 400 kg m{sup -2} s{sup -}2{sup 1} and a quality range from approximately 10-80%. For a given refrigerant mass flow rate, the results show that a significant reduction in refrigerant charge is possible. Pressure drop results show increases of pressure drop at a given mass flux and quality as a tube profile is flattened. Heat transfer results indicate enhancement of the condensation heat transfer coefficient as a tube is flattened. Flattened tubes with an 18{sup o} helix angle displayed the highest heat transfer coefficients. Smooth tubes and axial microfin tubes displayed similar levels of heat transfer enhancement. Heat transfer enhancement is dependent on the mass flux, quality and tube profile. (author)

Highly mobile charge-transfer excitons in two-dimensional WS2/tetracene heterostructures

Science.gov (United States)

Zhu, Tong; Yuan, Long; Zhao, Yan; Zhou, Mingwei; Wan, Yan; Mei, Jianguo; Huang, Libai

2018-01-01

Charge-transfer (CT) excitons at heterointerfaces play a critical role in light to electricity conversion using organic and nanostructured materials. However, how CT excitons migrate at these interfaces is poorly understood. We investigate the formation and transport of CT excitons in two-dimensional WS2/tetracene van der Waals heterostructures. Electron and hole transfer occurs on the time scale of a few picoseconds, and emission of interlayer CT excitons with a binding energy of ~0.3 eV has been observed. Transport of the CT excitons is directly measured by transient absorption microscopy, revealing coexistence of delocalized and localized states. Trapping-detrapping dynamics between the delocalized and localized states leads to stretched-exponential photoluminescence decay with an average lifetime of ~2 ns. The delocalized CT excitons are remarkably mobile with a diffusion constant of ~1 cm2 s−1. These highly mobile CT excitons could have important implications in achieving efficient charge separation. PMID:29340303

Quasi-four-body treatment of charge transfer in the collision of protons with atomic helium: I. Thomas related mechanisms

Science.gov (United States)

Safarzade, Zohre; Fathi, Reza; Shojaei Akbarabadi, Farideh; Bolorizadeh, Mohammad A.

2018-04-01

The scattering of a completely bare ion by atoms larger than hydrogen is at least a four-body interaction, and the charge transfer channel involves a two-step process. Amongst the two-step interactions of the high-velocity single charge transfer in an anion-atom collision, there is one whose amplitude demonstrates a peak in the angular distribution of the cross sections. This peak, the so-called Thomas peak, was predicted by Thomas in a two-step interaction, classically, which could also be described through three-body quantum mechanical models. This work discusses a four-body quantum treatment of the charge transfer in ion-atom collisions, where two-step interactions illustrating a Thomas peak are emphasized. In addition, the Pauli exclusion principle is taken into account for the initial and final states as well as the operators. It will be demonstrated that there is a momentum condition for each two-step interaction to occur in a single charge transfer channel, where new classical interactions lead to the Thomas mechanism.

Theoretical perspectives on electron transfer and charge separation events in photochemical water cleavage systems

International Nuclear Information System (INIS)

Kozak, J.J.; Lenoir, P.M.; Musho, M.K.; Tembe, B.L.

1984-01-01

We study in this paper the dynamics induced by models for photochemical water cleavage systems, focusing on the spatial and temporal factors influencing electron transfer and charge separation processes in such systems. The reaction-diffusion theory is formulated in full generality and the consequences explored in a number of spatio-temporal regimes, viz. the spatially homogeneous system in the long-time limit (i.e. the steady state for a well-stirred system), the spatially homogeneous system in evolution, and the spatially inhomogeneous system in evolution (where, in the latter study, we consider electron transfer at the cluster surface to be governed by a rate constant that reflects the localized nature of such processes). The results of numerical simulations are presented for all three cases and used to highlight the importance of heterogeneous environments in enhancing the cage escape yield of charge separated species, and to demonstrate the dependence of the hydrogen yield on the localization of electron-transfer processes in the vicinity of the microcatalyst surface

Problems of heat transfer and hydraulics of two-phase media

CERN Document Server

Kutateladze, S S

1969-01-01

Problems of Heat Transfer and Hydraulics of Two-Phase Media presents the theory of heat transfer and hydrodynamics. This book discusses the various aspects of heat transfer and the flow of two-phase systems. Organized into two parts encompassing 22 chapters, this book starts with an overview of the laws of similarity for heat transfer to or from a flowing liquid with various physical properties and allowed for variation in viscosity and thermal conductivity. This book then explores the general functional relationship that exists between viscosity and thermal conductivity for thermodynamically

An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings

Energy Technology Data Exchange (ETDEWEB)

Pavanello, Michele [Department of Chemistry, Rutgers University, Newark, New Jersey 07102-1811 (United States); Van Voorhis, Troy [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139-4307 (United States); Visscher, Lucas [Amsterdam Center for Multiscale Modeling, VU University, De Boelelaan 1083, 1081 HV Amsterdam (Netherlands); Neugebauer, Johannes [Theoretische Organische Chemie, Organisch-Chemisches Institut der Westfaelischen Wilhelms-Universitaet Muenster, Corrensstrasse 40, 48149 Muenster (Germany)

2013-02-07

Quantum-mechanical methods that are both computationally fast and accurate are not yet available for electronic excitations having charge transfer character. In this work, we present a significant step forward towards this goal for those charge transfer excitations that take place between non-covalently bound molecules. In particular, we present a method that scales linearly with the number of non-covalently bound molecules in the system and is based on a two-pronged approach: The molecular electronic structure of broken-symmetry charge-localized states is obtained with the frozen density embedding formulation of subsystem density-functional theory; subsequently, in a post-SCF calculation, the full-electron Hamiltonian and overlap matrix elements among the charge-localized states are evaluated with an algorithm which takes full advantage of the subsystem DFT density partitioning technique. The method is benchmarked against coupled-cluster calculations and achieves chemical accuracy for the systems considered for intermolecular separations ranging from hydrogen-bond distances to tens of Angstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.

Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

Energy Technology Data Exchange (ETDEWEB)

Van Tassle, Aaron Justin [Univ. of California, Berkeley, CA (United States)

2006-01-01

This dissertation describes the development andimplementation of a visible/near infrared pump/mid-infrared probeapparatus. Chapter 1 describes the background and motivation ofinvestigating optically induced structural dynamics, paying specificattention to solvation and the excitation selection rules of highlysymmetric molecules such as carotenoids. Chapter 2 describes thedevelopment and construction of the experimental apparatus usedthroughout the remainder of this dissertation. Chapter 3 will discuss theinvestigation of DCM, a laser dye with a fluorescence signal resultingfrom a charge transfer state. By studying the dynamics of DCM and of itsmethyl deuterated isotopomer (an otherwise identical molecule), we areable to investigate the origins of the charge transfer state and provideevidence that it is of the controversial twisted intramolecular (TICT)type. Chapter 4 introduces the use of two-photon excitation to the S1state, combined with one-photon excitation to the S2 state of thecarotenoid beta-apo-8'-carotenal. These 2 investigations show evidencefor the formation of solitons, previously unobserved in molecular systemsand found only in conducting polymers Chapter 5 presents an investigationof the excited state dynamics of peridinin, the carotenoid responsiblefor the light harvesting of dinoflagellates. This investigation allowsfor a more detailed understanding of the importance of structuraldynamics of carotenoids in light harvesting.

Exciplex: An Intermolecular Charge-Transfer Approach for TADF.

Science.gov (United States)

Sarma, Monima; Wong, Ken-Tsung

2018-04-03

Organic materials that display thermally activated delayed fluorescence (TADF) are a striking class of functional materials that have witnessed a booming progress in recent years. In addition to pure TADF emitters achieved by the subtle manipulations of intramolecular charge transfer processes with sophisticated molecular structures, a new class of efficient TADF-based OLEDs with emitting layer formed by blending electron donor and acceptor molecules that involve intermolecular charge transfer have also been fabricated. In contrast to pure TADF materials, the exciplex-based systems can realize small ΔEST (0-0.05 eV) much more easily since the electron and hole are positioned on two different molecules, thereby giving small exchange energy. Consequently, exciplex-based OLEDs have the prospective to maximize the TADF contribution and achieve theoretical 100% internal quantum efficiency. Therefore, the challenging issue of achieving small ΔEST in organic systems could be solved. In this article, we summarize and discuss the latest and most significant developments regarding these rapidly evolving functional materials, wherein the majority of the reported exciplex forming systems are categorized into two sub-groups, viz. (a) exciplex as TADF emitters and (b) those as hosts for fluorescent, phosphorescent and TADF dopants according to their structural features and applications. The working mechanisms of the direct electroluminescence from the donor/acceptor interface and the exciplex-forming systems as co-host for the realization of high efficiency OLEDs are reviewed and discussed. This article delivers a summary of the current progresses and achievements of exciplex-based researches and points out the future challenges to trigger more research endeavors to this growing field.

Synthesis of Stable Interfaces on SnO2 Surfaces for Charge-Transfer Applications

Science.gov (United States)

Benson, Michelle C.

The commercial market for solar harvesting devices as an alternative energy source requires them to be both low-cost and efficient to replace or reduce the dependence on fossil fuel burning. Over the last few decades there has been promising efforts towards improving solar devices by using abundant and non-toxic metal oxide nanomaterials. One particular metal oxide of interest has been SnO2 due to its high electron mobility, wide-band gap, and aqueous stability. However SnO2 based solar cells have yet to reach efficiency values of other metal oxides, like TiO2. The advancement of SnO2 based devices is dependent on many factors, including improved methods of surface functionalization that can yield stable interfaces. This work explores the use of a versatile functionalization method through the use of the Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. The CuAAC reaction is capable of producing electrochemically, photochemically, and electrocatalytically active surfaces on a variety of SnO2 materials. The resulting charge-transfer characteristics were investigated as well as an emphasis on understanding the stability of the resulting molecular linkage. We determined the CuAAC reaction is able to proceed through both azide-modified and alkyne-modified surfaces. The resulting charge-transfer properties showed that the molecular tether was capable of supporting charge separation at the interface. We also investigated the enhancement of electron injection upon the introduction of an ultra-thin ZrO2 coating on SnO2. Several complexes were used to fully understand the charge-transfer capabilities, including model systems of ferrocene and a ruthenium coordination complex, a ruthenium mononuclear water oxidation catalyst, and a commercial ruthenium based dye.

Physical adsorption and charge transfer of molecular Br2 on graphene.

Science.gov (United States)

Chen, Zheyuan; Darancet, Pierre; Wang, Lei; Crowther, Andrew C; Gao, Yuanda; Dean, Cory R; Taniguchi, Takashi; Watanabe, Kenji; Hone, James; Marianetti, Chris A; Brus, Louis E

2014-03-25

We present a detailed study of gaseous Br2 adsorption and charge transfer on graphene, combining in situ Raman spectroscopy and density functional theory (DFT). When graphene is encapsulated by hexagonal boron nitride (h-BN) layers on both sides, in a h-BN/graphene/h-BN sandwich structure, it is protected from doping by strongly oxidizing Br2. Graphene supported on only one side by h-BN shows strong hole doping by adsorbed Br2. Using Raman spectroscopy, we determine the graphene charge density as a function of pressure. DFT calculations reveal the variation in charge transfer per adsorbed molecule as a function of coverage. The molecular adsorption isotherm (coverage versus pressure) is obtained by combining Raman spectra with DFT calculations. The Fowler-Guggenheim isotherm fits better than the Langmuir isotherm. The fitting yields the adsorption equilibrium constant (∼0.31 Torr(-1)) and repulsive lateral interaction (∼20 meV) between adsorbed Br2 molecules. The Br2 molecule binding energy is ∼0.35 eV. We estimate that at monolayer coverage each Br2 molecule accepts 0.09 e- from single-layer graphene. If graphene is supported on SiO2 instead of h-BN, a threshold pressure is observed for diffusion of Br2 along the (somewhat rough) SiO2/graphene interface. At high pressure, graphene supported on SiO2 is doped by adsorbed Br2 on both sides.

Active pixel sensor having intra-pixel charge transfer with analog-to-digital converter

Science.gov (United States)

Fossum, Eric R. (Inventor); Mendis, Sunetra K. (Inventor); Pain, Bedabrata (Inventor); Nixon, Robert H. (Inventor); Zhou, Zhimin (Inventor)

2003-01-01

An imaging device formed as a monolithic complementary metal oxide semiconductor integrated circuit in an industry standard complementary metal oxide semiconductor process, the integrated circuit including a focal plane array of pixel cells, each one of the cells including a photogate overlying the substrate for accumulating photo-generated charge in an underlying portion of the substrate, a readout circuit including at least an output field effect transistor formed in the substrate, and a charge coupled device section formed on the substrate adjacent the photogate having a sensing node connected to the output transistor and at least one charge coupled device stage for transferring charge from the underlying portion of the substrate to the sensing node and an analog-to-digital converter formed in the substrate connected to the output of the readout circuit.

Detection of Intramolecular Charge Transfer and Dynamic Solvation in Eosin B by Femtosecond Two-Dimensional Electronic Spectroscopy

Science.gov (United States)

Ghosh, Soumen; Roscioli, Jerome D.; Beck, Warren F.

2014-06-01

We have employed 2D electronic photon echo spectroscopy to study intramolecular charge-transfer dynamics in eosin B. After preparation of the first excited singlet state (S_1) with 40-fs excitation pulses at 520 nm, the nitro group (--NO_2) in eosin B undergoes excited state torsional motion towards a twisted intramolecular charge transfer (TICT) state. As the viscosity of the surrounding solvent increases, the charge-transfer rate decreases because the twisting of the --NO_2 group is hindered. These conclusions are supported by the time evolution of the 2D spectrum, which provides a direct measure of the the ground-to-excited-state energy gap time-correlation function, M(t). In comparison to the inertial and diffusive solvation time scales exhibited by eosin Y, which lacks the nitro group, the M(t) function for eosin B exhibits under the same conditions an additional component on the 150-fs timescale that arises from quenching of the S_1 state by crossing to the TICT state. These results indicate that 2D electronic spectroscopy can be used as a sensitive probe of the rate of charge transfer in a molecular system and of the coupling to the motions of the surrounding solvent. (Supported by grant DE-SC0010847 from the Department of Energy, Office of Basic Energy Sciences, Photosynthetic Systems program.)

Crown ethers and phase transfer catalysis in polymer science

CERN Document Server

Carraher, Charles

1984-01-01

Phase transfer catalysis or interfacial catalysis is a syn­ thetic technique involving transport of an organic or inorganic salt from a solid or aqueous phase into an organic liquid where reaction with an organic-soluble substrate takes place. Over the past 15 years there has been an enormous amount of effort invested in the development of this technique in organic synthe­ sis. Several books and numerous review articles have appeared summarizing applications in which low molecular weight catalysts are employed. These generally include either crown ethers or onium salts of various kinds. While the term phase transfer catalysis is relatively new, the concept of using a phasetrans­ fer agent (PTA) is much older~ Both Schnell and Morgan employed such catalysts in synthesis of polymeric species in the early 1950's. Present developments are really extensions of these early applications. It has only been within the last several years that the use of phase transfer processes have been employed in polymer synthesis...

Four- and six-charge transfer reactions induced by 52Cr, 56Fe, 63Cu in rare-earths

International Nuclear Information System (INIS)

Mouchaty, G.

1977-01-01

The cross sections for transfer reactions in which 4 and 6 charges are gained by Sm and Nd targets have been measured, the projectiles being 52 Cr and 56 Fe at 343 and 377 MeV. These energies correspond to 1.5B, B being the interaction barrier. The results obtained indicate that the cross section increases when the number of charges transferred and the mass of the projectile are increased. The angular distributions and recoil ranges at each angle of 151 Dy produced through 52 Cr+ 148 Sm, 52 Cr+ 144 Nd, 56 Fe+ 144 Nd, 63 Cu+ 144 Nd reactions were determined for incident energies equivalent to 1.5B. After transformation into the c.m. system, the angular distributions exhibit a maximum close to 155 0 and a tail at small angles. The position of the maximum is independent of the incident ion and of the number of transferred charges. The analysis of the energy distributions indicate that the observed reactions can be explained by a two-step process: a transfer of nucleons followed by an evaporation step. The number of nucleons transferred in the 1st step and the associated excitation energies are higher for the events corresponding to the tail than for those corresponding to the maximum [fr

Study on charge transfer reaction of several organic molecules with accelerated rare gas ions

International Nuclear Information System (INIS)

Takahasi, Makoto; Okuda, Sachiko; Arai, Eiichi; Ichinose, Akira; Takakubo, Masaaki.

1984-01-01

Observing the charge transfer mass spectra of ethylbenzene, cyclobutane and methanol in Ar and Xe ion impacts, we investigated the dependence of the secondary ion peak intensities (normalized to primary ion current and target pressure) on the translational energy of primary ions (0-3500 eV).In the case of ethylbenzene, several maxima of the secondary i on peak intensities were observed in Ar and Xe ion impacts. The correlation between the maxima and the primary ion energy was examined in terms of near adiabatic theory of Massey. Supplementary studies on the energy distribution of primary ion, charge transfer cross section between methanol and Xe ion, and final product analysis in rare gas ion irradiation on cyclobutane were described. (author)

Negative thermal expansion induced by intermetallic charge transfer.

Science.gov (United States)

Azuma, Masaki; Oka, Kengo; Nabetani, Koichiro

2015-06-01

Suppression of thermal expansion is of great importance for industry. Negative thermal expansion (NTE) materials which shrink on heating and expand on cooling are therefore attracting keen attention. Here we provide a brief overview of NTE induced by intermetallic charge transfer in A-site ordered double perovskites SaCu 3 Fe 4 O 12 and LaCu 3 Fe 4- x Mn x O 12 , as well as in Bi or Ni substituted BiNiO 3 . The last compound shows a colossal dilatometric linear thermal expansion coefficient exceeding -70 × 10 -6 K -1 near room temperature, in the temperature range which can be controlled by substitution.

Theoretical investigation of the charge-transfer properties in different meso-linked zinc porphyrins for highly efficient dye-sensitized solar cells.

Science.gov (United States)

Namuangruk, Supawadee; Sirithip, Kanokkorn; Rattanatwan, Rattanawelee; Keawin, Tinnagon; Kungwan, Nawee; Sudyodsuk, Taweesak; Promarak, Vinich; Surakhot, Yaowarat; Jungsuttiwong, Siriporn

2014-06-28

The charge transfer effect of different meso-substituted linkages on porphyrin analogue 1 (A1, B1 and C1) was theoretically investigated using density functional theory (DFT) and time-dependent DFT (TDDFT) calculations. The calculated geometry parameters and natural bond orbital analysis reveal that the twisted conformation between porphyrin macrocycle and meso-substituted linkages leads to blocking of the conjugation of the conjugated backbone, and the frontier molecular orbital plot shows that the intramolecular charge transfer of A1, B1 and C1 hardly takes place. In an attempt to improve the photoinduced intramolecular charge transfer ability of the meso-linked zinc porphyrin sensitizer, a strong electron-withdrawing group (CN) was introduced into the anchoring group of analogue 1 forming analogue 2 (A2, B2 and C2). The density difference plot of A2, B2 and C2 shows that the charge transfer properties dramatically improved. The electron injection process has been performed using TDDFT; the direct charge-transfer transition in the A2-(TiO2)38 interacting system takes place; our results strongly indicated that introducing electron-withdrawing groups into the acceptor part of porphyrin dyes can fine-tune the effective conjugation length of the π-spacer and improve intramolecular charge transfer properties, consequently inducing the electron injection process from the anchoring group of the porphyrin dye to the (TiO2)38 surface which may improve the conversion efficiency of the DSSCs. Our calculated results can provide valuable information and a promising outlook for computation-aided sensitizer design with anticipated good properties in further experimental synthesis.

Berry phase in superconducting charge qubits interacting with a cavity field

International Nuclear Information System (INIS)

Abdel-Aty, Mahmoud

2009-01-01

We propose a method for analyzing Berry phase for a multi-qubit system of superconducting charge qubits interacting with a microwave field. By suitably choosing the system parameters and precisely controlling the dynamics, novel connection found between the Berry phase and entanglement creations.

Collisions of fast multicharged ions in gas targets: charge transfer and ionization

International Nuclear Information System (INIS)

Schlachter, A.S.

1981-05-01

Measurements of cross sections for charge transfer and ionization of H 2 and rare-gas targets have been made with fast, highly stripped projectiles in charge states as high as 59+. We have found an empirical scaling rule for electron-capture cross section in H 2 valid at energies above 275 keV/amu. Similar scaling might exist for other target gases. Cross sections are generally in good agreement with theory. We have found a scaling rule for electron loss from H in collisions with a fast highly stripped projectile, based on Olson's classical-trajectory Monte-Carlo calculations, and confirmed by measurements in an H 2 target. We have found a similar scaling rule for net ionization of rare-gas targets, based on Olson's CTMC calculations and the independent-electron model. Measurements are essentially consistent with the scaled cross sections. Calculations and measurements of recoil-ion charge-state spectra show large cross sections for the production of highly charged slow recoil ions

Structural dynamics of a noncovalent charge transfer complex from femtosecond stimulated Raman spectroscopy.

Science.gov (United States)

Fujisawa, Tomotsumi; Creelman, Mark; Mathies, Richard A

2012-09-06

Femtosecond stimulated Raman spectroscopy is used to examine the structural dynamics of photoinduced charge transfer within a noncovalent electron acceptor/donor complex of pyromellitic dianhydride (PMDA, electron acceptor) and hexamethylbenzene (HMB, electron donor) in ethylacetate and acetonitrile. The evolution of the vibrational spectrum reveals the ultrafast structural changes that occur during the charge separation (Franck-Condon excited state complex → contact ion pair) and the subsequent charge recombination (contact ion pair → ground state complex). The Franck-Condon excited state is shown to have significant charge-separated character because its vibrational spectrum is similar to that of the ion pair. The charge separation rate (2.5 ps in ethylacetate and ∼0.5 ps in acetonitrile) is comparable to solvation dynamics and is unaffected by the perdeuteration of HMB, supporting the dominant role of solvent rearrangement in charge separation. On the other hand, the charge recombination slows by a factor of ∼1.4 when using perdeuterated HMB, indicating that methyl hydrogen motions of HMB mediate the charge recombination process. Resonance Raman enhancement of the HMB vibrations in the complex reveals that the ring stretches of HMB, and especially the C-CH(3) deformations are the primary acceptor modes promoting charge recombination.

Simple Ion Transfer at Liquid|Liquid Interfaces

Directory of Open Access Journals (Sweden)

L. J. Sanchez Vallejo

2012-01-01

Full Text Available The main aspects related to the charge transfer reactions occurring at the interface between two immiscible electrolyte solutions (ITIES are described. The particular topics to be discussed involve simple ion transfer. Focus is given on theoretical approaches, numerical simulations, and experimental methodologies. Concerning the theoretical procedures, different computational simulations related to simple ion transfer are reviewed. The main conclusions drawn from the most accepted models are described and analyzed in regard to their relevance for explaining different aspects of ion transfer. We describe numerical simulations implementing different approaches for solving the differential equations associated with the mass transport and charge transfer. These numerical simulations are correlated with selected experimental results; their usefulness in designing new experiments is summarized. Finally, many practical applications can be envisaged regarding the determination of physicochemical properties, electroanalysis, drug lipophilicity, and phase-transfer catalysis.

Crossed beam study of He+-O2 charge transfer reactions in the collision energy range 0.5-200 eV

International Nuclear Information System (INIS)

Bischof, G.; Linder, F.

1986-01-01

Energy spectra and angular distributions of the O + and O 2 + product ions resulting from the He + -O 2 charge transfer reaction have been measured in the collision energy range 0.5-200 eV using the crossed-beam method. The O 2 + ions represent only a minor fraction of the reaction products (0.2-0.6% over the energy range measured). In the dissociative charge transfer reaction, four main processes are identified leading to O+O + reaction products in different electronic states. Two different mechanisms can be distinguished, each being responsible for two of the observed processes: (i) a long-distance energy-resonant charge transfer process involving the c 4 Σsub(u) - (upsilon'=0) state of O 2 + and (ii) a slightly exothermic charge transfer process via the (III) 2 PIsub(u) state of O 2 + (with the exothermicity depending on the collision energy). Angle-integrated branching ratios and partial cross sections (in absolute units) have been determined. The branching ratios of the individual processes show a pronounced dependence on the collision energy. At low energies, the O + product ions are preferentially formed in the 2 P 0 and 2 D 0 excited states. The angular distributions of the O + product ions show an anisotropic behaviour indicating an orientation-dependent charge transfer probability in the He + -O 2 reaction. (orig.)

The effect of structural changes on charge transfer states in a light-harvesting carotenoid-diaryl-porphyrin-C{sub 60} molecular triad

Energy Technology Data Exchange (ETDEWEB)

Olguin, Marco [Computational Science Program, University of Texas at El Paso, El Paso, Texas 79968 (United States); Basurto, Luis; Zope, Rajendra R. [Department of Physics, The University of Texas at El Paso, El Paso, Texas 79968 (United States); Baruah, Tunna, E-mail: tbaruah@utep.edu [Computational Science Program, University of Texas at El Paso, El Paso, Texas 79968 (United States); Department of Physics, The University of Texas at El Paso, El Paso, Texas 79968 (United States)

2014-05-28

We present a detailed study of charge transfer (CT) excited states for a large number of configurations in a light-harvesting Carotenoid-diaryl-Porphyrin-C{sub 60} (CPC{sub 60}) molecular triad. The chain-like molecular triad undergoes photoinduced charge transfer process exhibiting a large excited state dipole moment, making it suitable for application to molecular-scale opto-electronic devices. An important consideration is that the structural flexibility of the CPC{sub 60} triad impacts its dynamics in solvents. Since experimentally measured dipole moments for the triad of ∼110 D and ∼160 D strongly indicate a range in structural variability in the excited state, studying the effect of structural changes on the CT excited state energetics furthers the understanding of its charge transfer states. We have calculated the variation in the lowest CT excited state energies by performing a scan of possible variation in the structure of the triad. Some of these configurations were generated by incrementally scanning a 360° torsional (dihedral) twist at the C{sub 60}-porhyrin linkage and the porphyrin-carotenoid linkage. Additionally, five different CPC{sub 60} conformations were studied to determine the effect of pi-conjugation and particle-hole Coulombic attraction on the CT excitation energies. Our calculations show that configurational changes in the triad induces a variation of ∼0.6 eV in CT excited state energies in the gas-phase. The corresponding calculated excited state dipoles show a range of 47 D–188 D. The absorption spectra and density of states of these structures show little variation except for the structures where the porphyrin and aryl conjugation is changed.

Origin of Asymmetric Charge Partitioning in the Dissociation of Gas-Phase Protein Homodimers

OpenAIRE

Jurchen, John C.; Williams, Evan R.

2003-01-01

The origin of asymmetric charge and mass partitioning observed for gas-phase dissociation of multiply charged macromolecular complexes has been hotly debated. These experiments hold the potential to provide detailed information about the interactions between the macromolecules within the complex. Here, this unusual phenomenon of asymmetric charge partitioning is investigated for several protein homodimers. Asymmetric charge partitioning in these ions depends on a number of factors, including ...

Charge-Transfer-Induced p-Type Channel in MoS2 Flake Field Effect Transistors.

Science.gov (United States)

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.

Structural transition induced by charge-transfer in RbMn[Fe(CN) sub 6]. Investigation by synchrotron-radiation X-ray powder analysis

CERN Document Server

Moritomo, Y; Sakata, M; Kato, K; Kuriki, A; Tokoro, H; Ohkoshi, S I; Hashimoto, K

2002-01-01

Temperature dependence of atomic coordinates is determined for RbMn[Fe(CN) sub 6] by means of synchrotron-radiation (SR) X-ray powder structural analysis. We observed a structural transition from the cubic (F4-bar3m; Z=4) to the tetragonal (I4-barm2; Z=2) phase at approx. =210K in the cooling run and at approx. =300K in the warming run. In the low-temperature tetragonal phase, we found Jahn-Tellar type distortion of the MnN sub 6 octahedra and compression of the averaged Fe-C bond distance. These structural data suggest that the structural transition is triggered by the inter-metallic charge-transfer from the Mn(II) site to the Fe(III) site.

Excitation and charge transfer in low-energy hydrogen atom collisions with neutral iron

Science.gov (United States)

Barklem, P. S.

2018-05-01

Data for inelastic processes due to hydrogen atom collisions with iron are needed for accurate modelling of the iron spectrum in late-type stars. Excitation and charge transfer in low-energy Fe+H collisions is studied theoretically using a previously presented method based on an asymptotic two-electron linear combination of atomic orbitals model of ionic-covalent interactions in the neutral atom-hydrogen-atom system, together with the multi-channel Landau-Zener model. An extensive calculation including 166 covalent states and 25 ionic states is presented and rate coefficients are calculated for temperatures in the range 1000-20 000 K. The largest rates are found for charge transfer processes to and from two clusters of states around 6.3 and 6.6 eV excitation, corresponding in both cases to active 4d and 5p electrons undergoing transfer. Excitation and de-excitation processes among these two sets of states are also significant. Full Tables and rate coefficient data are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/612/A90

Mechanism of the Primary Charge Transfer Reaction in the Cytochrome bc1 Complex

DEFF Research Database (Denmark)

Barragan, Angela M; Schulten, Klaus; Solov'yov, Ilia A

2016-01-01

, the quinol-protein interaction, which initiates the Q-cycle, has not yet been completely described. Furthermore, the initial charge transfer reactions of the Q-cycle lack a physical description. The present investigation utilizes classical molecular dynamics simulations in tandem with quantum density...

Engineering Interfacial Charge Transfer in CsPbBr3 Perovskite Nanocrystals by Heterovalent Doping

KAUST Repository

Begum, Raihana; Parida, Manas R.; Abdelhady, Ahmed L.; Banavoth, Murali; AlYami, Noktan; Ahmed, Ghada H.; Hedhili, Mohamed N.; Bakr, Osman; Mohammed, Omar F.

2016-01-01

Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT

Oxygen-assisted charge transfer between ZnO quantum dots and graphene.

Science.gov (United States)

Guo, Wenhao; Xu, Shuigang; Wu, Zefei; Wang, Ning; Loy, M M T; Du, Shengwang

2013-09-23

Efficient charge transfer between ZnO quantum dots (QDs) and graphene is demonstrated by decorating ZnO QDs on top of graphene, with the assistance of oxygen molecules from the air. The electrical response of the device to UV light is greatly enhanced, and a photoconductive gain of up to 10(7) can be obtained. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Collisions of highly stripped ions at MeV energies in gas targets: charge transfer and ionization

International Nuclear Information System (INIS)

Schlachter, A.S.

1980-01-01

Cross sections have been measured for charge transfer and ionization in H 2 and rare-gas targets by fast, highly ionized carbon, iron, niobium, and lead ions in charge states +3 to +59, with energies in the range 0.1 to 4.8 MeV/amu. Experimental results are compared with classical-trajectory calculations; agreement is generally good. For a given target, the cross sections for net ionization reduce to a common curve when plotted as cross section divided by charge state versus energy per nucleon divided by charge state

Excited State Structural Dynamics of Carotenoids and Charge Transfer Systems

International Nuclear Information System (INIS)

Van Tassle, Aaron Justin

2006-01-01

This dissertation describes the development and implementation of a visible/near infrared pump/mid-infrared probe apparatus. Chapter 1 describes the background and motivation of investigating optically induced structural dynamics, paying specific attention to solvation and the excitation selection rules of highly symmetric molecules such as carotenoids. Chapter 2 describes the development and construction of the experimental apparatus used throughout the remainder of this dissertation. Chapter 3 will discuss the investigation of DCM, a laser dye with a fluorescence signal resulting from a charge transfer state. By studying the dynamics of DCM and of its methyl deuterated isotopomer (an otherwise identical molecule), we are able to investigate the origins of the charge transfer state and provide evidence that it is of the controversial twisted intramolecular (TICT) type. Chapter 4 introduces the use of two-photon excitation to the S1 state, combined with one-photon excitation to the S2 state of the carotenoid beta-apo-8'-carotenal. These 2 investigations show evidence for the formation of solitons, previously unobserved in molecular systems and found only in conducting polymers Chapter 5 presents an investigation of the excited state dynamics of peridinin, the carotenoid responsible for the light harvesting of dinoflagellates. This investigation allows for a more detailed understanding of the importance of structural dynamics of carotenoids in light harvesting

Phase Fluctuations and the Absence of Topological Defects in Photo-excited Charge Ordered Nickelate

Energy Technology Data Exchange (ETDEWEB)

Lee, W.S.; Chuang, Y.D.; Moore, R.G.; Zhu, Y.; Patthey, L.; Trigo, M.; Lu, D.H.; Kirchmann, P.S.; Krupin, O.; Yi, M.; Langner, M.; Huse, N.; Robinson, J.S.; Chen, Y.; Zhou, S.Y.; Coslovich, G.; Huber, B.; Reis, D.A.; Kaindl, R.A.; Schoenlein, R.W.; Doering, D.

2012-05-15

The dynamics of an order parameter's amplitude and phase determines the collective behaviour of novel states emerging in complex materials. Time- and momentum-resolved pump-probe spectroscopy, by virtue of measuring material properties at atomic and electronic time scales out of equilibrium, can decouple entangled degrees of freedom by visualizing their corresponding dynamics in the time domain. Here we combine time-resolved femotosecond optical and resonant X-ray diffraction measurements on charge ordered La{sub 1.75}Sr{sub 0.25}NiO{sub 4} to reveal unforeseen photoinduced phase fluctuations of the charge order parameter. Such fluctuations preserve long-range order without creating topological defects, distinct from thermal phase fluctuations near the critical temperature in equilibrium. Importantly, relaxation of the phase fluctuations is found to be an order of magnitude slower than that of the order parameter's amplitude fluctuations, and thus limits charge order recovery. This new aspect of phase fluctuations provides a more holistic view of the phase's importance in ordering phenomena of quantum matter.

Cash Impact of the Consumable Item Transfer, Phase II

National Research Council Canada - National Science Library

1998-01-01

...). This report is the third in a series of reports regarding the consumable item transfer (CIT), phase II. The Deputy Secretary of Defense directed the transfer of the management of consumable items to Defense Logistics Agency...

D- production by multiple charge-transfer collisions in metal-vapor targets. [1 to 50 keV D/sup +/

Energy Technology Data Exchange (ETDEWEB)

Schlachter, A.S.

1977-09-01

A beam of D/sup -/ions can be produced by multiple charge-transfer collisions of a D/sup +/ beam in a thick metal-vapor target. Cross sections and equilibrium charge-state fractions are presented and discussed.

Determination of gas phase protein ion densities via ion mobility analysis with charge reduction.

Science.gov (United States)

Maisser, Anne; Premnath, Vinay; Ghosh, Abhimanyu; Nguyen, Tuan Anh; Attoui, Michel; Hogan, Christopher J

2011-12-28

We use a charge reduction electrospray (ESI) source and subsequent ion mobility analysis with a differential mobility analyzer (DMA, with detection via both a Faraday cage electrometer and a condensation particle counter) to infer the densities of single and multiprotein ions of cytochrome C, lysozyme, myoglobin, ovalbumin, and bovine serum albumin produced from non-denaturing (20 mM aqueous ammonium acetate) and denaturing (1 : 49.5 : 49.5, formic acid : methanol : water) ESI. Charge reduction is achieved through use of a Po-210 radioactive source, which generates roughly equal concentrations of positive and negative ions. Ions produced by the source collide with and reduce the charge on ESI generated drops, preventing Coulombic fissions, and unlike typical protein ESI, leading to gas-phase protein ions with +1 to +3 excess charges. Therefore, charge reduction serves to effectively mitigate any role that Coulombic stretching may play on the structure of the gas phase ions. Density inference is made via determination of the mobility diameter, and correspondingly the spherical equivalent protein volume. Through this approach it is found that for both non-denaturing and denaturing ESI-generated ions, gas-phase protein ions are relatively compact, with average densities of 0.97 g cm(-3) and 0.86 g cm(-3), respectively. Ions from non-denaturing ESI are found to be slightly more compact than predicted from the protein crystal structures, suggesting that low charge state protein ions in the gas phase are slightly denser than their solution conformations. While a slight difference is detected between the ions produced with non-denaturing and denaturing ESI, the denatured ions are found to be much more dense than those examined previously by drift tube mobility analysis, in which charge reduction was not employed. This indicates that Coulombic stretching is typically what leads to non-compact ions in the gas-phase, and suggests that for gas phase

Tunable spin-charge conversion through topological phase transitions in zigzag nanoribbons

KAUST Repository

Li, Hang

2016-06-29

We study spin-orbit torques and charge pumping in magnetic quasi-one-dimensional zigzag nanoribbons with a hexagonal lattice, in the presence of large intrinsic spin-orbit coupling. Such a system experiences a topological phase transition from a trivial band insulator to a quantum spin Hall insulator by tuning of either the magnetization direction or the intrinsic spin-orbit coupling. We find that the spin-charge conversion efficiency (i.e., spin-orbit torque and charge pumping) is dramatically enhanced at the topological transition, displaying a substantial angular anisotropy.

Tunable spin-charge conversion through topological phase transitions in zigzag nanoribbons

KAUST Repository

Li, Hang; Manchon, Aurelien

2016-01-01

We study spin-orbit torques and charge pumping in magnetic quasi-one-dimensional zigzag nanoribbons with a hexagonal lattice, in the presence of large intrinsic spin-orbit coupling. Such a system experiences a topological phase transition from a trivial band insulator to a quantum spin Hall insulator by tuning of either the magnetization direction or the intrinsic spin-orbit coupling. We find that the spin-charge conversion efficiency (i.e., spin-orbit torque and charge pumping) is dramatically enhanced at the topological transition, displaying a substantial angular anisotropy.

Electronic structure, charge transfer, and intrinsic luminescence of gadolinium oxide nanoparticles: Experiment and theory

Science.gov (United States)

Zatsepin, D. A.; Boukhvalov, D. W.; Zatsepin, A. F.; Kuznetsova, Yu. A.; Mashkovtsev, M. A.; Rychkov, V. N.; Shur, V. Ya.; Esin, A. A.; Kurmaev, E. Z.

2018-04-01

The cubic (c) and monoclinic (m) polymorphs of Gd2O3 were studied using the combined analysis of several materials science techniques - X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectroscopy. Density functional theory (DFT) based calculations for the samples under study were performed as well. The cubic phase of gadolinium oxide (c-Gd2O3) synthesized using a precipitation method exhibits spheroidal-like nanoclusters with well-defined edges assembled from primary nanoparticles with an average size of 50 nm, whereas the monoclinic phase of gadolinium oxide (m-Gd2O3) deposited using explosive pyrolysis has a denser structure compared with natural gadolinia. This phase also has a structure composed of three-dimensional complex agglomerates without clear-edged boundaries that are ∼21 nm in size plus a cubic phase admixture of only 2 at.% composed of primary edge-boundary nanoparticles ∼15 nm in size. These atomic features appear in the electronic structure as different defects ([Gd…Osbnd OH] and [Gd…Osbnd O]) and have dissimilar contributions to the charge-transfer processes among the appropriate electronic states with ambiguous contributions in the Gd 5р - O 2s core-like levels in the valence band structures. The origin of [Gd…Osbnd OH] defects found by XPS was well-supported by PL analysis. The electronic and atomic structures of the synthesized gadolinias calculated using DFT were compared and discussed on the basis of the well-known joint OKT-van der Laan model, and good agreement was established.

Charge transfer and bond lengths in YBa2Cu3-xMxO6+y

International Nuclear Information System (INIS)

Jorgensen, J.D.; Rhyne, J.J.; Neumann, D.A.; Miceli, P.F.; Tarascon, J.M.; Greene, L.H.; Barboux, P.

1989-01-01

We discuss the effects of doping on the Cu chain sites in YBa 2 Cu 3-x M x O 6+y . The relationship between bond lengths obtained from neutron scattering and charge transfer is evaluated in terms of bond valence. In particular, it is concluded that removing an oxygen from the chains transfers one electron to the planes. 24 refs., 3 figs

Fermi level alignment in molecular nanojunctions and its relation to charge transfer

DEFF Research Database (Denmark)

Stadler, Robert; Jacobsen, Karsten Wedel

2006-01-01

The alignment of the Fermi level of a metal electrode within the gap of the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of a molecule is a key quantity in molecular electronics, which can vary the electron transparency of a single-molecule junction...... by orders of magnitude. We present a quantitative analysis of the relation between this level alignment (which can be estimated from charging free molecules) and charge transfer for bipyridine and biphenyl dithiolate (BPDT) molecules attached to gold leads based on density functional theory calculations...... end of the gap in the transmission function for bipyridine and at its lower end for BPDT....

Quantum computing based on space states without charge transfer

International Nuclear Information System (INIS)

Vyurkov, V.; Filippov, S.; Gorelik, L.

2010-01-01

An implementation of a quantum computer based on space states in double quantum dots is discussed. There is no charge transfer in qubits during a calculation, therefore, uncontrolled entanglement between qubits due to long-range Coulomb interaction is suppressed. Encoding and processing of quantum information is merely performed on symmetric and antisymmetric states of the electron in double quantum dots. Other plausible sources of decoherence caused by interaction with phonons and gates could be substantially suppressed in the structure as well. We also demonstrate how all necessary quantum logic operations, initialization, writing, and read-out could be carried out in the computer.

State-selective charge transfer and excitation in ion-ion interactions at intermediate and high energies

International Nuclear Information System (INIS)

Samanta, R; Purkait, M

2012-01-01

Boundary Corrected Continuum Intermediate State (BCCIS) approximation and Classical Trajectory Monte Carlo (CTMC) methods are applied to calculate the charge transfer and excitation cross sections for ion-ion collisions.

Energy and charge transfer dynamics between Alq3 and CdSeS nanocrystals.

Science.gov (United States)

Zhang, Shuping; Liu, Yuqiang; Yang, Yanqiang

2010-03-01

The photoluminescence properties of the blend films consisting of organic small molecules and nanocrystals (NCs)--Alq3 and CdSeS NCs--were studied by steady-state and time-resolved photoluminescence (PL) spectroscopy with different excited wavelengths. Both the fluorescence intensity and lifetime are intensively dependent on the NC concentration. The detailed analysis of experiment data proves that Forster energy transfer from the Alq3 to the NCs exists simultaneously with the charge transfer and both compete with each other in the blend films.

Simple heuristic derivation of some charge-transfer probabilities at asymptotically high incident velocities

International Nuclear Information System (INIS)

Spruch, L.; Shakeshaft, R.

1984-01-01

For asymptotically high incident velocities we provide simple, heuristic, almost classical, derivations of the cross section for forward charge transfer, and of the ratio of the cross section for capture to the elastic-scattering cross section for the projectile scattered through an angle close to π/3

Single Molecule Spectroelectrochemistry of Interfacial Charge Transfer Dynamics In Hybrid Organic Solar Cell

Energy Technology Data Exchange (ETDEWEB)

Pan, Shanlin [Univ. of Alabama, Tuscaloosa, AL (United States)

2014-11-16

Our research under support of this DOE grant is focused on applied and fundamental aspects of model organic solar cell systems. Major accomplishments are: 1) we developed a spectroelectorchemistry technique of single molecule single nanoparticle method to study charge transfer between conjugated polymers and semiconductor at the single molecule level. The fluorescence of individual fluorescent polymers at semiconductor surfaces was shown to exhibit blinking behavior compared to molecules on glass substrates. Single molecule fluorescence excitation anisotropy measurements showed the conformation of the polymer molecules did not differ appreciably between glass and semiconductor substrates. The similarities in molecular conformation suggest that the observed differences in blinking activity are due to charge transfer between fluorescent polymer and semiconductor, which provides additional pathways between states of high and low fluorescence quantum efficiency. Similar spectroelectrochemistry work has been done for small organic dyes for understand their charge transfer dynamics on various substrates and electrochemical environments; 2) We developed a method of transferring semiconductor nanoparticles (NPs) and graphene oxide (GO) nanosheets into organic solvent for a potential electron acceptor in bulk heterojunction organic solar cells which employed polymer semiconductor as the electron donor. Electron transfer from the polymer semiconductor to semiconductor and GO in solutions and thin films was established through fluorescence spectroscopy and electroluminescence measurements. Solar cells containing these materials were constructed and evaluated using transient absorption spectroscopy and dynamic fluorescence techniques to understand the charge carrier generation and recombination events; 3) We invented a spectroelectorchemistry technique using light scattering and electroluminescence for rapid size determination and studying electrochemistry of single NPs in an

Impact of speciation on the electron charge transfer properties of nanodiamond drug carriers.

Science.gov (United States)

Sun, Baichuan; Barnard, Amanda S

2016-08-07

Unpassivated diamond nanoparticles (bucky-diamonds) exhibit a unique surface reconstruction involving graphitization of certain crystal facets, giving rise to hybrid core-shell particles containing both aromatic and aliphatic carbon. Considerable effort is directed toward eliminating the aromatic shell, but persistent graphitization of subsequent subsurface-layers makes perdurable purification a challenge. In this study we use some simple statistical methods, in combination with electronic structure simulations, to predict the impact of different fractions of aromatic and aliphatic carbon on the charge transfer properties of the ensembles of bucky-diamonds. By predicting quality factors for a variety of cases, we find that perfect purification is not necessary to preserve selectivity, and there is a clear motivation for purifying samples to improve the sensitivity of charge transfer reactions. This may prove useful in designing drug delivery systems where the release of (selected) drugs needs to be sensitive to specific conditions at the point of delivery.

Size-Induced Segregation in the Stepwise Microhydration of Hydantoin and Its Role in Proton-Induced Charge Transfer

Science.gov (United States)

Calvo, Florent; Bacchus-Montabonel, Marie-Christine

2018-01-01

Recent photochemistry experiments provided evidence for the formation of hydantoin by irradiation of interstellar ice analogues. The significance of these results and the importance of hydantoin in prebiotic chemistry and polypeptide synthesis motivate the present theoretical investigation, in which we analyzed the effects of stepwise hydration on the electronic and thermodynamical properties of the structure of microhydrated hydantoin using a variety of computational approaches. We generally find microhydration to proceed around the hydantoin heterocycle until 5 water molecules are reached, at which stage hydration becomes segregated with a water cluster forming aside the heterocycle. The reactivity of microhydrated hydantoin caused by an impinging proton was evaluated through charge transfer collision cross sections for microhydrated compounds but also for hydantoin on icy grains modeled using a cluster approach mimicking the true hexagonal ice surface. The effects of hydration on charge transfer efficiency are mostly significant when few water molecules are present, and they progressively weaken and stabilize in larger clusters. On the ice substrate, charge transfer essentially contributes to a global increase in the cross sections.

Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

Energy Technology Data Exchange (ETDEWEB)

Haverkate, Lucas A.; Mulder, Fokko M. [Reactor Institute Delft, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629JB Delft (Netherlands); Zbiri, Mohamed, E-mail: zbiri@ill.fr; Johnson, Mark R. [Institut Laue Langevin, 38042 Grenoble Cedex 9 (France); Carter, Elizabeth [Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, NSW 2008 (Australia); Kotlewski, Arek; Picken, S. [ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL/136 Delft (Netherlands); Kearley, Gordon J. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia)

2014-01-07

Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup −2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

Alternating phase focussing including space charge

International Nuclear Information System (INIS)

Cheng, W.H.; Gluckstern, R.L.

1992-01-01

Longitudinal stability can be obtained in a non-relativistic drift tube accelerator by traversing each gap as the rf accelerating field rises. However, the rising accelerating field leads to a transverse defocusing force which is usually overcome by magnetic focussing inside the drift tubes. The radio frequency quadrupole is one way of providing simultaneous longitudinal and transverse focusing without the use of magnets. One can also avoid the use of magnets by traversing alternate gaps between drift tubes as the field is rising and falling, thus providing an alternation of focussing and defocusing forces in both the longitudinal and transverse directions. The stable longitudinal phase space area is quite small, but recent efforts suggest that alternating phase focussing (APF) may permit low velocity acceleration of currents in the 100-300 ma range. This paper presents a study of the parameter space and a test of crude analytic predictions by adapting the code PARMILA, which includes space charge, to APF. 6 refs., 3 figs

Atomic and electronic structure of trilayer graphene/SiC(0001): Evidence of Strong Dependence on Stacking Sequence and charge transfer.

Science.gov (United States)

Pierucci, Debora; Brumme, Thomas; Girard, Jean-Christophe; Calandra, Matteo; Silly, Mathieu G; Sirotti, Fausto; Barbier, Antoine; Mauri, Francesco; Ouerghi, Abdelkarim

2016-09-15

The transport properties of few-layer graphene are the directly result of a peculiar band structure near the Dirac point. Here, for epitaxial graphene grown on SiC, we determine the effect of charge transfer from the SiC substrate on the local density of states (LDOS) of trilayer graphene using scaning tunneling microscopy/spectroscopy and angle resolved photoemission spectroscopy (ARPES). Different spectra are observed and are attributed to the existence of two stable polytypes of trilayer: Bernal (ABA) and rhomboedreal (ABC) staking. Their electronic properties strongly depend on the charge transfer from the substrate. We show that the LDOS of ABC stacking shows an additional peak located above the Dirac point in comparison with the LDOS of ABA stacking. The observed LDOS features, reflecting the underlying symmetry of the two polytypes, were reproduced by explicit calculations within density functional theory (DFT) including the charge transfer from the substrate. These findings demonstrate the pronounced effect of stacking order and charge transfer on the electronic structure of trilayer or few layer graphene. Our approach represents a significant step toward understand the electronic properties of graphene layer under electrical field.

Imidazole as a parent π-conjugated backbone in charge-transfer chromophores

Directory of Open Access Journals (Sweden)

Jiří Kulhánek

2012-01-01

Full Text Available Research activities in the field of imidazole-derived push–pull systems featuring intramolecular charge transfer (ICT are reviewed. Design, synthetic pathways, linear and nonlinear optical properties, electrochemistry, structure–property relationships, and the prospective application of such D-π-A organic materials are described. This review focuses on Y-shaped imidazoles, bi- and diimidazoles, benzimidazoles, bis(benzimidazoles, imidazole-4,5-dicarbonitriles, and imidazole-derived chromophores chemically bound to a polymer chain.

Chemical and physical investigations on the charge transfer interaction of organic donors with iodine and its application as non-traditional organic conductors

Science.gov (United States)

Refat, Moamen S.; Sharshar, T.; Adam, Abdel Majid A.; Elsabawy, Khaled M.; Hemeda, O. M.

2014-09-01

The iso-leucine-iodide and methionine-iodide charge-transfer complexes were prepared and characterized using different spectroscopic techniques. The iodide charge-transfer complexes were synthesized by grinding KI-I2-amino acid with 1:1:1 M ratio in presence of few drops of methanol solvent. The structures of both solid amino acid iodide charge-transfer complexes are discussed with the help of the obtained results of the infrared and Raman laser spectra, Uv-vis. electronic spectra and thermal analyses. The electrical properties (AC resistivity and dielectric constant) of both complexes were investigated. The positron annihilation Doppler broadening (PADB) spectroscopies were also used to probe the structural changes of both complexes. The PADB line-shape parameters (S and W) were found to be dependent on the structure, electronic configuration of the charge transfer complex. The PADB technique is a powerful tool to probe the structural features of the KI-I2-amino acid complexes.

Charge-Transfer States in Organic Solar Cells: Understanding the Impact of Polarization, Delocalization, and Disorder

KAUST Repository

Zheng, Zilong

2017-05-08

We investigate the impact of electronic polarization, charge delocalization, and energetic disorder on the charge-transfer (CT) states formed at a planar C60/pentacene interface. The ability to examine large complexes containing up to seven pentacene molecules and three C60 molecules allows us to take explicitly into account the electronic polarization effects. These complexes are extracted from a bilayer architecture modeled by molecular dynamics simulations and evaluated by means of electronic-structure calculations based on long-range-separated functionals (ωB97XD and BNL) with optimized range-separation parameters. The energies of the lowest charge-transfer states derived for the large complexes are in very good agreement with the experimentally reported values. The average singlet-triplet energy splittings of the lowest CT states are calculated not to exceed 10 meV. The rates of geminate recombination as well as of dissociation of the triplet excitons are also evaluated. In line with experiment, our results indicate that the pentacene triplet excitons generated through singlet fission can dissociate into separated charges on a picosecond time scale, despite the fact that their energy in C60/pentacene heterojunctions is slightly lower than the energies of the lowest CT triplet states.

Incorporating space charge in the transverse phase-space matching and tomography at PITZ

Energy Technology Data Exchange (ETDEWEB)

Kourkafas, Georgios

2015-11-15

The ever-expanding achievements in the field of particle accelerators push their specifications to very demanding levels. The performance of many modern applications depends on their ability to be operated with high bunch charges confined in small volumes. However, the consequence of increased intensity is strong space-charge forces, which perplex the beam manipulation and undermine the beam quality. As a result, reliable methods are needed to control and measure the accelerated particles under these extraordinary conditions. The phase space tomography is a diagnostic technique which can reveal details of the transverse beam parameters for a wide range of intensities and energies, with minimal influence from the machine instabilities, in a quasi non-destructive way. The accuracy of this method relies on the precise knowledge and control of the particle dynamics under the influence of space charge in different stages of the measurement. On the one hand, the matching of the beam to the measurement's design transverse parameters requires a procedure which efficiently compensates the effects of space charge. Depending on the structure of the magnetic lattice, different aspects of these effects prevail, therefore different strategies have to be developed. On the other hand, the impact of the space-charge forces on the phase-space transformations during the data acquisition has to be included in the model which is used for the tomographic reconstruction. The aim of this thesis is to provide and test time-efficient solutions for the incorporation of space charge in the transverse beam matching and phase space tomography.

Incorporating space charge in the transverse phase-space matching and tomography at PITZ

International Nuclear Information System (INIS)

Kourkafas, Georgios

2015-11-01

The ever-expanding achievements in the field of particle accelerators push their specifications to very demanding levels. The performance of many modern applications depends on their ability to be operated with high bunch charges confined in small volumes. However, the consequence of increased intensity is strong space-charge forces, which perplex the beam manipulation and undermine the beam quality. As a result, reliable methods are needed to control and measure the accelerated particles under these extraordinary conditions. The phase space tomography is a diagnostic technique which can reveal details of the transverse beam parameters for a wide range of intensities and energies, with minimal influence from the machine instabilities, in a quasi non-destructive way. The accuracy of this method relies on the precise knowledge and control of the particle dynamics under the influence of space charge in different stages of the measurement. On the one hand, the matching of the beam to the measurement's design transverse parameters requires a procedure which efficiently compensates the effects of space charge. Depending on the structure of the magnetic lattice, different aspects of these effects prevail, therefore different strategies have to be developed. On the other hand, the impact of the space-charge forces on the phase-space transformations during the data acquisition has to be included in the model which is used for the tomographic reconstruction. The aim of this thesis is to provide and test time-efficient solutions for the incorporation of space charge in the transverse beam matching and phase space tomography.

Charge-transfer collisions involving few-electron systems

International Nuclear Information System (INIS)

Kirchner, T.

2016-01-01

Ion-atom collision systems that involve more than one electron constitute nonseparable few-body problems, whose full solution is difficult to say the least. At impact energies well below 1 keV/amu an expansion of the stationary scattering wave function in terms of a limited number of products of nuclear and molecular state wave functions (amended to satisfy scattering boundary conditions) is feasible and usually sufficient to obtain accurate charge-transfer cross sections provided the electronic wave functions include configuration interaction. At energies above 1 keV/amu this approach becomes inefficient and close-coupling methods within the semi classical approximation are better suited to treat the problem. For bare-ion collisions from helium target atoms explicit solutions of the two-electron time-dependent Schrödinger equation can be achieved, but are computationally costly and cannot be extended to problems which involve more than two electrons.

Direct evidence of charge separation in a metal-organic framework: efficient and selective photocatalytic oxidative coupling of amines via charge and energy transfer.

Science.gov (United States)

Xu, Caiyun; Liu, Hang; Li, Dandan; Su, Ji-Hu; Jiang, Hai-Long

2018-03-28

The selective aerobic oxidative coupling of amines under mild conditions is an important laboratory and commercial procedure yet a great challenge. In this work, a porphyrinic metal-organic framework, PCN-222, was employed to catalyze the reaction. Upon visible light irradiation, the semiconductor-like behavior of PCN-222 initiates charge separation, evidently generating oxygen-centered active sites in Zr-oxo clusters indicated by enhanced porphyrin π-cation radical signals. The photogenerated electrons and holes further activate oxygen and amines, respectively, to give the corresponding redox products, both of which have been detected for the first time. The porphyrin motifs generate singlet oxygen based on energy transfer to further promote the reaction. As a result, PCN-222 exhibits excellent photocatalytic activity, selectivity and recyclability, far superior to its organic counterpart, for the reaction under ambient conditions via combined energy and charge transfer.

Bane of Hydrogen-Bond Formation on the Photoinduced Charge-Transfer Process in Donor–Acceptor Systems

KAUST Repository

Alsam, Amani Abdu; Adhikari, Aniruddha; Parida, Manas R.; Aly, Shawkat Mohammede; Bakr, Osman; Mohammed, Omar F.

2017-01-01

Controlling the ultrafast dynamical process of photoinduced charge transfer at donor acceptor interfaces remains a major challenge for physical chemistry and solar cell communities. The process is complicated by the involvement of other complex

Influence of Coherent Tunneling and Incoherent Hopping on the Charge Transfer Mechanism in Linear Donor-Bridge-Acceptor Systems.

Science.gov (United States)

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.

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

International Nuclear Information System (INIS)

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. (orig.)

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

Energy Technology Data Exchange (ETDEWEB)

Li, Hui-Ling [University of Electronic Science and Technology of China, School of Physical Electronics, Chengdu (China); Shenyang Normal University, College of Physics Science and Technology, Shenyang (China); Feng, Zhong-Wen [China West Normal University, College of Physics and Space Science, Nanchong (China); Zu, Xiao-Tao [University of Electronic Science and Technology of China, School of Physical Electronics, Chengdu (China)

2018-01-15

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. (orig.)

Models of charge transport and transfer in molecular switch tunnel junctions of bistable catenanes and rotaxanes

International Nuclear Information System (INIS)

Flood, Amar H.; Wong, Eric W.; Stoddart, J. Fraser

2006-01-01

The processes by which charge transfer can occur play a foundational role in molecular electronics. Here we consider simplified models of the transfer processes that could be present in bistable molecular switch tunnel junction (MSTJ) devices during one complete cycle of the device from its low- to high- and back to low-conductance state. The bistable molecular switches, which are composed of a monolayer of either switchable catenanes or rotaxanes, exist in either a ground-state co-conformation or a metastable one in which the conduction properties of the two co-conformations, when measured at small biases (+0.1 V), are significantly different irrespective of whether transport is dominated by tunneling or hopping. The voltage-driven generation (±2 V) of molecule-based redox states, which are sufficiently long-lived to allow the relative mechanical movements necessary to switch between the two co-conformations, rely upon unequal charge transfer rates on to and/or off of the molecules. Surface-enhanced Raman spectroscopy has been used to image the ground state of the bistable rotaxane in MSTJ-like devices. Consideration of these models provide new ways of looking at molecular electronic devices that rely, not only on nanoscale charge-transport, but also upon the bustling world of molecular motion in mechanically interlocked bistable molecules

Quantum phases for point-like charged particles and for electrically neutral dipoles in an electromagnetic field

Science.gov (United States)

Kholmetskii, A. L.; Missevitch, O. V.; Yarman, T.

2018-05-01

We point out that the known quantum phases for an electric/magnetic dipole moving in an electromagnetic (EM) field must be presented as the superposition of more fundamental quantum phases emerging for elementary charges. Using this idea, we find two new fundamental quantum phases for point-like charges, next to the known electric and magnetic Aharonov-Bohm (A-B) phases, named by us as the complementary electric and magnetic phases, correspondingly. We further demonstrate that these new phases can indeed be derived via the Schrödinger equation for a particle in an EM field, where however the operator of momentum is re-defined via the replacement of the canonical momentum of particle by the sum of its mechanical momentum and interactional field momentum for a system "charged particle and a macroscopic source of EM field". The implications of the obtained results are discussed.

Phase fluctuations and the absence of topological defects in a photo-excited charge-ordered nickelate

Energy Technology Data Exchange (ETDEWEB)

Lee, W. S.; Chuang, Y. D.; Moore, R. G.; Zhu, Y.; Patthey, L.; Trigo, M.; Lu, D. H.; Kirchmann, P. S.; Krupin, O.; Yi, M.; Langner, M.; Huse, N.; Robinson, J. S.; Chen, Y.; Zhou, S. Y.; Coslovich, G.; Huber, B.; Reis, D. A.; Kaindl, R. A.; Schoenlein, R. W.; Doering, D.; Denes, P.; Schlotter, W. F.; Turner, J. J.; Johnson, S. L.; Först, M.; Sasagawa, T.; Kung, Y. F.; Sorini, A. P.; Kemper, A. F.; Moritz, B.; Devereaux, T. P.; Lee, D. -H.; Shen, Z. X.; Hussain, Z.

2012-05-15

The dynamics of an order parameter's amplitude and phase determines the collective behaviour of novel states emerging in complex materials. Time- and momentum-resolved pump-probe spectroscopy, by virtue of measuring material properties at atomic and electronic time scales out of equilibrium, can decouple entangled degrees of freedom by visualizing their corresponding dynamics in the time domain. Here we combine time-resolved femotosecond optical and resonant X-ray diffraction measurements on charge ordered La1.75Sr0.25NiO4 to reveal unforeseen photoinduced phase fluctuations of the charge order parameter. Such fluctuations preserve long-range order without creating topological defects, distinct from thermal phase fluctuations near the critical temperature in equilibrium. Importantly, relaxation of the phase fluctuations is found to be an order of magnitude slower than that of the order parameter's amplitude fluctuations, and thus limits charge order recovery. This new aspect of phase fluctuations provides a more holistic view of the phase's importance in ordering phenomena of quantum matter.

Fragment-orbital tunneling currents and electronic couplings for analysis of molecular charge-transfer systems.

Science.gov (United States)

Hwang, Sang-Yeon; Kim, Jaewook; Kim, Woo Youn

2018-04-04

In theoretical charge-transfer research, calculation of the electronic coupling element is crucial for examining the degree of the electronic donor-acceptor interaction. The tunneling current (TC), representing the magnitudes and directions of electron flow, provides a way of evaluating electronic couplings, along with the ability of visualizing how electrons flow in systems. Here, we applied the TC theory to π-conjugated organic dimer systems, in the form of our fragment-orbital tunneling current (FOTC) method, which uses the frontier molecular-orbitals of system fragments as diabatic states. For a comprehensive test of FOTC, we assessed how reasonable the computed electronic couplings and the corresponding TC densities are for the hole- and electron-transfer databases HAB11 and HAB7. FOTC gave 12.5% mean relative unsigned error with regard to the high-level ab initio reference. The shown performance is comparable with that of fragment-orbital density functional theory, which gave the same error by 20.6% or 13.9% depending on the formulation. In the test of a set of nucleobase π stacks, we showed that the original TC expression is also applicable to nondegenerate cases under the condition that the overlap between the charge distributions of diabatic states is small enough to offset the energy difference. Lastly, we carried out visual analysis on the FOTC densities of thiophene dimers with different intermolecular alignments. The result depicts an intimate topological connection between the system geometry and electron flow. Our work provides quantitative and qualitative grounds for FOTC, showing it to be a versatile tool in characterization of molecular charge-transfer systems.

Microscopic description of pair transfer between two superfluid Fermi systems: Combining phase-space averaging and combinatorial techniques

Science.gov (United States)

Regnier, David; Lacroix, Denis; Scamps, Guillaume; Hashimoto, Yukio

2018-03-01

In a mean-field description of superfluidity, particle number and gauge angle are treated as quasiclassical conjugated variables. This level of description was recently used to describe nuclear reactions around the Coulomb barrier. Important effects of the relative gauge angle between two identical superfluid nuclei (symmetric collisions) on transfer probabilities and fusion barrier have been uncovered. A theory making contact with experiments should at least average over different initial relative gauge-angles. In the present work, we propose a new approach to obtain the multiple pair transfer probabilities between superfluid systems. This method, called phase-space combinatorial (PSC) technique, relies both on phase-space averaging and combinatorial arguments to infer the full pair transfer probability distribution at the cost of multiple mean-field calculations only. After benchmarking this approach in a schematic model, we apply it to the collision 20O+20O at various energies below the Coulomb barrier. The predictions for one pair transfer are similar to results obtained with an approximated projection method, whereas significant differences are found for two pairs transfer. Finally, we investigated the applicability of the PSC method to the contact between nonidentical superfluid systems. A generalization of the method is proposed and applied to the schematic model showing that the pair transfer probabilities are reasonably reproduced. The applicability of the PSC method to asymmetric nuclear collisions is investigated for the 14O+20O collision and it turns out that unrealistically small single- and multiple pair transfer probabilities are obtained. This is explained by the fact that relative gauge angle play in this case a minor role in the particle transfer process compared to other mechanisms, such as equilibration of the charge/mass ratio. We conclude that the best ground for probing gauge-angle effects in nuclear reaction and/or for applying the proposed

Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives and thermodynamic study on intermolecular charge transfer for developing efficient organic solar cell

Energy Technology Data Exchange (ETDEWEB)

Zhang, Chao-Zhi, E-mail: zhangchaozhi@nuist.edu.cn [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Shen, Dan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Yuan, Yang [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Song, Ming-Xia; Li, Shi-Juan [Department of Chemistry, Nanjing University of Information Science & Technology, Nanjing 210044 (China); Cao, Hui, E-mail: yccaoh@hotmail.com [Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control, Nanjing University of Information Science & Technology, Nanjing 210044 (China)

2016-07-01

A series of planar 1,5,2,4,6,8-dithiotetrazocine derivatives were synthesized for study on charge transfer at donor/acceptor interface. The fluorescence quenching spectra, and the highest occupied molecular orbital (−6.10 ∼ −6.25 eV) and the lowest unoccupied molecular orbital (−3.45 ∼ −3.58 eV) energy levels of these 1,5,2,4,6,8-dithiotetrazocine derivatives show that they would be potential acceptor materials. Based on theoretical calculations, thermodynamic study on charge transfer at donor/acceptor interface was carried out. The results of experiments and theoretical calculations show that the electrons could transfer spontaneously from poly(3-hexylthiophene) to these acceptors. The percentages of fluorescence quenching increase with negative Gibbs free energy values increasing in the charge transfer procedures. Therefore, short circuit current values of organic solar cells would increase with the Gibbs free energy values increasing. This paper suggests a useful way for developing efficient organic solar cells. - Highlights: • Syntheses of planar 1,5,2,4,6,8-dithiotetrazocine derivatives for develop effective acceptor. • Electrons at excited state in P3HT could transfer spontaneously to these acceptors. • Thermodynamic study on charge transfer at donor/acceptor interface. • Short circuit currents would be predicted by Gibbs free energy in procedure of charge transfer.

Modeling the effect of shunt current on the charge transfer efficiency of an all-vanadium redox flow battery

Science.gov (United States)

Chen, Yong-Song; Ho, Sze-Yuan; Chou, Han-Wen; Wei, Hwa-Jou

2018-06-01

In an all-vanadium redox flow battery (VRFB), a shunt current is inevitable owing to the electrically conductive electrolyte that fills the flow channels and manifolds connecting cells. The shunt current decreases the performance of a VRFB stack as well as the energy conversion efficiency of a VRFB system. To understand the shunt-current loss in a VRFB stack with various designs and operating conditions, a mathematical model is developed to investigate the effects of the shunt current on battery performance. The model is calibrated with experimental data under the same operating conditions. The effects of the battery design, including the number of cells, state of charge (SOC), operating current, and equivalent resistance of the electrolytes in the flow channels and manifolds, on the shunt current are analyzed and discussed. The charge-transfer efficiency is calculated to investigate the effects of the battery design parameters on the shunt current. When the cell number is increased from 5 to 40, the charge transfer efficiency is decreased from 0.99 to a range between 0.76 and 0.88, depending on operating current density. The charge transfer efficiency can be maintained at higher than 0.9 by limiting the cell number to less than 20.

Charge transfer to a dielectric target by guided ionization waves using electric field measurements

NARCIS (Netherlands)

Slikboer, E.T.; Garcia-Caurel, E.; Guaitella, O.; Sobota, A.

2017-01-01

A kHz-operated atmospheric pressure plasma jet is investigated by measuring charge transferred to a dielectric electro-optic surface (BSO crystal) allowing for the measurement of electric field by exploiting the Pockels effect. The electric field values, distribution of the surface discharge and

Surface characterization and surface electronic structure of organic quasi-one-dimensional charge transfer salts

DEFF Research Database (Denmark)

Sing, M.; Schwingenschlögl, U.; Claessen, R.

2003-01-01

We have thoroughly characterized the surfaces of the organic charge-transfer salts TTF-TCNQ and (TMTSF)(2)PF6 which are generally acknowledged as prototypical examples of one-dimensional conductors. In particular x-ray-induced photoemission spectroscopy turns out to be a valuable nondestructive...

Charge transfer through single molecule contacts: How reliable are rate descriptions?

Directory of Open Access Journals (Sweden)

Denis Kast

2011-08-01

Full Text Available Background: The trend for the fabrication of electrical circuits with nanoscale dimensions has led to impressive progress in the field of molecular electronics in the last decade. However, a theoretical description of molecular contacts as the building blocks of future devices is challenging, as it has to combine the properties of Fermi liquids in the leads with charge and phonon degrees of freedom on the molecule. Outside of ab initio schemes for specific set-ups, generic models reveal the characteristics of transport processes. Particularly appealing are descriptions based on transfer rates successfully used in other contexts such as mesoscopic physics and intramolecular electron transfer. However, a detailed analysis of this scheme in comparison with numerically exact solutions is still elusive.Results: We show that a formulation in terms of transfer rates provides a quantitatively accurate description even in domains of parameter space where strictly it is expected to fail, e.g., at lower temperatures. Typically, intramolecular phonons are distributed according to a voltage driven steady state that can only roughly be captured by a thermal distribution with an effective elevated temperature (heating. An extension of a master equation for the charge–phonon complex, to effectively include the impact of off-diagonal elements of the reduced density matrix, provides very accurate solutions even for stronger electron–phonon coupling.Conclusion: Rate descriptions and master equations offer a versatile model to describe and understand charge transfer processes through molecular junctions. Such methods are computationally orders of magnitude less expensive than elaborate numerical simulations that, however, provide exact solutions as benchmarks. Adjustable parameters obtained, e.g., from ab initio calculations allow for the treatment of various realizations. Even though not as rigorously formulated as, e.g., nonequilibrium Green’s function

A statewide teleradiology system reduces radiation exposure and charges in transferred trauma patients.

Science.gov (United States)

Watson, Justin J J; Moren, Alexis; Diggs, Brian; Houser, Ben; Eastes, Lynn; Brand, Dawn; Bilyeu, Pamela; Schreiber, Martin; Kiraly, Laszlo

2016-05-01

Trauma transfer patients routinely undergo repeat imaging because of inefficiencies within the radiology system. In 2009, the virtual private network (VPN) telemedicine system was adopted throughout Oregon allowing virtual image transfer between hospitals. The startup cost was a nominal $3,000 per hospital. A retrospective review from 2007 to 2012 included 400 randomly selected adult trauma transfer patients based on a power analysis (200 pre/200 post). The primary outcome evaluated was reduction in repeat computed tomography (CT) scans. Secondary outcomes included cost savings, emergency department (ED) length of stay (LOS), and spared radiation. All data were analyzed using Mann-Whitney U and chi-square tests. P less than .05 indicated significance. Spared radiation was calculated as a weighted average per body region, and savings was calculated using charges obtained from Oregon Health and Science University radiology current procedural terminology codes. Four-hundred patients were included. Injury Severity Score, age, ED and overall LOS, mortality, trauma type, and gender were not statistically different between groups. The percentage of patients with repeat CT scans decreased after VPN implementation: CT abdomen (13.2% vs 2.8%, P < .01) and cervical spine (34.4% vs 18.2%, P < .01). Post-VPN, the total charges saved in 2012 for trauma transfer patients was $333,500, whereas the average radiation dose spared per person was 1.8 mSV. Length of stay in the ED for patients with Injury Severity Score less than 15 transferring to the ICU was decreased (P < .05). Implementation of a statewide teleradiology network resulted in fewer total repeat CT scans, significant savings, decrease in radiation exposure, and decreased LOS in the ED for patients with less complex injuries. The potential for health care savings by widespread adoption of a VPN is significant. Copyright © 2016 Elsevier Inc. All rights reserved.

Phase behaviour and structure of stable complexes of oppositely charged polyelectrolytes

Science.gov (United States)

Mengarelli, V.; Auvray, L.; Zeghal, M.

2009-03-01

We study the formation and structure of stable electrostatic complexes between oppositely charged polyelectrolytes, a long polymethacrylic acid and a shorter polyethylenimine, at low pH, where the polyacid is weakly charged. We explore the phase diagram as a function of the charge and concentration ratio of the constituents. In agreement with theory, turbidity and ζ potential measurements show two distinct regimes of weak and strong complexation, which appear successively as the pH is increased and are separated by a well-defined limit. Weak complexes observed by neutron scattering and contrast matching have an open, non-compact structure, while strong complexes are condensed.

Solvent control of charge transfer excited state relaxation pathways in [Fe(2,2 '-bipyridine)(CN)4]2-

DEFF Research Database (Denmark)

Kjær, Kasper Skov; Kunnus, Kristjan; Harlang, Tobias C. B.

2018-01-01

The excited state dynamics of solvated [Fe(bpy)(CN)4]2-, where bpy = 2,2'-bipyridine, show significant sensitivity to the solvent Lewis acidity. Using a combination of optical absorption and X-ray emission transient spectroscopies, we have previously shown that the metal to ligand charge transfer...... the MLCT excited state relaxation dynamics of [Fe(bpy)(CN)4]2- in water, a strong Lewis acid solvent. The charge-transfer excited state is now found to decay in less than 100 femtoseconds, forming a quasi-stable metal centered excited state with a 13 picosecond lifetime. We find that this MC excited state...... developed for solar applications....

TTF/TCNQ-based thin films and microcrystals. Growth and charge transport phenomena

Energy Technology Data Exchange (ETDEWEB)

Solovyeva, Vita

2011-05-26

The thesis adresses several problems related to growth and charge transport phenomena in thin films of TTF-TCNQ and (BEDT-TTF)TCNQ. The following main new problems are addressed: - The influence of thin-film specific factors, such as the substrate material and growth-induced defects, on the Peierls transition temperature in TTF-TCNQ thin films was studied; - finite-size effects in TTF-TCNQ were investigated by considering transport properties in TTF-TCNQ microcrystals. The influence of the size of the crystal on the Peierls transition temperature was studied. In this context a new method of microcontact fabrication was employed to favor the measurements; - an analysis of radiation-induced defects in TTF-TCNQ thin films and microcrystals was performed. It was demonstrated than an electron beam can induce appreciable damage to the sample such that its electronic properties are strongly modified; - a bilayer growth method was established to fabricate (BEDT-TTF)TCNQ from the gas phase. This newly developed bilayer growth method was showed to be suitable for testing (BEDT-TTF)TCNQ charge-transfer phase formation; - the structure of the formed (BEDT-TTF)TCNQ charge-transfer compounds was analyzed by using a wide range of experimental techniques. An overview and the description of the basic physical principles underlying charge-transfer compounds is given in chapter 2. Experimental techniques used for the growth and characterization of thin films and microcrystals are presented in chapter 3. Chapter 4 gives an overview of the physical properties of the studied organic materials. Chapter 5 discussed the experimental study of TTF-TCNQ thin films. he Peierls transition in TTF-TCNQ is a consequence of the quasi-one-dimensional structure of the material and depends on different factors, studied in chapters 5 and 6. In contradistinction to TTF-TTCNQ, the (BEDT-TTF)TCNQ charge-transfer compound crystallizes in several different modifications with different physical properties

Ab initio study of charge transfer between lithium and aromatic hydrocarbons. Can the results be directly transferred to the lithium-graphene interaction?

Science.gov (United States)

Sadlej-Sosnowska, N

2014-08-28

We have used electronic density calculations to study neutral complexes of Li with aromatic hydrocarbons. The charge transferred between a Li atom and benzene, coronene, circumcoronene, and circumcircumcoronene has been studied by ab initio methods (at the HF and MP2 level). Toward this aim, the method of integrating electron density in two cuboid fragments of space was applied. One of the fragments was constructed so that it enclosed the bulk of the electron density of lithium; the second, the bulk of the electron density of hydrocarbon. It was found that for each complex two conformations were identified: the most stable with a greater vertical Li-hydrocarbon distance, on the order of 2.5 Å, and another of higher energy with a corresponding distance less than 2 Å. In all cases the transfer of a fractional number, 0.1-0.3 electrons, between Li and hydrocarbon was found; however, the direction of the transfer was not the same in all complexes investigated. The structures of complexes of the first configuration could be represented as Li(σ-)···AH(σ+), whereas the opposite direction of charge transfer was found for complexes of the second configuration, with higher energy. The directions of the dipole moments in the complexes supported these conclusions because they directly measure the redistribution of electron density in a complex with respect to substrates.

Phased Array Focusing for Acoustic Wireless Power Transfer.

Science.gov (United States)

Tseng, Victor Farm-Guoo; Bedair, Sarah S; Lazarus, Nathan

2018-01-01

Wireless power transfer (WPT) through acoustic waves can achieve higher efficiencies than inductive coupling when the distance is above several times the transducer size. This paper demonstrates the use of ultrasonic phased arrays to focus power to receivers at arbitrary locations to increase the power transfer efficiency. Using a phased array consisting of 37 elements at a distance nearly 5 times the receiver transducer diameter, a factor of 2.6 increase in efficiency was achieved when compared to a case equivalent to a single large transducer with the same peak efficiency distance. The array has a total diameter of 7 cm, and transmits through air at 40 kHz to a 1.1-cm diameter receiver, achieving a peak overall efficiency of 4% at a distance of 5 cm. By adjusting the focal distance, the efficiency can also be maintained relatively constant at distances up to 9 cm. Numerical models were developed and shown to closely match the experimental energy transfer behavior; modeling results indicate that the efficiency can be further doubled by increasing the number of elements. For comparison, an inductive WPT system was also built with the diameters of the transmitting and receiving coils equivalent to the dimensions of the transmitting ultrasonic phased array and receiver transducer, and the acoustic WPT system achieved higher efficiencies than the inductive WPT system when the transmit-to-receive distance is above 5 cm. In addition, beam angle steering was demonstrated by using a simplified seven-element 1-D array, achieving power transfer less dependent on receiver placement.

State-selective charge transfer cross sections for light ion impact of atomic hydrogen

Energy Technology Data Exchange (ETDEWEB)

Schultz, D. R. [University of North Texas; Stancil, Phillip C. [University of Georgia, Athens; Havener, C. C. [Oak Ridge National Laboratory (ORNL)

2015-01-01

Owing to the utility of diagnosing plasma properties such as impurity concentration and spatial distribution, and plasma temperature and rotation, by detection of photon emission following capture of electrons from atomic hydrogen to excited states of multiply charged ions, new calculations of state-selective charge transfer involving light ions have been carried out using the atomic orbital close-coupling and the classical trajectory Monte Carlo methods. By comparing these with results of other approaches applicable in a lower impact energy regime, and by benchmarking them using key experimental data, knowledge of the cross sections can be made available across the range parameters needed by fusion plasma diagnostics.

Spectroscopic and theoretical investigations on intramolecular charge transfer phenomenon in 1-3-dioxolane derivative

Science.gov (United States)

Zhang, Zhiyong; Zhang, Zhongzhi; Luo, Yijing; Sun, Shanshan; Zhang, Guangqing

2018-02-01

High fluorescence quantum yield (FQY) and large Stokes shift (SS) cannot be easily achieved simultaneously by traditional PICT or TICT fluorescent probe. However, an 1-3-dioxolane derivative named 5-methyl-8,9-dihydro-5H-[1,3]dioxolo[4,5-b]carbazol-6(7H)-one (MDDCO) features both high FQY and large SS. The purpose of this study is to search the mechanism behind this phenomenon by theoretical method. Simulated structure changes and charge transfer suggest ICT process in MDDCO is similar to PLICT (Planarized Intramolecular Charge Transfer) process. Calculated UV-Vis spectra and fluorescence spectra show that PLICT-like state (S1 state) of MDDCO leads to large SS. Computed transient-absorption spectra and radiative decay rates indicate that PLICT-like state is key factor for high FQY of MDDCO. These findings suggest that PLICT-like state in 1,3-dioxolane derivatives can achieve both large SS and high FQY, which presents a new method for high-performance fluorescent probe design.

Oxidation and Metal-Insertion in Molybdenite Surfaces: Evaluation of Charge-Transfer Mechanisms and Dynamics

Energy Technology Data Exchange (ETDEWEB)

Ramana, Chintalapalle V.; Becker, U.; Shutthanandan, V.; Julien, C. M.

2008-06-05

Molybdenum sulfide (MoS2), an important representative member of the layered transition-metal dichalcogenides, has been of special importance to the research community of geochemistry, materials and environmental chemistry, and industrial science and technology. Understanding the oxidation behavior and charge-transfer mechanisms in MoS2 is important to gain better insight into the degradation of this mineral in the environment. On the other hand understanding the insertion of metals into molybdenite and evaluation of charge-transfer mechanism and dynamics is quite important to utilize these minerals in technological applications. Furthermore, such a detailed investigation of thermal oxidation behavior and intercalation process will provide a basis to further explore and model the mechanism of adsorption of metal ions on to geomedia. Therefore, the present work was performed to understand the oxidation and intercalation processes of molybdenite surfaces. The results obtained, using a wide variety of analytical techniques, are presented and discussed in this paper.

Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

Energy Technology Data Exchange (ETDEWEB)

Ramakrishnan, Raghunathan, E-mail: r.ramakrishnan@unibas.ch [Institute of Physical Chemistry, National Center for Computational Design and Discovery of Novel Materials (MARVEL), Department of Chemistry, University of Basel, Klingelbergstrasse 80, CH-4056 Basel (Switzerland); Nest, Mathias [Theoretische Chemie, Technische Universität München, Lichtenbergstr. 4, 85747 Garching (Germany)

2015-01-13

Highlights: • We model electron dynamics across cyano alkanethiolates attached to gold cluster. • We present electron transfer time scales from TD-DFT and TD-CI based simulations. • Both DFT and CI methods qualitatively predict the trend in time scales. • TD-CI predicts the experimental relative time scale very accurately. - Abstract: We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual π{sup ∗} molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process.

An Electronic Structure Approach to Charge Transfer and Transport in Molecular Building Blocks for Organic Optoelectronics

Science.gov (United States)

Hendrickson, Heidi Phillips

A fundamental understanding of charge separation in organic materials is necessary for the rational design of optoelectronic devices suited for renewable energy applications and requires a combination of theoretical, computational, and experimental methods. Density functional theory (DFT) and time-dependent (TD)DFT are cost effective ab-initio approaches for calculating fundamental properties of large molecular systems, however conventional DFT methods have been known to fail in accurately characterizing frontier orbital gaps and charge transfer states in molecular systems. In this dissertation, these shortcomings are addressed by implementing an optimally-tuned range-separated hybrid (OT-RSH) functional approach within DFT and TDDFT. The first part of this thesis presents the way in which RSH-DFT addresses the shortcomings in conventional DFT. Environmentally-corrected RSH-DFT frontier orbital energies are shown to correspond to thin film measurements for a set of organic semiconducting molecules. Likewise, the improved RSH-TDDFT description of charge transfer excitations is benchmarked using a model ethene dimer and silsesquioxane molecules. In the second part of this thesis, RSH-DFT is applied to chromophore-functionalized silsesquioxanes, which are currently investigated as candidates for building blocks in optoelectronic applications. RSH-DFT provides insight into the nature of absorptive and emissive states in silsesquioxanes. While absorption primarily involves transitions localized on one chromophore, charge transfer between chromophores and between chromophore and silsesquioxane cage have been identified. The RSH-DFT approach, including a protocol accounting for complex environmental effects on charge transfer energies, was tested and validated against experimental measurements. The third part of this thesis addresses quantum transport through nano-scale junctions. The ability to quantify a molecular junction via spectroscopic methods is crucial to their

Multiple nucleon transfer in damped nuclear collisions. [Lectures, mass charge, and linear and angular momentum transport

Energy Technology Data Exchange (ETDEWEB)

Randrup, J.

1979-07-01

This lecture discusses a theory for the transport of mass, charge, linear, and angular momentum and energy in damped nuclear collisions, as induced by multiple transfer of individual nucleons. 11 references.

On the charge transfer between single-walled carbon nanotubes and graphene

International Nuclear Information System (INIS)

Rao, Rahul; Pierce, Neal; Dasgupta, Archi

2014-01-01

It is important to understand the electronic interaction between single-walled carbon nanotubes (SWNTs) and graphene in order to use them efficiently in multifunctional hybrid devices. Here, we deposited SWNT bundles on graphene-covered copper and SiO 2 substrates by chemical vapor deposition and investigated the charge transfer between them by Raman spectroscopy. Our results revealed that, on both copper and SiO 2 substrates, graphene donates electrons to the SWNTs, resulting in p-type doped graphene and n-type doped SWNTs.

Gas phase ion chemistry

CERN Document Server

Bowers, Michael T

1979-01-01

Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

Lifetimes of partial charge transfer exciplexes of 9-cyanophenanthrene and 9-cyanoanthracene

OpenAIRE

Dolotova, Elena; Dogadkin, Denis; Soboleva, Irina; Kuzmin, Michael; Nicolet, Olivier; Vauthey, Eric

2003-01-01

The fluorescence decays of several exciplexes with partial charge transfer have been investigated in solvents of various polarity. The measured lifetimes are found to be in reasonable agreement with the activation enthalpy and entropy of exciplex decay obtained earlier from the temperature dependence of the exciplex emission quantum yields. For exciplexes with 9-cyanophenanthrene substantial contribution of the higher local excited state into the exciplex electronic structure is found and bor...

Modeling and analysis of LiFePO4/Carbon battery considering two-phase transition during galvanostatic charging/discharging

International Nuclear Information System (INIS)

Li, Xueyan; Xiao, Meng; Choe, Song-Yul; Joe, Won Tae

2015-01-01

Highlights: • Reduced order model for LiFePO 4 particles considering two-phase transition • Model validation with experimental results of current and voltage • Analysis of two-phase transition and path dependence - Abstract: Batteries with lithium iron phosphate (LFP) cathode and carbon anode have shown various advantages over those with other chemistries, but the plateau and path dependence caused by the two-phase transition taking place during charging and discharging make it difficult to estimate the states of battery. Thus, based on electrochemical principles we propose a new reduced order model that has been validated against experimental data obtained during galvanostatic charging/discharging. The mechanism of the two-phase transition during lithiation and delithiation in LFP particles is approximated using a shrinking corewith a moving interface between the two phases and is described by modified diffusion equations that take into account multiple layers formed within LFP particles. The shrinking core model is integrated into a cell model developed previously, which is used to analyze the path dependence at different load profiles. The results show that the model is capable of representing the characteristics of the plateau and path dependence. Particularly, the available charge at a certain State of Charge (SOC) varies dependent upon paths to reach the SOC. When an initial SOC is reached by discharging, the cell can accept more charges during charging, while when an initial SOC is reached by charging, more charge will be available during discharging

Laser-induced charge transfer in the CH6+ quasimolecule

International Nuclear Information System (INIS)

Errea, L.F.; Mendez, L.; Riera, A.

1985-01-01

The charge transfer cross section is calculated for C 6+ +CH(1s) collisions, through photon assisted 5gsigma--6hsigma, 5gsigma--4fsigma, 5gsigma--4fπ, and 5gsigma--4dsigma transitions. The theory developed by Copeland and Tang, and ourselves, is employed, and the validity of the approximations used is tested. The four processes considered have widely different characteristics with regards to the laser wavelength needed, the collision dynamics and the applicability of back-of-the-envelope estimates based on the Landau--Zener approximation. We point out the relevance of those processes to the impurity diagnostics of magnetically confined fusion plasmas and to the development of short wavelength lasers

Experiment of forced convection heat transfer using microencapsulated phase-change-material slurries

International Nuclear Information System (INIS)

Kubo, Shinji; Akino, Norio; Tanaka, Amane; Nagashima, Akira.

1997-01-01

The present study describes an experiment on forced convective heat transfer using a water slurry of Microencapsulated Phase-change-material. A normal paraffin hydrocarbon is microencapsulated by melamine resin, melting point of 28.1degC. The heat transfer coefficient and pressure drop in a circular tube were evaluated. The heat transfer coefficient using the slurry in case with and without phase change were compared to in case of using pure water. (author)

Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells

Energy Technology Data Exchange (ETDEWEB)

Wu, Qinghe [Department of Chemistry, Key Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province, Shantou University, Guangdong 515063, P. R. China; Zhao, Donglin [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Goldey, Matthew B. [Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Filatov, Alexander S. [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Sharapov, Valerii [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Colón, Yamil J. [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Cai, Zhengxu [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States; Chen, Wei [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; de Pablo, Juan [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Galli, Giulia [Institute for Molecular Engineering, Materials Science Division, Argonne National Laboratory, 9700 Cass Avenue, Lemont, Illinois 60439, United States; Institute for Molecular Engineering, The University of Chicago, 5747 South Ellis Avenue, Chicago, Illinois 60637, United States; Yu, Luping [Department of Chemistry, The James Franck Institute, The University of Chicago, 929 E 57th Street, Chicago, Illinois 60637, United States

2018-03-02

Two types of electron acceptors were synthesized by coupling two kinds of electron-rich cores with four equivalent perylene diimides (PDIs) at the a position. With fully aromatic cores, TPB and TPSe have pi-orbitals spread continuously over the whole aromatic conjugated backbone, unlike TPC and TPSi, which contain isolated PDI units due to the use of a tetrahedron carbon or silicon linker. Density functional theory calculations of the projected density of states showed that the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) for TPB are localized in separate regions of space. Further, the LUMO of TPB shows a greater contribution from the orbitals belonging to the connective core of the molecules than that of TPC. Overall, the properties of the HOMO and LUMO point at increased intra-molecular delocalization of negative charge carriers for TPB and TPSe than for TPC and TPSi and hence at a more facile intra-molecular charge transfer for the former. The film absorption and emission spectra showed evidences for the inter -molecular electron delocalization in TPB and TPSe, which is consistent with the network structure revealed by X-ray diffraction studies on single crystals of TPB. These features benefit the formation of charge transfer states and/or facilitate charge transport. Thus, higher electron mobility and higher charge dissociation probabilities under J(sc) condition were observed in blend films of TPB:PTB7-Th and TPSe:PTB7-Th than those in TPC:PTB7Th and TPSi:PTB7-Th blend films. As a result, the J(sc) and fill factor values of 15.02 mA/cm(2), 0.58 and 14.36 mA/cm(2), 0.55 for TPB- and TPSe-based solar cell are observed, whereas those for TPC and TPSi are 11.55 mA/cm2, 0.47 and 10.35 mA/cm(2), 0.42, respectively.

Determination of charge transfer resistance and capacitance of microbial fuel cell through a transient response analysis of cell voltage.

Science.gov (United States)

Ha, Phuc Thi; Moon, Hyunsoo; Kim, Byung Hong; Ng, How Yong; Chang, In Seop

2010-03-15

An alternative method for determining the charge transfer resistance and double-layer capacitance of microbial fuel cells (MFCs), easily implemented without a potentiostat, was developed. A dynamic model with two parameters, the charge transfer resistance and double-layer capacitance of electrodes, was derived from a linear differential equation to depict the current generation with respect to activation overvoltage. This model was then used to fit the transient cell voltage response to the current step change during the continuous operation of a flat-plate type MFC fed with acetate. Variations of the charge transfer resistance and the capacitance value with respect to the MFC design conditions (biocatalyst existence and electrode area) and operating parameters (acetate concentration and buffer strength in the catholyte) were then determined to elucidate the validity of the proposed method. This model was able to describe the dynamic behavior of the MFC during current change in the activation loss region; having an R(2) value of over 0.99 in most tests. Variations of the charge transfer resistance value (thousands of Omega) according to the change of the design factors and operational factors were well-correlated with the corresponding MFC performances. However, though the capacitance values (approximately 0.02 F) reflected the expected trend according to the electrode area change and catalyst property, they did not show significant variation with changes in either the acetate concentration or buffer strength. (c) 2009 Elsevier B.V. All rights reserved.

Modelling of the concentration-time relationship based on global diffusion-charge transfer parameters in a flow-by reactor with a 3D electrode

International Nuclear Information System (INIS)

Nava, J.L.; Sosa, E.; Carreno, G.; Ponce-de-Leon, C.; Oropeza, M.T.

2006-01-01

A concentration versus time relationship model based on the isothermal diffusion-charge transfer mechanism was developed for a flow-by reactor with a three-dimensional (3D) reticulated vitreous carbon (RVC) electrode. The relationship was based on the effectiveness factor (η) which lead to the simulation of the concentration decay at different electrode polarisation conditions, i.e. -0.1, -0.3 and -0.59 V versus SCE; the charge transfer process was used for the former and mix and a mass transport control was used for the latter. Charge transfer and mass transport parameters were estimated from experimental data using Electrochemical Impedance Spectroscopy (EIS) and Linear Voltammetry (LV) techniques, respectively

Modelling of the concentration-time relationship based on global diffusion-charge transfer parameters in a flow-by reactor with a 3D electrode

Energy Technology Data Exchange (ETDEWEB)

Nava, J.L. [Universidad Autonoma Metropolitana-Iztapalapa, Departamento de Quimica, Av. San Rafael Atlixco 186, A.P. 55-534, C.P. 09340, Mexico D.F. (Mexico); Sosa, E. [Instituto Mexicano del Petroleo, Programa de Investigacion en Ingenieria Molecular, Eje Central 152, C.P. 07730, Mexico D.F. (Mexico); Carreno, G. [Universidad de Guanajuato, Facultad de Ingenieria en Geomatica e Hidraulica, Av. Juarez 77, C.P. 36000, Guanajuato, Gto. (Mexico); Ponce-de-Leon, C. [Electrochemical Engineering Group, School of Engineering Sciences, University of Southampton, Highfield, Southampton SO17 1BJ (United Kingdom)]. E-mail: capla@soton.ac.uk; Oropeza, M.T. [Centro de Graduados e Investigacion del Instituto Tecnologico de Tijuana, Blvd. Industrial, s/n, C.P. 22500, Tijuana B.C. (Mexico)

2006-05-25

A concentration versus time relationship model based on the isothermal diffusion-charge transfer mechanism was developed for a flow-by reactor with a three-dimensional (3D) reticulated vitreous carbon (RVC) electrode. The relationship was based on the effectiveness factor ({eta}) which lead to the simulation of the concentration decay at different electrode polarisation conditions, i.e. -0.1, -0.3 and -0.59 V versus SCE; the charge transfer process was used for the former and mix and a mass transport control was used for the latter. Charge transfer and mass transport parameters were estimated from experimental data using Electrochemical Impedance Spectroscopy (EIS) and Linear Voltammetry (LV) techniques, respectively.

Topological charge algebra of optical vortices in nonlinear interactions.

Science.gov (United States)

Zhdanova, Alexandra A; Shutova, Mariia; Bahari, Aysan; Zhi, Miaochan; Sokolov, Alexei V

2015-12-28

We investigate the transfer of orbital angular momentum among multiple beams involved in a coherent Raman interaction. We use a liquid crystal light modulator to shape pump and Stokes beams into optical vortices with various integer values of topological charge, and cross them in a Raman-active crystal to produce multiple Stokes and anti-Stokes sidebands. We measure the resultant vortex charges using a tilted-lens technique. We verify that in every case the generated beams' topological charges obey a simple relationship, resulting from angular momentum conservation for created and annihilated photons, or equivalently, from phase-matching considerations for multiple interacting beams.

Site-dependent charge transfer at the Pt(111)-ZnPc interface and the effect of iodine

International Nuclear Information System (INIS)

Ahmadi, Sareh; Wojek, Bastian M.; Noël, Quentin; Göthelid, Mats; Agnarsson, Björn; Bidermane, Ieva; Sun, Chenghua

2014-01-01

The electronic structure of ZnPc, from sub-monolayers to thick films, on bare and iodated Pt(111) is studied by means of X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and scanning tunneling microscopy. Our results suggest that at low coverage ZnPc lies almost parallel to the Pt(111) substrate, in a non-planar configuration induced by Zn-Pt attraction, leading to an inhomogeneous charge distribution within the molecule and an inhomogeneous charge transfer to the molecule. ZnPc does not form a complete monolayer on the Pt surface, due to a surface-mediated intermolecular repulsion. At higher coverage ZnPc adopts a tilted geometry, due to a reduced molecule-substrate interaction. Our photoemission results illustrate that ZnPc is practically decoupled from Pt, already from the second layer. Pre-deposition of iodine on Pt hinders the Zn-Pt attraction, leading to a non-distorted first layer ZnPc in contact with Pt(111)-I(√3×√3) or Pt(111)-I(√7×√7), and a more homogeneous charge distribution and charge transfer at the interface. On increased ZnPc thickness iodine is dissolved in the organic film where it acts as an electron acceptor dopant

DFT and TD-DFT computation of charge transfer complex between o-phenylenediamine and 3,5-dinitrosalicylic acid

International Nuclear Information System (INIS)

Afroz, Ziya; Zulkarnain,; Ahmad, Afaq; Alam, Mohammad Jane; Faizan, Mohd; Ahmad, Shabbir

2016-01-01

DFT and TD-DFT studies of o-phenylenediamine (PDA), 3,5-dinitrosalicylic acid (DNSA) and their charge transfer complex have been carried out at B3LYP/6-311G(d,p) level of theory. Molecular geometry and various other molecular properties like natural atomic charges, ionization potential, electron affinity, band gap, natural bond orbital (NBO) and frontier molecular analysis have been presented at same level of theory. Frontier molecular orbital and natural bond orbital analysis show the charge delocalization from PDA to DNSA.

Symbolic phase transfer entropy method and its application

Science.gov (United States)

Zhang, Ningning; Lin, Aijing; Shang, Pengjian

2017-10-01

In this paper, we introduce symbolic phase transfer entropy (SPTE) to infer the direction and strength of information flow among systems. The advantages of the proposed method are investigated by simulations on synthetic signals and real-world data. We demonstrate that symbolic phase transfer entropy is a robust and efficient tool to infer the information flow between complex systems. Based on the study of the synthetic data, we find a significant advantage of SPTE is its reduced sensitivity to noise. In addition, SPTE requires less amount of data than symbolic transfer entropy(STE). We analyze the direction and strength of information flow between six stock markets during the period from 2006 to 2016. The results indicate that the information flow among stocks varies over different periods. We also find that the interaction network pattern among stocks undergoes hierarchial reorganization with transition from one period to another. It is shown that the clusters are mainly classified according to period, and then by region. The stocks during the same time period are shown to drop into the same cluster.

Charge Mediated Compaction and Rearrangement of Gas-Phase Proteins: A Case Study Considering Two Proteins at Opposing Ends of the Structure-Disorder Continuum

Science.gov (United States)

Jhingree, Jacquelyn R.; Bellina, Bruno; Pacholarz, Kamila J.; Barran, Perdita E.

2017-07-01

Charge reduction in the gas phase provides a direct means of manipulating protein charge state, and when coupled to ion mobility mass spectrometry (IM-MS), it is possible to monitor the effect of charge on protein conformation in the absence of solution. Use of the electron transfer reagent 1,3-dicyanobenzene, coupled with IM-MS, allows us to monitor the effect of charge reduction on the conformation of two proteins deliberately chosen from opposite sides of the order to disorder continuum: bovine pancreatic trypsin inhibitor (BPTI) and beta casein. The ordered BPTI presents compact conformers for each of three charge states accompanied by narrow collision cross-section distributions (TWCCSDN2→He). Upon reduction of BPTI, irrespective of precursor charge state, the TWCCSN2→He decreases to a similar distribution as found for the nESI generated ion of identical charge. The behavior of beta casein upon charge reduction is more complex. It presents over a wide charge state range (9-28), and intermediate charge states (13-18) have broad TWCCSDN2→He with multiple conformations, where both compaction and rearrangement are seen. Further, we see that the TWCCSDN2→He of the latter charge states are even affected by the presence of radical anions. Overall, we conclude that the flexible nature of some proteins result in broad conformational distributions comprised of many families, even for single charge states, and the barrier between different states can be easily overcome by an alteration of the net charge.

Heat exchange between a microparticle and plasma. Contribution of charge transfer processes

International Nuclear Information System (INIS)

Uglov, A.A.; Gnedovets, A.G.

1983-01-01

Heat- and mass-transfer in interaction of a microparticle with a dense plasma have been considered analytically. At that, calculation methods developed as applied to probe diagnostics of slightly ionized plasma are also used in the case of relatively high degrees of ionization, at which heat flows of plasma charged particles Qe and Qi become comparable with molecular ones. High efficiency of energy transfer during electron and ion collisions with a microparticle is due to the following: 1) effective cross section of ion collision with a microparticle, which acquires in a quasineutral plasma the potential phisub(f) < 0, surpasses the geometric one; the maximum contribution of electron and ion constituent is achieved when the cross section ion collisions with a microparticle is linearly connected with its potential, 2) with a charged microparticle electrons from distribution function ''tail'' collide, their energy exceeds potential barrier near the surface and, consequently, the mean heat energy; 3) besides the energy of a microparticle thermal movement during electron recombination and ion neutralization on its surface the heat Qsub(e) and Qsub(i), which considerably exceed the heat of molecular adsorption and mean heat energy of plasma particles at kT approximately 1 eV, are transmitted to the microparticle

Application of New Electrolyte Model to Phase Transfer Catalyst (PTC) Systems

DEFF Research Database (Denmark)

Hyung Kim, Sun; Anantpinijwatna, Amata; Kang, Jeong Won

2015-01-01

Abstract Phase transfer catalyst (PTC) is used to transfer the desirable active form of an anion from the aqueous phase to organic phase where the reaction occurs. One of major challenges for process design of the PTC system is to establish a reliable thermodynamic model capable of describing pha...... in PTC systems, thereby, extending the application range of the PTC-system model. The solubility of PTC in organic solvents, which is a key factor for strategy of PTC and solvent selection, has been calculated using the e-NRTL-SAC model....

Transverse Schottky spectra and beam transfer functions of coasting ion beams with space charge

International Nuclear Information System (INIS)

Paret, Stefan

2010-01-01

A study of the transverse dynamics of coasting ion beams with moderate space charge is presented in this work. From the dispersion relation with linear space charge, an analytic model describing the impact of space charge on transverse beam transfer functions (BTFs) and the stability limits of a beam is derived. The dielectric function obtained in this way is employed to describe the transverse Schottky spectra with linear space charge as well. The difference between the action of space charge and impedances is highlighted. The setup and the results of an experiment performed in the heavy ion synchrotron SIS-18 at GSI to detect space-charge effects at different beam intensities are explicated. The measured transverse Schottky spectra and BTFs are compared with the linear space-charge model. The stability diagrams constructed from the BTFs are presented. The space-charge parameters evaluated from the Schottky and BTF measurements are compared with estimations based on measured beam parameters. The impact of collective effects on the Schottky and BTF diagnostics is also investigated through numerical simulations. For this purpose the self-field of beams with linear and non-linear transverse density-distributions is computed on a twodimensional grid. The noise of the random particle distribution causes fluctuations of the dipole moment of the beam which produce the Schottky spectrum. BTFs are simulated by exciting the beam with transverse kicks. The simulation results are used to verify the space-charge model. (orig.)

Transverse Schottky spectra and beam transfer functions of coasting ion beams with space charge

Energy Technology Data Exchange (ETDEWEB)

Paret, Stefan

2010-02-22

A study of the transverse dynamics of coasting ion beams with moderate space charge is presented in this work. From the dispersion relation with linear space charge, an analytic model describing the impact of space charge on transverse beam transfer functions (BTFs) and the stability limits of a beam is derived. The dielectric function obtained in this way is employed to describe the transverse Schottky spectra with linear space charge as well. The difference between the action of space charge and impedances is highlighted. The setup and the results of an experiment performed in the heavy ion synchrotron SIS-18 at GSI to detect space-charge effects at different beam intensities are explicated. The measured transverse Schottky spectra and BTFs are compared with the linear space-charge model. The stability diagrams constructed from the BTFs are presented. The space-charge parameters evaluated from the Schottky and BTF measurements are compared with estimations based on measured beam parameters. The impact of collective effects on the Schottky and BTF diagnostics is also investigated through numerical simulations. For this purpose the self-field of beams with linear and non-linear transverse density-distributions is computed on a twodimensional grid. The noise of the random particle distribution causes fluctuations of the dipole moment of the beam which produce the Schottky spectrum. BTFs are simulated by exciting the beam with transverse kicks. The simulation results are used to verify the space-charge model. (orig.)

Muon transfer from muonic hydrogen to heavier atoms; Transfert de charge muonique

Energy Technology Data Exchange (ETDEWEB)

Dupays, A

2004-06-01

This work concerns muon transfer from muonic hydrogen to heavier atoms. Recently, a method of measurement of the hyperfine structure of ground-state muonic hydrogen based on the collision energy dependence of the muon transfer rate to oxygen has been proposed. This proposal is based on measurements which where performed at the Paul Scherrer Institute in the early nineties which indicate that the muon transfer from muonic hydrogen to oxygen increases by a factor of 4 going from thermal to 0.12 eV energies. The motivation of our calculations was to confirm this behaviour. To study the collision energy dependence of the muon transfer rate, we have used a time-independent close-coupling method. We have set up an hyperspherical elliptic formalism valid for nonzero total angular momentum which allows accurate computations of state-to-state reactive and charge exchange processes. We have applied this formalism to muon-transfer process to oxygen and neon. The comparison with experimental results is in both cases excellent. Finally, the neon transfer rate dependence with energy suggests to use neon instead of oxygen to perform a measurement of the hyperfine structure of muonic hydrogen. The results of accurate calculations of the muon transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen and neon are also reported. Very good agreement with measured rates is obtained and for the three systems, the isotopic effect is perfectly reproduced. (author)

Phase space properties of charged fields in theories of local observables

International Nuclear Information System (INIS)

Buchholz, D.; D'Antoni, C.

1994-10-01

Within the setting of algebraic quantum field theory a relation between phase-space properties of observables and charged fields is established. These properties are expressed in terms of compactness and nuclarity conditions which are the basis for the characterization of theories with physically reasonable causal and thermal features. Relevant concepts and results of phase space analysis in algebraic qunatum field theory are reviewed and the underlying ideas are outlined. (orig.)

Charge transfer in carbon nanotube actuators investigated using in situ Raman spectroscopy

International Nuclear Information System (INIS)

Gupta, S.; Hughes, M.; Windle, A.H.; Robertson, J.

2004-01-01

Charge transfer dynamics on the surface of single-wall carbon nanotube sheets is investigated using in situ Raman spectroscopy in order to understand the actuation mechanism of an electrochemical actuator and to determine associated parameters. We built an actuator from single-wall carbon nanotube mat and studied its actuation in several alkali metal (Li, Na, and K) and alkaline earth (Ca) halide and sulfate solutions in order to clarify the role of counterion as mobile ions in the film. The variation of bonding with applied potential was monitored using in situ Raman spectroscopy. This is because Raman can detect changes in C-C bond length: the radial breathing mode at ∼190 cm-1 varies inversely with the nanotube diameter, and the G band at ∼1590 cm-1 varies with the axial bond length. In addition, the intensities of both the modes vary with the emptying/depleting or filling of the bonding and antibonding states due to electrochemical charge injection. We discussed the variation of peak height and wave numbers of these modes providing valuable information concerning electrochemical charge injection on the carbon nanotube mat surface. We found in-plane microscopic compressive strain (∼-0.25%) and the equivalent charge transfer per carbon atom (f c ∼-0.005) as an upper bound for the actuators studied hereby. It is demonstrated that though the present analysis does comply with the proposition for the actuation principle made earlier, the quantitative estimates are significantly lower if compared with those of reported values. Furthermore, the extent of variation, i.e., coupled electro-chemo-mechanical response of single-wall carbon nanotubes (SWNT) mat depended upon the type of counterion used (Group I versus Group II). The cyclic voltammetry and ac electrochemical impedance spectroscopy results were described briefly, which help to demonstrate well-developed capacitive behavior of SWNT mat and to estimate the specific capacitances as well. Summarizing, the

Absolute Charge Transfer and Fragmentation Cross Sections in He2+-C60 Collisions

International Nuclear Information System (INIS)

Rentenier, A.; Moretto-Capelle, P.; Bordenave-Montesquieu, D.; Bordenave-Montesquieu, A.; Ruiz, L. F.; Diaz-Tendero, S.; Alcami, M.; Martin, F.; Zarour, B.; Hanssen, J.; Hervieux, P.-A.; Politis, M. F.

2008-01-01

We have determined absolute charge transfer and fragmentation cross sections in He 2+ +C 60 collisions in the impact-energy range 0.1-250 keV by using a combined experimental and theoretical approach. We have found that the cross sections for the formation of He + and He 0 are comparable in magnitude, which cannot be explained by the sole contribution of pure single and double electron capture but also by contribution of transfer-ionization processes that are important even at low impact energies. The results show that multifragmentation is important only at impact energies larger than 40 keV; at lower energies, sequential C 2 evaporation is the dominant process

A simple transferable adaptive potential to study phase separation in large-scale xMgO-(1-x)SiO2 binary glasses.

Science.gov (United States)

Bidault, Xavier; Chaussedent, Stéphane; Blanc, Wilfried

2015-10-21

A simple transferable adaptive model is developed and it allows for the first time to simulate by molecular dynamics the separation of large phases in the MgO-SiO2 binary system, as experimentally observed and as predicted by the phase diagram, meaning that separated phases have various compositions. This is a real improvement over fixed-charge models, which are often limited to an interpretation involving the formation of pure clusters, or involving the modified random network model. Our adaptive model, efficient to reproduce known crystalline and glassy structures, allows us to track the formation of large amorphous Mg-rich Si-poor nanoparticles in an Mg-poor Si-rich matrix from a 0.1MgO-0.9SiO2 melt.

Angular distribution in proton-hydrogen charge-transfer collisions

International Nuclear Information System (INIS)

Glembocki, O.; Halpern, A.M.

1977-01-01

Theoretical angular distributions for p-H charge transfer to the 1s state for energies of 1 keV and above have been examined and compared for three approximation schemes: the plane-wave Born approximation of Jackson and Schiff (JS), the Coulomb projected Born approximation of Geltman (G), and the distorted-wave eikonal approximation of one of the authors (D). The sharp dip in the forward distribution characteristic of JS is found to exist in G and D as well. As expected, G and D give identical results for all but the lowest energies. In the cases of G and D the dip, which is located close to that of JS, disappears and then reappears as the energy rises. Analytic high-energy limits for the angular dependence in both the JS and G cases have been found and are discussed

Scaling of the helium--nitrogen charge transfer laser

International Nuclear Information System (INIS)

Collins, C.B.; Cunningham, A.J.

1975-01-01

The scaling to high powers of the nitrogen ion laser pumped by charge transfer from He + 2 is reported. Intense emission has been found from three laser lines at 3914, 4278, and 4709 A upon discharge of a fast-pulsed electron beam gun, APEX-1, into several atmospheres of a mixture of helium and nitrogen. Excitation current densities were 1.3 kA/cm 2 at 1 MV over a 1times10-cm transverse geometry. The efficiency of the 4278-A laser emission was found to be proportional to the total pressure raised to the 1.2 power. Outputs of 36 mJ have been obtained from the 16-cm 3 working volume at 30-atm pressure and a peak efficiency of 1.6% relative to the energy lost by the electron beam in this radiating volume has been achieved

SiC MOSFET Based Single Phase Active Boost Rectifier with Power Factor Correction for Wireless Power Transfer Applications

Energy Technology Data Exchange (ETDEWEB)

Onar, Omer C [ORNL; Tang, Lixin [ORNL; Chinthavali, Madhu Sudhan [ORNL; Campbell, Steven L [ORNL; Miller (JNJ), John M. [JNJ-Miller PLC

2014-01-01

Wireless Power Transfer (WPT) technology is a novel research area in the charging technology that bridges the utility and the automotive industries. There are various solutions that are currently being evaluated by several research teams to find the most efficient way to manage the power flow from the grid to the vehicle energy storage system. There are different control parameters that can be utilized to compensate for the change in the impedance due to variable parameters such as battery state-of-charge, coupling factor, and coil misalignment. This paper presents the implementation of an active front-end rectifier on the grid side for power factor control and voltage boost capability for load power regulation. The proposed SiC MOSFET based single phase active front end rectifier with PFC resulted in >97% efficiency at 137mm air-gap and >95% efficiency at 160mm air-gap.

The simplest equivalent circuit of a pulsed dielectric barrier discharge and the determination of the gas gap charge transfer

Science.gov (United States)

Pipa, A. V.; Koskulics, J.; Brandenburg, R.; Hoder, T.

2012-11-01

The concept of the simplest equivalent circuit for a dielectric barrier discharge (DBD) is critically reviewed. It is shown that the approach is consistent with experimental data measured either in large-scale sinusoidal-voltage driven or miniature pulse-voltage driven DBDs. An expression for the charge transferred through the gas gap q(t) is obtained with an accurate account for the displacement current and the values of DBD reactor capacitance. This enables (i) the significant reduction of experimental error in the determination of q(t) in pulsed DBDs, (ii) the verification of the classical electrical theory of ozonizers about maximal transferred charge qmax, and (iii) the development of a graphical method for the determination of qmax from charge-voltage characteristics (Q-V plots, often referred as Lissajous figures) measured under pulsed excitation. The method of graphical presentation of qmax is demonstrated with an example of a Q-V plot measured under pulsed excitation. The relations between the discharge current jR(t), the transferred charge q(t), and the measurable parameters are presented in new forms, which enable the qualitative interpretation of the measured current and voltage waveforms without the knowledge about the value of the dielectric barrier capacitance Cd. Whereas for quantitative evaluation of electrical measurements, the accurate estimation of the Cd is important.

Effect of three-body forces on the phase behavior of charged colloids

International Nuclear Information System (INIS)

Wu, J. Z.; Bratko, D.; Blanch, H. W.; Prausnitz, J. M.

2000-01-01

Statistical-thermodynamic theory for predicting the phase behavior of a colloidal solution requires the pair interaction potential between colloidal particles in solution. In practice, it is necessary to assume pairwise additivity for the potential of mean force between colloidal particles, but little is known concerning the validity of this assumption. This paper concerns interaction between small charged colloids, such as surfactant micelles or globular proteins, in electrolyte solutions and the multibody effect on phase behavior. Monte Carlo simulations for isolated colloidal triplets in equilateral configurations show that, while the three-body force is repulsive when the three particles are near contact, it becomes short-ranged attractive at further separations, contrary to a previous study where the triplet force is attractive at all separations. The three-body force arises mainly from hard-sphere collisions between colloids and small ions; it is most significant in solutions of monovalent salt at low concentration where charged colloids experience strong electrostatic interactions. To illustrate the effect of three-body forces on the phase behavior of charged colloids, we calculated the densities of coexisting phases using van der Waals-type theories for colloidal solutions and for crystals. For the conditions investigated in this work, even though the magnitude of the three-body force may be as large as 10% of the total force at small separations, three-body forces do not have a major effect on the densities of binary coexisting phases. However, coexisting densities calculated using Derjaguin-Landau-Verwey-Overbeek theory are much different from those calculated using our simulated potential of mean force. (c) 2000 American Institute of Physics

Phase space imaging of a beam of charged particles by frictional forces

International Nuclear Information System (INIS)

Daniel, H.

1977-01-01

In the case of frictional forces, defined by always acting opposite to the particle motion, Liouville's theorem does not apply. The effect of such forces on a beam of charged particles is calculated in closed form. Emphasis is given to the phase space imaging by a moderator. Conditions for an increase in phase space density are discussed. (Auth.)

Heat transfer in multi-phase materials

CERN Document Server

Öchsner, Andreas

2011-01-01

This book provides a profound understanding, which physical processes and mechanisms cause the heat transfer in composite and cellular materials. It shows models for all important classes of composite materials and introduces into the latest advances. In three parts, the book covers Composite Materials (Part A), Porous and Cellular Materials (Part B) and the appearance of a conjoint solid phase and fluid aggregate (Part C).

Charge transfer complex in diketopyrrolopyrrole polymers and fullerene blends: Implication for organic solar cell efficiency

Science.gov (United States)

Moghe, D.; Yu, P.; Kanimozhi, C.; Patil, S.; Guha, S.

2012-02-01

Copolymers based on diketopyrrolopyrrole (DPP) have recently gained potential in organic photovoltaics. When blended with another acceptor such as PCBM, intermolecular charge transfer occurs which may result in the formation of charge transfer (CT) states. We present here the spectral photocurrent characteristics of two donor-acceptor DPP based copolymers, PDPP-BBT and TDPP-BBT, blended with PCBM to identify the CT states. The spectral photocurrent measured using Fourier-transform photocurrent spectroscopy (FTPS) and monochromatic photocurrent (PC) methods are compared with P3HT:PCBM, where the CT state is well known. PDPP-BBT:PCBM shows a stable CT state while TDPP-BBT does not. Our analysis shows that the larger singlet state energy difference between TDPP-BBT and PCBM along with the lower optical gap of TDPP-BBT obliterates the formation of a midgap CT state resulting in an enhanced photovoltaic efficiency over PDPP-BBT:PCBM.

Charge transfer properties and photoelectrocatalytic activity of TiO{sub 2}/MWCNT hybrid

Energy Technology Data Exchange (ETDEWEB)

Jiang Liaochuan [Nano Science Research Center, School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou 510640 (China); Zhang Weide, E-mail: zhangwd@scut.edu.c [Nano Science Research Center, School of Chemistry and Chemical Engineering, South China University of Technology, 381 Wushan Road, Guangzhou 510640 (China)

2010-12-15

The vertically aligned multiwalled carbon nanotube (MWCNT) arrays on tantalum foils were successfully coated with TiO{sub 2} nanoparticles by a hydrothermal process. The prepared TiO{sub 2}/MWCNT hybrid was characterized by scanning electron microscopy and transmission electron microscopy. The charge transfer properties and photocatalytic degradation of rhodamine B with and without bias potential under UV irradiation were investigated. The MWCNTs promoted the separation of photoinduced carriers in the TiO{sub 2}, thus enhanced photocatalytic activity. Applying bias potential on the photoanode further enhanced its catalytic activity. The efficient charge transportation and high photoelectrocatalytic activity towards degradation of rhodamine B made this hybrid material promising for photocatalyst and for the development of photoelectrical devices.

Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

Science.gov (United States)

Kim, Jeong Soo; Kim, Byung-Man; Kim, Un-Young; Shin, HyeonOh; Nam, Jung Seung; Roh, Deok-Ho; Park, Jun-Hyeok; Kwon, Tae-Hyuk

2017-10-11

We developed three types of dithieno[3,2-b;2',3'-d]thiophene (DTT)-based organic sensitizers for high-performance thin photoactive TiO 2 films and investigated the simple but powerful molecular engineering of different types of bonding between the triarylamine electron donor and the conjugated DTT π-bridge by the introduction of single, double, and triple bonds. As a result, with only 1.3 μm transparent and 2.5-μm TiO 2 scattering layers, the triple-bond sensitizer (T-DAHTDTT) shows the highest power conversion efficiency (η = 8.4%; V OC = 0.73 V, J SC = 15.4 mA·cm -2 , and FF = 0.75) in an iodine electrolyte system under one solar illumination (AM 1.5, 1000 W·m -2 ), followed by the single-bond sensitizer (S-DAHTDTT) (η = 7.6%) and the double-bond sensitizer (D-DAHTDTT) (η = 6.4%). We suggest that the superior performance of T-DAHTDTT comes from enhanced intramolecular charge transfer (ICT) induced by the triple bond. Consequently, T-DAHTDTT exhibits the most active photoelectron injection and charge transport on a TiO 2 film during operation, which leads to the highest photocurrent density among the systems studied. We analyzed these correlations mainly in terms of charge injection efficiency, level of photocharge storage, and charge-transport kinetics. This study suggests that the molecular engineering of a triple bond between the electron donor and the π-bridge of a sensitizer increases the performance of dye-sensitized solar cell (DSC) with a thin photoactive film by enhancing not only J SC through improved ICT but also V OC through the evenly distributed sensitizer surface coverage.

Charge-transfer energy in the water-hydrogen molecular aggregate revealed by molecular-beam scattering experiments, charge displacement analysis, and ab initio calculations.

Science.gov (United States)

Belpassi, Leonardo; Reca, Michael L; Tarantelli, Francesco; Roncaratti, Luiz F; Pirani, Fernando; Cappelletti, David; Faure, Alexandre; Scribano, Yohann

2010-09-22

Integral cross-section measurements for the system water-H(2) in molecular-beam scattering experiments are reported. Their analysis demonstrates that the average attractive component of the water-H(2) intermolecular potential in the well region is about 30% stronger than dispersion and induction forces would imply. An extensive and detailed theoretical analysis of the electron charge displacement accompanying the interaction, over several crucial sections of the potential energy surface (PES), shows that water-H(2) interaction is accompanied by charge transfer (CT) and that the observed stabilization energy correlates quantitatively with CT magnitude at all distances. Based on the experimentally determined potential and the calculated CT, a general theoretical model is devised which reproduces very accurately PES sections obtained at the CCSD(T) level with large basis sets. The energy stabilization associated with CT is calculated to be 2.5 eV per electron transferred. Thus, CT is shown to be a significant, strongly stereospecific component of the interaction, with water functioning as electron donor or acceptor in different orientations. The general relevance of these findings for water's chemistry is discussed.

Trajectory phases of a quantum dot model

International Nuclear Information System (INIS)

Genway, Sam; Hickey, James M; Garrahan, Juan P; Armour, Andrew D

2014-01-01

We present a thermodynamic formalism to study the trajectories of charge transport through a quantum dot coupled to two leads in the resonant-level model. We show that a close analogue of equilibrium phase transitions exists for the statistics of transferred charge; by tuning an appropriate ‘counting field’, crossovers to different trajectory phases are possible. Our description reveals a mapping between the statistics of a given device and current measurements over a range of devices with different dot–lead coupling strengths. Furthermore insight into features of the trajectory phases are found by studying the occupation of the dot conditioned on the transported charge between the leads; this is calculated from first principles using a trajectory biased two-point projective measurement scheme. (paper)

Charge states of ions, and mechanisms of charge ordering transitions

Science.gov (United States)

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.

Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

Science.gov (United States)

Fortage, Jérôme; Boixel, Julien; Blart, Errol; Hammarström, Leif; Becker, Hans Christian; Odobel, Fabrice

2008-01-01

The synthesis, electrochemical properties, and photoinduced electron transfer processes of a series of three novel zinc(II)-gold(III) bisporphyrin dyads (ZnP--S--AuP(+)) are described. The systems studied consist of two trisaryl porphyrins connected directly in the meso position via an alkyne unit to tert-(phenylenethynylene) or penta(phenylenethynylene) spacers. In these dyads, the estimated center to center interporphyrin separation distance varies from 32 to 45 A. The absorption, emission, and electrochemical data indicate that there are strong electronic interactions between the linked elements, thanks to the direct attachment of the spacer on the porphyrin ring through the alkyne unit. At room temperature in toluene, light excitation of the zinc porphyrin results in almost quantitative formation of the charge shifted state (.+)ZnP--S--AuP(.), whose lifetime is in the order of hundreds of picoseconds. In this solvent, the charge-separated state decays to the ground state through the intermediate population of the zinc porphyrin triplet excited state. Excitation of the gold porphyrin leads instead to rapid energy transfer to the triplet ZnP. In dichloromethane the charge shift reactions are even faster, with time constants down to 2 ps, and may be induced also by excitation of the gold porphyrin. In this latter solvent, the longest charge-shifted lifetime (tau=2.3 ns) was obtained with the penta-(phenylenethynylene) spacer. The charge shift reactions are discussed in terms of bridge-mediated super-exchange mechanisms as electron or hole transfer. These new bis-porphyrin arrays, with strong electronic coupling, represent interesting molecular systems in which extremely fast and efficient long-range photoinduced charge shift occurs over a long distance. The rate constants are two to three orders of magnitude larger than for corresponding ZnP--AuP(+) dyads linked via meso-phenyl groups to oligo-phenyleneethynylene spacers. This study demonstrates the critical

Experimental and modeling study on charge storage/transfer mechanism of graphene-based supercapacitors

Science.gov (United States)

Ban, Shuai; Jing, Xie; Zhou, Hongjun; Zhang, Lei; Zhang, Jiujun

2014-12-01

A symmetrical graphene-based supercapacitor is constructed for studying the charge-transfer mechanism within the graphene-based electrodes using both experiment measurements and molecular simulation. The in-house synthesized graphene is characterized by XRD, SEM and BET measurements for morphology and surface area. It is observed that the electric capacity of graphene electrode can be reduced by both high internal resistance and limited mass transfer. Computer modeling is conducted at the molecular level to characterize the diffusion behavior of electrolyte ions to the interior of electrode with emphasis on the unique 2D confinement imposed by graphene layers. Although graphene powder poses a moderate internal surface of 400 m2 g-1, the capacitance performance of graphene electrode can be as good as that of commercial activated carbon which has an overwhelming surface area of 1700 m2 g-1. An explanation to this abnormal correlation is that graphene material has an intrinsic capability of adaptively reorganizing its microporous structure in response to intercalation of ions and immergence of electrolyte solvent. The accessible surface of graphene is believed to be dramatically enlarged for ion adsorption during the charging process of capacitor.

Theory of interfacial charge-transfer complex photophysics in π-conjugated polymer-fullerene blends

Science.gov (United States)

Aryanpour, K.; Psiachos, D.; Mazumdar, S.

2010-03-01

We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes [1]. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component π-conjugated polymers [2], we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend [3], observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component π-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground state charge-transfer to the case of excited state charge-transfer. [1] K. Aryanpour, D. Psiachos, and S. Mazumdar, arXiv:0908.0366 [2] D. Psiachos and S. Mazumdar, Phys. Rev. B. 79 155106 (2009) [3] T. Drori et al., Phys. Rev. Lett. 101, 037402 (2008)

Enhanced intersystem crossing via a high energy charge transfer state in a perylenediimide-perylenemonoimide dyad

NARCIS (Netherlands)

Veldman, D.; Chopin-Cado, S.M.A; Meskers, S.C.J.; Janssen, R.A.J.

2008-01-01

The electronic relaxation processes of a photoexcited linear perylenediimide-perylenemonoimide (PDI-PMI) acceptor-donor dyad were studied. PDI-PMI serves as a model compound for donor-acceptor systems in photovoltaic devices and has been designed to have a high-energy PDI--PMI + charge transfer (CT)

Final Technical Report for the Energy Frontier Research Center Understanding Charge Separation and Transfer at Interfaces in Energy Materials (EFRC:CST)

Energy Technology Data Exchange (ETDEWEB)

Vanden Bout, David A. [Univ. of Texas, Austin, TX (United States)

2015-09-14

Our EFRC was founded with the vision of creating a broadly collaborative and synergistic program that would lead to major breakthroughs in the molecular-level understanding of the critical interfacial charge separation and charge transfer (CST) processes that underpin the function of candidate materials for organic photovoltaic (OPV) and electrical-energy-storage (EES) applications. Research in these energy contexts shares an imposing challenge: How can we understand charge separation and transfer mechanisms in the presence of immense materials complexity that spans multiple length scales? To address this challenge, our 50-member Center undertook a total of 28 coordinated research projects aimed at unraveling the CST mechanisms that occur at interfaces in these nanostructured materials. This rigorous multi-year study of CST interfaces has greatly illuminated our understanding of early-timescale processes (e.g., exciton generation and dissociation dynamics at OPV heterojunctions; control of Li+-ion charging kinetics by surface chemistry) occurring in the immediate vicinity of interfaces. Program outcomes included: training of 72 graduate student and postdoctoral energy researchers at 5 institutions and spanning 7 academic disciplines in science and engineering; publication of 94 peer-reviewed journal articles; and dissemination of research outcomes via 340 conference, poster and other presentations. Major scientific outcomes included: implementation of a hierarchical strategy for understanding the electronic communication mechanisms and ultimate fate of charge carriers in bulk heterojunction OPV materials; systematic investigation of ion-coupled electron transfer processes in model Li-ion battery electrode/electrolyte systems; and the development and implementation of 14 unique technologies and instrumentation capabilities to aid in probing sub-ensemble charge separation and transfer mechanisms.

Dissolved organic carbon enhances the mass transfer of hydrophobic organic compounds from Nonaqueous Phase Liquids (NAPLs) into the aqueous phase

NARCIS (Netherlands)

Smith, K.E.C.; Thullner, M.; Wick, L.Y.; Harms, H.

2011-01-01

The hypothesis that dissolved organic carbon (DOC) enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase above that attributable to dissolved molecular diffusion alone was tested. In controlled experiments, mass transfer rates of

Application of double-hybrid density functionals to charge transfer in N-substituted pentacenequinones.

Science.gov (United States)

Sancho-García, J C

2012-05-07

A set of N-heteroquinones, deriving from oligoacenes, have been recently proposed as n-type organic semiconductors with high electron mobilities in thin-film transistors. Generally speaking, this class of compounds self-assembles in neighboring π-stacks linked by weak hydrogen bonds. We aim at theoretically characterizing here the sequential charge transport (hopping) process expected to take place across these arrays of molecules. To do so, we need to accurately address the preferred packing of these materials simultaneously to single-molecule properties related to charge-transfer events, carefully employing dispersion-corrected density functional theory methods to accurately extract the key molecular parameters governing this phenomenon at the nanoscale. This study confirms the great deal of interest around these compounds, since controlled functionalization of model molecules (i.e., pentacene) allows to efficiently tune the corresponding charge mobilities, and the capacity of modern quantum-chemical methods to predict it after rationalizing the underlying structure-property relationships.

Longitudinal Phase Space Tomography with Space Charge

CERN Document Server

Hancock, S; Lindroos, M

2000-01-01

Tomography is now a very broad topic with a wealth of algorithms for the reconstruction of both qualitative and quantitative images. In an extension in the domain of particle accelerators, one of the simplest algorithms has been modified to take into account the non-linearity of large-amplitude synchrotron motion. This permits the accurate reconstruction of longitudinal phase space density from one-dimensional bunch profile data. The method is a hybrid one which incorporates particle tracking. Hitherto, a very simple tracking algorithm has been employed because only a brief span of measured profile data is required to build a snapshot of phase space. This is one of the strengths of the method, as tracking for relatively few turns relaxes the precision to which input machine parameters need to be known. The recent addition of longitudinal space charge considerations as an optional refinement of the code is described. Simplicity suggested an approach based on the derivative of bunch shape with the properties of...

Spectroscopic investigation and computational analysis of charge transfer hydrogen bonded reaction between 3-aminoquinoline with chloranilic acid in 1:1 stoichiometric ratio

Science.gov (United States)

Al-Ahmary, Khairia M.; Alenezi, Maha S.; Habeeb, Moustafa M.

2015-10-01

Charge transfer hydrogen bonded reaction between the electron donor (proton acceptor) 3-aminoquinoline with the electron acceptor (proton donor) chloranilic acid (H2CA) has been investigated experimentally and theoretically. The experimental work included the application of UV-vis spectroscopy to identify the charge transfer band of the formed complex, its molecular composition as well as estimating its formation constants in different solvent included acetonitrile (AN), methanol (MeOH), ethanol (EtOH) and chloroform (CHL). It has been recorded the presence of new absorption bands in the range 500-550 nm attributing to the formed complex. The molecular composition of the HBCT complex was found to be 1:1 (donor:acceptor) in all studied solvents based on continuous variation and photometric titration methods. In addition, the calculated formation constants from Benesi-Hildebrand equation recorded high values, especially in chloroform referring to the formation of stable HBCT complex. Infrared spectroscopy has been applied for the solid complex where formation of charge and proton transfer was proven in it. Moreover, 1H and 13C NMR spectroscopies were used to characterize the formed complex where charge and proton transfers were reconfirmed. Computational analysis included the use of GAMESS computations as a package of ChemBio3D Ultr12 program were applied for energy minimization and estimation of the stabilization energy for the produced complex. Also, geometrical parameters (bond lengths and bond angles) of the formed HBCT complex were computed and analyzed. Furthermore, Mullikan atomic charges, molecular potential energy surface, HOMO and LUMO molecular orbitals as well as assignment of the electronic spectra of the formed complex were presented. A full agreement between experimental and computational analysis has been found especially in the existence of the charge and proton transfers and the assignment of HOMO and LUMO molecular orbitals in the formed complex as

On the development of a grid-enhanced single-phase convective heat transfer correlation

International Nuclear Information System (INIS)

Miller, D.J.; Cheung, F.B.; Bajorek, S.M.

2011-01-01

A new single-phase convective heat transfer augmentation correlation has been developed using single phase steam cooling experimental data obtained from the Penn State/NRC Rod Bundle Heat Transfer (RBHT) facility. Experimental data obtained from the RBHT single phase steam cooling tests have been evaluated and new findings identified. Previous rod bundle tests showed the importance of spacer grid on the local heat transfer, and that the augmentation in heat transfer downstream of a grid decays exponentially. The RBHT data also shows that the Reynolds number affects the rate at which this augmentation decays. The new correlation includes the strong dependence of heat transfer on both the Reynolds number and the grid blockage ratio. While the effects of both parameters were clearly evident in the RBHT experimental data, existing correlations do not account for the Reynolds number effect. The developed correlation incorporates Reynolds number in the decay curve of heat transfer. The newly developed correlation adequately accounts for the dependence of the heat transfer augmentation decay rate on the local flow Reynolds number. (author)

Two-Phase Equilibrium Properties in Charged Topological Dilaton AdS Black Holes

Directory of Open Access Journals (Sweden)

Hui-Hua Zhao

2016-01-01

Full Text Available We discuss phase transition of the charged topological dilaton AdS black holes by Maxwell equal area law. The two phases involved in the phase transition could coexist and we depict the coexistence region in P-v diagrams. The two-phase equilibrium curves in P-T diagrams are plotted, the Clapeyron equation for the black hole is derived, and the latent heat of isothermal phase transition is investigated. We also analyze the parameters of the black hole that could have an effect on the two-phase coexistence. The results show that the black holes may go through a small-large phase transition similar to that of a usual nongravity thermodynamic system.

Molecular distortion and charge transfer effects in ZnPc/Cu(111)

KAUST Repository

Amin, B.; Nazir, S.; Schwingenschlö gl, Udo

2013-01-01

The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

Molecular distortion and charge transfer effects in ZnPc/Cu(111)

KAUST Repository

Amin, B.

2013-04-23

The adsorption geometry and electronic properties of a zinc-phthalocyanine molecule on a Cu(111) substrate are studied by density functional theory. In agreement with experiment, we find remarkable distortions of the molecule, mainly as the central Zn atom tends towards the substrate to minimize the Zn-Cu distance. As a consequence, the Zn-N chemical bonding and energy levels of the molecule are significantly modified. However, charge transfer induces metallic states on the molecule and therefore is more important for the ZnPc/Cu(111) system than the structural distortions.

Direct numerical simulations of fluid flow, heat transfer and phase changes

Science.gov (United States)

Juric, D.; Tryggvason, G.; Han, J.

1997-01-01

Direct numerical simulations of fluid flow, heat transfer, and phase changes are presented. The simulations are made possible by a recently developed finite difference/front tracking method based on the one-field formulation of the governing equations where a single set of conservation equations is written for all the phases involved. The conservation equations are solved on a fixed rectangular grid, but the phase boundaries are kept sharp by tracking them explicitly by a moving grid of lower dimension. The method is discussed and applications to boiling heat transfer and the solidification of drops colliding with a wall are shown.

Manipulating the dipole layer of polar organic molecules on metal surfaces via different charge-transfer channels

Science.gov (United States)

Lin, Meng-Kai; Nakayama, Yasuo; Zhuang, Ying-Jie; Wang, Chin-Yung; Pi, Tun-Wen; Ishii, Hisao; Tang, S.-J.

The key properties of organic films such as energy level alignment (ELA), work functions, and injection barriers are closely linked to this dipole layer. Using angle resolved photoemission spectroscopy (ARPES), we systemically investigate the coverage-dependent work functions and spectra line shapes of occupied molecular orbital states of a polar molecule, chloroaluminium phthalocyanine (ClAlPc), grown on Ag(111) to show that the orientations of the first ClAlPc layer can be manipulated via the molecule deposition rate and post annealing, causing ELA at organic-metal interface to differ for about 0.3 eV between Cl-up and Cl-down configuration. Moreover, by comparing the experimental results with the calculations based on both gas-phase model and realistic model of ClAlPc on Ag(111) , we evidence that the different orientations of ClAlPc dipole layers lead to different charge-transfer channels between ClAlPc and Ag, a key factor that controls the ELA at organic-metal interface.

Phase separation in strongly correlated electron systems with two types of charge carriers

International Nuclear Information System (INIS)

Kugel, K.I.; Rakhmanov, A.L.; Sboychakov, A.O.

2007-01-01

Full text: A competition between the localization of the charge carriers due to Jahn-Teller distortions and the energy gain due to their delocalization in doped manganite and related magnetic oxides is analyzed based on a Kondo-lattice type model. The resulting effective Hamiltonian is, in fact, a generalization of the Falicov-Kimball model. We find that the number of itinerant charge carriers can be significantly lower than that implied by the doping level x. The phase diagram of the model in the T plane is constructed. The system exhibits magnetic ordered (antiferromagnetic, ferromagnetic, or canted) states as well the paramagnetic states with zero and nonzero density of the itinerant electrons. It is shown that a phase-separation is favorable in energy for a wide doping range. The characteristic size of inhomogeneities in a phase-separated state is of the order of several lattice constants. We also analyzed the two-band Hubbard model in the limit of strong on-site Coulomb repulsion. It was shown that such a system has a tendency to phase separation into the regions with different charge densities even in the absence of magnetic or any other ordering, if the ratio of the bandwidths is large enough. The work was supported by the European project CoMePhS and by the Russian Foundation for Basic Research, project no. 05-02-17600. (authors)

Quantum phases for a charged particle and electric/magnetic dipole in an electromagnetic field

Science.gov (United States)