Sample records for double charge transfer

  1. TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4‧-dimethylaminoflavonol in ethanol solvent

    NASA Astrophysics Data System (ADS)

    Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

    2015-02-01

    Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4‧-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

  2. Experimental and theoretical studies of the He(2+)-He system - Differential cross sections for direct, single-, and double-charge-transfer scattering at keV energies

    NASA Technical Reports Server (NTRS)

    Gao, R. S.; Dutta, C. M.; Lane, N. F.; Smith, K. A.; Stebbings, R. F.; Kimura, M.

    1992-01-01

    Measurements and calculations of differential cross sections for direct scattering, single-charge transfer, and double-charge transfer in collisions of 1.5-, 2.0-, 6.0-, and 10.0-keV (He-3)2+ with an He-4 target are reported. The measurements cover laboratory scattering angles below 1.5 deg with an angular resolution of about 0.03 deg. A quantum-mechanical molecular-state representation is employed in the calculations; in the case of single-charge transfer a two-state close-coupling calculation is carried out taking into account electron-translation effects. The theoretical calculations agree well with the experimental results for direct scattering and double-charge transfer. The present calculation identifies the origins of oscillatory structures observed in the differential cross sections.

  3. Charge Transfer in Saturation Doping of Double-Wall Carbon Nanotubes

    NASA Astrophysics Data System (ADS)

    Tchernatinsky, Alexander; Jayanthi, Chakram; Sumanasekera, Gamini; Wu, Shi-Yu

    2004-03-01

    Recent experimental evidences suggest that the outer tube of a double-wall carbon nanotube (DWCNT) may serve as a 'Faraday' cage (G. Chen, et al., Phys. Rev. Lett., 90, 257403 (2003)). In this presentation, we report the result of our systematic study of the effect of saturation doping of a (10,10) single-wall carbon nanotube, a (5,5)@(10,10) DWCNT, and a C_60@(10,10) peapod using DFT-based VASP computational package (G. Kresse and J. Hafner, Phys. Rev. B, 47, 558 (1993)). By comparing the resulting charge transfer of the above mentioned cases we shall provide the physics underlying the Faraday cage behavior of DWCNTs. Acknowledgments: This work was supported by the NSF (DMR-0112824) and the U.S.DOE (DE-FG02-00ER45832).

  4. Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion

    NASA Astrophysics Data System (ADS)

    Li, Zheng; Vendrell, Oriol; Santra, Robin

    2015-10-01

    We explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K -shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we find that the double hole is transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. The nuclear displacements along specific vibrational modes are of the order of 15% of a typical chemical bond between carbon, oxygen, and nitrogen atoms and about 30% for bonds involving hydrogen atoms. The time required for the hole transfer corresponds to less than half a vibrational period of the involved nuclear modes. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. It also indicates that in x-ray imaging experiments, in which ionization is unavoidable, valence electron redistribution caused by nuclear dynamics might be much faster than previously anticipated. Thus, non-Born-Oppenheimer effects may affect the apparent electron densities extracted from such measurements.

  5. Ultrafast Charge Transfer of a Valence Double Hole in Glycine Driven Exclusively by Nuclear Motion.

    PubMed

    Li, Zheng; Vendrell, Oriol; Santra, Robin

    2015-10-02

    We explore theoretically the ultrafast transfer of a double electron hole between the functional groups of glycine after K-shell ionization and subsequent Auger decay. Although a large energy gap of about 15 eV initially exists between the two electronic states involved and coherent electronic dynamics play no role in the hole transfer, we find that the double hole is transferred within 3 to 4 fs between both functional ends of the glycine molecule driven solely by specific nuclear displacements and non-Born-Oppenheimer effects. The nuclear displacements along specific vibrational modes are of the order of 15% of a typical chemical bond between carbon, oxygen, and nitrogen atoms and about 30% for bonds involving hydrogen atoms. The time required for the hole transfer corresponds to less than half a vibrational period of the involved nuclear modes. This finding challenges the common wisdom that nuclear dynamics of the molecular skeleton are unimportant for charge transfer processes at the few-femtosecond time scale and shows that they can even play a prominent role. It also indicates that in x-ray imaging experiments, in which ionization is unavoidable, valence electron redistribution caused by nuclear dynamics might be much faster than previously anticipated. Thus, non-Born-Oppenheimer effects may affect the apparent electron densities extracted from such measurements.

  6. An Ab Initio Exciton Model Including Charge-Transfer Excited States

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

    Li, Xin; Parrish, Robert M.; Liu, Fang

    Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited statesmore » and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.« less

  7. An Ab Initio Exciton Model Including Charge-Transfer Excited States

    DOE PAGES

    Li, Xin; Parrish, Robert M.; Liu, Fang; ...

    2017-06-15

    Here, the Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited statesmore » and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.« less

  8. An Ab Initio Exciton Model Including Charge-Transfer Excited States.

    PubMed

    Li, Xin; Parrish, Robert M; Liu, Fang; Kokkila Schumacher, Sara I L; Martínez, Todd J

    2017-08-08

    The Frenkel exciton model is a useful tool for theoretical studies of multichromophore systems. We recently showed that the exciton model could be used to coarse-grain electronic structure in multichromophoric systems, focusing on singly excited exciton states [ Acc. Chem. Res. 2014 , 47 , 2857 - 2866 ]. However, our previous implementation excluded charge-transfer excited states, which can play an important role in light-harvesting systems and near-infrared optoelectronic materials. Recent studies have also emphasized the significance of charge-transfer in singlet fission, which mediates the coupling between the locally excited states and the multiexcitonic states. In this work, we report on an ab initio exciton model that incorporates charge-transfer excited states and demonstrate that the model provides correct charge-transfer excitation energies and asymptotic behavior. Comparison with TDDFT and EOM-CC2 calculations shows that our exciton model is robust with respect to system size, screening parameter, and different density functionals. Inclusion of charge-transfer excited states makes the exciton model more useful for studies of singly excited states and provides a starting point for future construction of a model that also includes double-exciton states.

  9. Utilizing Electrical Characteristics of Individual Nanotube Devices to Study the Charge Transfer between CdSe Quantum Dots and Double-Walled Nanotubes

    DOE PAGES

    Zhu, Yuqi; Zhou, Ruiping; Wang, Lei; ...

    2017-03-02

    To study the charge transfer between cadmium selenide (CdSe) quantum dots (QDs) and double-walled nanotubes (DWNTs), various sizes of CdSe-ligand-DWNT structures are synthesized, and field-effect transistors (FETs) from individual functionalized DWNTs rather than networks of the same are fabricated. From the electrical measurements, two distinct electron transfer mechanisms from the QD system to the nanotube are identified. By the formation of the CdSe-ligand-DWNT heterostructure, an effectively n-doped nanotube is created due to the smaller work function of CdSe as compared with the nanotube. In addition, once the QD-DWNT system is exposed to laser light, further electron transfer from the QDmore » through the ligand, i.e. 4-mercaptophenol (MTH), to the nanotube occurs and a clear QD-size dependent tunneling process is observed. Furthermore, the detailed analysis of a large set of devices and the particular methodology employed here for the first time allowed for extracting a wavelength and quantum dot size dependent charge transfer efficiency – a quantity that is evaluated for the first time through electrical measurement.« less

  10. Utilizing Electrical Characteristics of Individual Nanotube Devices to Study the Charge Transfer between CdSe Quantum Dots and Double-Walled Nanotubes

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

    Zhu, Yuqi; Zhou, Ruiping; Wang, Lei

    To study the charge transfer between cadmium selenide (CdSe) quantum dots (QDs) and double-walled nanotubes (DWNTs), various sizes of CdSe-ligand-DWNT structures are synthesized, and field-effect transistors (FETs) from individual functionalized DWNTs rather than networks of the same are fabricated. From the electrical measurements, two distinct electron transfer mechanisms from the QD system to the nanotube are identified. By the formation of the CdSe-ligand-DWNT heterostructure, an effectively n-doped nanotube is created due to the smaller work function of CdSe as compared with the nanotube. In addition, once the QD-DWNT system is exposed to laser light, further electron transfer from the QDmore » through the ligand, i.e. 4-mercaptophenol (MTH), to the nanotube occurs and a clear QD-size dependent tunneling process is observed. Furthermore, the detailed analysis of a large set of devices and the particular methodology employed here for the first time allowed for extracting a wavelength and quantum dot size dependent charge transfer efficiency – a quantity that is evaluated for the first time through electrical measurement.« less

  11. Charge migration and charge transfer in molecular systems

    PubMed Central

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

    2017-01-01

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

  12. Double Charge Exchange Reactions and Double Beta Decay

    NASA Astrophysics Data System (ADS)

    Auerbach, N.

    2018-05-01

    The subject of this presentation is at the forefront of nuclear physics, namely double beta decay. In particular one is most interested in the neutrinoless process of double beta decay, when the decay proceeds without the emission of two neutrinos. The observation of such decay would mean that the lepton conservation symmetry is violated and that the neutrinos are of Majorana type, meaning that they are their own anti-particles. The life time of this process has two unknowns, the mass of the neutrino and the nuclear matrix element. Determining the nuclear matrix element and knowing the cross-section well will set limits on the neutrino mass. There is a concentrated effort among the nuclear physics community to calculate this matrix element. Usually these matrix elements are a very small part of the total strength of the transition operators involved in the process. There is no simple way to “calibrate” the nuclear double beta decay matrix element. The double beta decay is a double charge exchange process, therefore it is proposed that double charge exchange reactions using ion projectiles on nuclei that are candidates for double beta decay, will provide additional necessary information about the nuclear matrix elements.

  13. Electric Double-Layer Interaction between Dissimilar Charge-Conserved Conducting Plates.

    PubMed

    Chan, Derek Y C

    2015-09-15

    Small metallic particles used in forming nanostructured to impart novel optical, catalytic, or tribo-rheological can be modeled as conducting particles with equipotential surfaces that carry a net surface charge. The value of the surface potential will vary with the separation between interacting particles, and in the absence of charge-transfer or electrochemical reactions across the particle surface, the total charge of each particle must also remain constant. These two physical conditions require the electrostatic boundary condition for metallic nanoparticles to satisfy an equipotential whole-of-particle charge conservation constraint that has not been studied previously. This constraint gives rise to a global charge conserved constant potential boundary condition that results in multibody effects in the electric double-layer interaction that are either absent or are very small in the familiar constant potential or constant charge or surface electrochemical equilibrium condition.

  14. Revealing the Double-Edged Sword Role of Graphene on Boosted Charge Transfer versus Active Site Control in TiO2 Nanotube Arrays@RGO/MoS2 Heterostructure.

    PubMed

    Quan, Quan; Xie, Shunji; Weng, Bo; Wang, Ye; Xu, Yi-Jun

    2018-05-01

    Charge separation/transfer is generally believed to be the most key factor affecting the efficiency of photocatalysis, which however will be counteracted if not taking the active site engineering into account for a specific photoredox reaction. Here, a 3D heterostructure composite is designed consisting of MoS 2 nanoplatelets decorated on reduced graphene oxide-wrapped TiO 2 nanotube arrays (TNTAs@RGO/MoS 2 ). Such a cascade configuration renders a directional migration of charge carriers and controlled immobilization of active sites, thereby showing much higher photoactivity for water splitting to H 2 than binary TNTAs@RGO and TNTAs/MoS 2 . The photoactivity comparison and mechanistic analysis reveal the double-edged sword role of RGO on boosted charge separation/transfer versus active site control in this composite system. The as-observed inconsistency between boosted charge transfer and lowered photoactivity over TNTAs@RGO is attributed to the decrease of active sites for H 2 evolution, which is significantly different from the previous reports in literature. The findings of the intrinsic relationship of balanced benefits from charge separation/transfer and active site control could promote the rational optimization of photocatalyst design by cooperatively manipulating charge flow and active site control, thereby improving the efficiency of photocatalysis for target photoredox processes. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Electrochemical capacitance modulation in an interacting mesoscopic capacitor induced by internal charge transfer

    NASA Astrophysics Data System (ADS)

    Liu, Wei; He, Jianhong; Guo, Huazhong; Gao, Jie

    2018-04-01

    We report experiments on the dynamic response of an interacting mesoscopic capacitor consisting of a quantum dot with two confined spin-split levels of the lowest Landau level. In high magnetic fields, states inside the dot are regulated by a mixture of Coulomb interaction and Landau-level quantization, and electrons distribute on two spatially separated regions. Quantum point contact voltage and magnetic field are employed to manipulate the number and distribution of electrons inside the quantum dot. We find that the periodicity of the electrochemical capacitance oscillations is dominated by the charging energy, and their amplitudes, due to internal charge transfer and strong internal capacitive coupling, show rich variations of modulations. Magnetocapacitance displays a sawtoothlike manner and may differ in tooth directions for different voltages, which, we demonstrate, result from a sawtoothlike electrochemical potential change induced by internal charge transfer and field-sensitive electrostatic potential. We further build a charge stability diagram, which, together with all other capacitance properties, is consistently interpreted in terms of a double-dot model. The demonstrated technique is of interest as a tool for fast and sensitive charge state readout of a double-quantum-dot qubit in the gigahertz frequency quantum electronics.

  16. Engineering and Probing Topological Properties of Dirac Semimetal Films by Asymmetric Charge Transfer.

    PubMed

    Villanova, John W; Barnes, Edwin; Park, Kyungwha

    2017-02-08

    Dirac semimetals (DSMs) have topologically robust three-dimensional Dirac (doubled Weyl) nodes with Fermi-arc states. In heterostructures involving DSMs, charge transfer occurs at the interfaces, which can be used to probe and control their bulk and surface topological properties through surface-bulk connectivity. Here we demonstrate that despite a band gap in DSM films, asymmetric charge transfer at the surface enables one to accurately identify locations of the Dirac-node projections from gapless band crossings and to examine and engineer properties of the topological Fermi-arc surface states connecting the projections, by simulating adatom-adsorbed DSM films using a first-principles method with an effective model. The positions of the Dirac-node projections are insensitive to charge transfer amount or slab thickness except for extremely thin films. By varying the amount of charge transfer, unique spin textures near the projections and a separation between the Fermi-arc states change, which can be observed by gating without adatoms.

  17. Charge Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Dennerl, Konrad

    2010-12-01

    Charge transfer, or charge exchange, describes a process in which an ion takes one or more electrons from another atom. Investigations of this fundamental process have accompanied atomic physics from its very beginning, and have been extended to astrophysical scenarios already many decades ago. Yet one important aspect of this process, i.e. its high efficiency in generating X-rays, was only revealed in 1996, when comets were discovered as a new class of X-ray sources. This finding has opened up an entirely new field of X-ray studies, with great impact due to the richness of the underlying atomic physics, as the X-rays are not generated by hot electrons, but by ions picking up electrons from cold gas. While comets still represent the best astrophysical laboratory for investigating the physics of charge transfer, various studies have already spotted a variety of other astrophysical locations, within and beyond our solar system, where X-rays may be generated by this process. They range from planetary atmospheres, the heliosphere, the interstellar medium and stars to galaxies and clusters of galaxies, where charge transfer may even be observationally linked to dark matter. This review attempts to put the various aspects of the study of charge transfer reactions into a broader historical context, with special emphasis on X-ray astrophysics, where the discovery of cometary X-ray emission may have stimulated a novel look at our universe.

  18. Charge transfer between O6+ and atomic hydrogen

    NASA Astrophysics Data System (ADS)

    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.

  19. Double Transfer Voltammetry in Two-Polarizable Interface Systems: Effects of the Lipophilicity and Charge of the Target and Compensating Ions.

    PubMed

    Molina, Ángela; Laborda, Eduardo; Olmos, José Manuel; Millán-Barrios, Enrique

    2018-03-06

    Analytical expressions are obtained for the study of the net current and individual fluxes across macro- and micro-liquid/liquid interfaces in series as those found in ion sensing with solvent polymeric membranes and in ion-transfer batteries. The mathematical solutions deduced are applicable to any voltammetric technique, independently of the lipophilicity and charge number of the target and compensating ions. When supporting electrolytes of semihydrophilic ions are employed, the so-called double transfer voltammograms have a tendency to merge into a single signal, which complicates notably the modeling and analysis of the electrochemical response. The present theoretical results point out that the appearance of one or two voltammetric waves is highly dependent on the size of the interfaces and on the viscosity of the organic solution. Hence, the two latter can be adjusted experimentally in order to "split" the voltammograms and extract information about the ions involved. This has been illustrated in this work with the experimental study in water | 1,2-dichloroethane | water cells of the transfer of the monovalent tetraethylammonium cation compensated by anions of different lipophilicity, and also of the divalent hexachloroplatinate anion.

  20. Spontaneous charged lipid transfer between lipid vesicles.

    PubMed

    Richens, Joanna L; Tyler, Arwen I I; Barriga, Hanna M G; Bramble, Jonathan P; Law, Robert V; Brooks, Nicholas J; Seddon, John M; Ces, Oscar; O'Shea, Paul

    2017-10-03

    An assay to study the spontaneous charged lipid transfer between lipid vesicles is described. A donor/acceptor vesicle system is employed, where neutrally charged acceptor vesicles are fluorescently labelled with the electrostatic membrane probe Fluoresceinphosphatidylethanolamine (FPE). Upon addition of charged donor vesicles, transfer of negatively charged lipid occurs, resulting in a fluorescently detectable change in the membrane potential of the acceptor vesicles. Using this approach we have studied the transfer properties of a range of lipids, varying both the headgroup and the chain length. At the low vesicle concentrations chosen, the transfer follows a first-order process where lipid monomers are transferred presumably through the aqueous solution phase from donor to acceptor vesicle. The rate of transfer decreases with increasing chain length which is consistent with energy models previously reported for lipid monomer vesicle interactions. Our assay improves on existing methods allowing the study of a range of unmodified lipids, continuous monitoring of transfer and simplified experimental procedures.

  1. Application of double-hybrid density functionals to charge transfer in N-substituted pentacenequinones.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  3. Charge transfer in TATB and HMX under extreme conditions.

    PubMed

    Zhang, Chaoyang; Ma, Yu; Jiang, Daojian

    2012-11-01

    Charge transfer is usually accompanied by structural changes in materials under different conditions. However, the charge transfer in energetic materials that are subjected to extreme conditions has seldom been explored by researchers. In the work described here, the charge transfer in single molecules and unit cells of the explosives TATB and HMX under high temperatures and high pressures was investigated by performing static and dynamic calculations using three DFT methods, including the PWC functional of LDA, and the BLYP and PBE functionals of GGA. The results showed that negative charge is transferred from the nitro groups of molecular or crystalline TATB and HMX when they are heated. All DFT calculations for the compressed TATB unit cell indicate that, generally, negative charge transfer occurs to its nitro groups as the compression increases. PWC and PBE calculations for crystalline HMX show that negative charge is first transferred to the nitro groups but, as the compression increases, the negative charge is transferred from the nitro groups. However, the BLYP calculations indicated that there was gradual negative charge transfer to the nitro groups of HMX, similar to the case for TATB. The unrelaxed state of the uniformly compressed TATB causes negative charge to be transferred from its nitro groups, in contrast to what is seen in the relaxed state. Charge transfer in TATB is predicted to occur much more easily than in HMX.

  4. Molecular control of pentacene/ZnO photoinduced charge transfer

    NASA Astrophysics Data System (ADS)

    Spalenka, Josef W.; Paoprasert, Peerasak; Franking, Ryan; Hamers, Robert J.; Gopalan, Padma; Evans, Paul G.

    2011-03-01

    Photoinduced charge transfer modifies the device properties of illuminated pentacene field effect transistors (FETs) incorporating ZnO quantum dots at the gate insulator/pentacene interface. The transferred charge is trapped on electronic states associated with the ZnO quantum dots, with a steady state population approximately proportional to the rate of organic-inorganic charge transfer. Trapped charge shifts the threshold voltage of the FETs, providing the means to evaluate the rate of organic/inorganic charge transfer and the effects of interface modification. Monolayers of the wide-gap alkane stearic acid and the conjugated oligomer terthiophene attached to the ZnO suppress or permit charge transfer, respectively.

  5. Ligand-induced dependence of charge transfer in nanotube–quantum dot heterostructures

    DOE PAGES

    Wang, Lei; Han, Jinkyu; Sundahl, Bryan; ...

    2016-07-01

    As a model system to probe ligand-dependent charge transfer in complex composite heterostructures, we fabricated double-walled carbon nanotube (DWNT) – CdSe quantum dot (QD) composites. Whereas the average diameter of the QDs probed was kept fixed at ~4.1 nm and the nanotubes analyzed were similarly oxidatively processed, by contrast, the ligands used to mediate the covalent attachment between the QDs and DWNTs were systematically varied to include p-phenylenediamine (PPD), 2-aminoethanethiol (AET), and 4-aminothiophenol (ATP). Herein, we have put forth a unique compilation of complementary data from experiment and theory, including results from transmission electron microscopy (TEM), near-edge X-ray absorption finemore » structure (NEXAFS) spectroscopy, Raman spectroscopy, electrical transport measurements, and theoretical modeling studies, in order to fundamentally assess the nature of the charge transfer between CdSe QDs and DWNTs, as a function of the structure of various, intervening bridging ligand molecules. Specifically, we correlated evidence of charge transfer as manifested by changes and shifts associated with NEXAFS intensities, Raman peak positions, and threshold voltages both before and after CdSe QD deposition onto the underlying DWNT surface. Importantly, for the first time ever in these types of nanoscale composite systems, we have sought to use theoretical modeling to justify and account for our experimental results. Finally, our overall data suggest that (i) QD coverage density on the DWNTs varies, based upon the different ligand pendant groups used and that (ii) the presence of a π-conjugated carbon framework within the ligands themselves and the electron affinity of the pendant groups collectively play important roles in the resulting charge transfer from QDs to the underlying CNTs.« less

  6. Charge transfer in iridate-manganite superlattices

    DOE PAGES

    Okamoto, Satoshi; Nichols, John; Sohn, Changhee; ...

    2017-03-03

    Charge transfer in superlattices consisting of SrIrOmore » $$_3$$ and SrMnO$$_3$$ is investigated using density functional theory. Despite the nearly identical work function and non-polar interfaces between SrIrO$$_3$$ and SrMnO$$_3$$, rather large charge transfer was experimentally reported between them. Our results provide a qualitative understanding to such experimental reports. We further develop a microscopic model that captures the mechanism behind this phenomenon. This leads to unique strain dependence of such charge transfer in iridate-manganite superlattices. The predicted behavior is consistently verified by experiment. Lastly, our work thus demonstrates a new route to control electronic states in non-polar oxide heterostructures.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Charge Transfer Processes in Collisions of Si4+ Ions with He Atoms at Intermediate Energies

    NASA Astrophysics Data System (ADS)

    Suzuki, R.; Watanabe, A.; Sato, H.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Kimura, M.; Stancil, P. C.

    Charge transfer in collisions of Si4+ ions with He atoms below 100 keV/u is studied by using a molecular orbital representation within both the semiclassical and quantal representations. Single transfer reaction Si4++He →Si3++He+ has been studied by a number of theoretical investigations. In addition to the reaction (1), the first semiclassical MOCC calculations are performed for the double transfer channel Si4++HE→Si2++He2+ Nine molecular states that connect both with single and double electron transfer processes are considered in the present model. Electronic states and corresponding couplings are determined by the multireference single- and double- excitation configuration interaction method. The present cross sections tie well with the earlier calculations of Stancil et al., Phys. Rev. A 55, 1064 (1997) at lower energies, but show a rather different magnitude from those of Bacchus-Montabonel and Ceyzeriat, Phys. Rev. A 58, 1162 (1998). The present rate constant is found to be significantly different from the experimental finding of Fang and Kwong, Phys. Rev. A 59, 342 (1996) at 4,600 K, and hence does not support the experiment.

  9. Quantum Theory of Atoms in Molecules Charge-Charge Transfer-Dipolar Polarization Classification of Infrared Intensities.

    PubMed

    Duarte, Leonardo J; Richter, Wagner E; Silva, Arnaldo F; Bruns, Roy E

    2017-10-26

    Fundamental infrared vibrational transition intensities of gas-phase molecules are sensitive probes of changes in electronic structure accompanying small molecular distortions. Models containing charge, charge transfer, and dipolar polarization effects are necessary for a successful classification of the C-H, C-F, and C-Cl stretching and bending intensities. C-H stretching and in-plane bending vibrations involving sp 3 carbon atoms have small equilibrium charge contributions and are accurately modeled by the charge transfer-counterpolarization contribution and its interaction with equilibrium charge movement. Large C-F and C═O stretching intensities have dominant equilibrium charge movement contributions compared to their charge transfer-dipolar polarization ones and are accurately estimated by equilibrium charge and the interaction contribution. The C-F and C-Cl bending modes have charge and charge transfer-dipolar polarization contribution sums that are of similar size but opposite sign to their interaction values resulting in small intensities. Experimental in-plane C-H bends have small average intensities of 12.6 ± 10.4 km mol -1 owing to negligible charge contributions and charge transfer-counterpolarization cancellations, whereas their average out-of-plane experimental intensities are much larger, 65.7 ± 20.0 km mol -1 , as charge transfer is zero and only dipolar polarization takes place. The C-F bending intensities have large charge contributions but very small intensities. Their average experimental out-of-plane intensity of 9.9 ± 12.6 km mol -1 arises from the cancellation of large charge contributions by dipolar polarization contributions. The experimental average in-plane C-F bending intensity, 5.8 ± 7.3 km mol -1 , is also small owing to charge and charge transfer-counterpolarization sums being canceled by their interaction contributions. Models containing only atomic charges and their fluxes are incapable of describing electronic structure

  10. Double-layered cell transfer technology for bone regeneration

    PubMed Central

    Akazawa, Keiko; Iwasaki, Kengo; Nagata, Mizuki; Yokoyama, Naoki; Ayame, Hirohito; Yamaki, Kazumasa; Tanaka, Yuichi; Honda, Izumi; Morioka, Chikako; Kimura, Tsuyoshi; Komaki, Motohiro; Kishida, Akio; Izumi, Yuichi; Morita, Ikuo

    2016-01-01

    For cell-based medicine, to mimic in vivo cellular localization, various tissue engineering approaches have been studied to obtain a desirable arrangement of cells on scaffold materials. We have developed a novel method of cell manipulation called “cell transfer technology”, enabling the transfer of cultured cells onto scaffold materials, and controlling cell topology. Here we show that using this technique, two different cell types can be transferred onto a scaffold surface as stable double layers or in patterned arrangements. Various combinations of adherent cells were transferred to a scaffold, amniotic membrane, in overlapping bilayers (double-layered cell transfer), and transferred cells showed stability upon deformations of the material including folding and trimming. Transplantation of mesenchymal stem cells from periodontal ligaments (PDLSC) and osteoblasts, using double-layered cell transfer significantly enhanced bone formation, when compared to single cell type transplantation. Our findings suggest that this double-layer cell transfer is useful to produce a cell transplantation material that can bear two cell layers. Moreover, the transplantation of an amniotic membrane with PDLSCs/osteoblasts by cell transfer technology has therapeutic potential for bone defects. We conclude that cell transfer technology provides a novel and unique cell transplantation method for bone regeneration. PMID:27624174

  11. Determination of charge transfer resistance and capacitance of microbial fuel cell through a transient response analysis of cell voltage.

    PubMed

    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.

  12. Study of the Charge Transfer Process of LaNi5 Type Electrodes in Ni-MH Batteries

    NASA Astrophysics Data System (ADS)

    Le, Xuan Que; Nguyen, Phu Thuy

    2002-12-01

    As a result of the charge process of LaNi5 type electrode, hydrogen is reversibly absorbed on the electrode surface. The process consists two principal steps. During the both processes, the first reaction step occurs in the interface solid/liquid, negatively charged, with high static electric field, where the double layer structure became more compact. The transfer of charge under high electric field depends on many factors, principally on compositions of the electrode materials. Effects on that of Co, Fe, Mn substitutes, with different concentrations, have been comparatively studied using electrochemical technique. The analyse of interface C -.V study results has been realised, respecting Mott-Schottky relation. Optimal contents of some additives have been discussed. Some advantages of the applied electrochemical methods have been confirmed. The mechanism of the charges transfer and of the hydrogen reversible storage in the crystal structure in the batteries has been discussed. With the proposed mechanism, one can more explicitly understand the difference of the magnetic effect of the electrode materials before and after charge-discharge process can be explained.

  13. Dynamics of charge-transfer excitons in type-II semiconductor heterostructures

    NASA Astrophysics Data System (ADS)

    Stein, M.; Lammers, C.; Richter, P.-H.; Fuchs, C.; Stolz, W.; Koch, M.; Vänskä, O.; Weseloh, M. J.; Kira, M.; Koch, S. W.

    2018-03-01

    The formation, decay, and coherence properties of charge-transfer excitons in semiconductor heterostructures are investigated by applying four-wave-mixing and terahertz spectroscopy in combination with a predictive microscopic theory. A charge-transfer process is identified where the optically induced coherences decay directly into a charge-transfer electron-hole plasma and exciton states. It is shown that charge-transfer excitons are more sensitive to the fermionic electron-hole substructure than regular excitons.

  14. Molecular Engineering for Enhanced Charge Transfer in Thin-Film Photoanode.

    PubMed

    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.

  15. Charge-transfer crystallites as molecular electrical dopants

    PubMed Central

    Méndez, Henry; Heimel, Georg; Winkler, Stefanie; Frisch, Johannes; Opitz, Andreas; Sauer, Katrein; Wegner, Berthold; Oehzelt, Martin; Röthel, Christian; Duhm, Steffen; Többens, Daniel; Koch, Norbert; Salzmann, Ingo

    2015-01-01

    Ground-state integer charge transfer is commonly regarded as the basic mechanism of molecular electrical doping in both, conjugated polymers and oligomers. Here, we demonstrate that fundamentally different processes can occur in the two types of organic semiconductors instead. Using complementary experimental techniques supported by theory, we contrast a polythiophene, where molecular p-doping leads to integer charge transfer reportedly localized to one quaterthiophene backbone segment, to the quaterthiophene oligomer itself. Despite a comparable relative increase in conductivity, we observe only partial charge transfer for the latter. In contrast to the parent polymer, pronounced intermolecular frontier-orbital hybridization of oligomer and dopant in 1:1 mixed-stack co-crystallites leads to the emergence of empty electronic states within the energy gap of the surrounding quaterthiophene matrix. It is their Fermi–Dirac occupation that yields mobile charge carriers and, therefore, the co-crystallites—rather than individual acceptor molecules—should be regarded as the dopants in such systems. PMID:26440403

  16. Impact of charge-transfer excitons in regioregular polythiophene on the charge separation at polythiophene-fullerene heterojunctions

    NASA Astrophysics Data System (ADS)

    Polkehn, M.; Tamura, H.; Burghardt, I.

    2018-01-01

    This study addresses the mechanism of ultrafast charge separation in regioregular oligothiophene-fullerene assemblies representative of poly-3-hexylthiophene (P3HT)-[6,6]-phenyl-C61 butyric acid methyl ester (PCBM) heterojunctions, with special emphasis on the inclusion of charge transfer excitons in the oligothiophene phase. The formation of polaronic inter-chain charge separated species in highly ordered oligothiophene has been demonstrated in recent experiments and could have a significant impact on the net charge transfer to the fullerene acceptor. The present approach combines a first-principles parametrized multi-site Hamiltonian, based on time-dependent density functional theory calculations, with accurate quantum dynamics simulations using the multi-layer multi-configuration time-dependent Hartree method. Quantum dynamical studies are carried out for up to 182 electronic states and 112 phonon modes. The present analysis follows up on our previous study of (Huix-Rotllant et al 2015 J. Phys. Chem. Lett. 6 1702) and significantly expands the scope of this analysis by including the dynamical role of charge transfer excitons. Our investigation highlights the pronounced mixing of photogenerated Frenkel excitons with charge transfer excitons in the oligothiophene domain, and the opening of new transfer channels due the creation of such charge-separated species. As a result, it turns out that the interfacial donor/acceptor charge transfer state can be largely circumvented due to the presence of charge transfer excitons. However, the latter states in turn act as a trap, such that the free carrier yield observed on ultrafast time scales is tangibly reduced. The present analysis underscores the complexity of the transfer pathways at P3HT-PCBM type junctions.

  17. High-surface-area architectures for improved charge transfer kinetics at the dark electrode in dye-sensitized solar cells.

    PubMed

    Hoffeditz, William L; Katz, Michael J; Deria, Pravas; Martinson, Alex B F; Pellin, Michael J; Farha, Omar K; Hupp, Joseph T

    2014-06-11

    Dye-sensitized solar cell (DSC) redox shuttles other than triiodide/iodide have exhibited significantly higher charge transfer resistances at the dark electrode. This often results in poor fill factor, a severe detriment to device performance. Rather than moving to dark electrodes of untested materials that may have higher catalytic activity for specific shuttles, the surface area of platinum dark electrodes could be increased, improving the catalytic activity by simply presenting more catalyst to the shuttle solution. A new copper-based redox shuttle that experiences extremely high charge-transfer resistance at conventional Pt dark electrodes yields cells having fill-factors of less than 0.3. By replacing the standard Pt dark electrode with an inverse opal Pt electrode fabricated via atomic layer deposition, the dark electrode surface area is boosted by ca. 50-fold. The resulting increase in interfacial electron transfer rate (decrease in charge-transfer resistance) nearly doubles the fill factor and therefore the overall energy conversion efficiency, illustrating the utility of this high-area electrode for DSCs.

  18. Photon induced non-linear quantized double layer charging in quaternary semiconducting quantum dots.

    PubMed

    Nair, Vishnu; Ananthoju, Balakrishna; Mohapatra, Jeotikanta; Aslam, M

    2018-03-15

    Room temperature quantized double layer charging was observed in 2 nm Cu 2 ZnSnS 4 (CZTS) quantum dots. In addition to this we observed a distinct non-linearity in the quantized double layer charging arising from UV light modulation of double layer. UV light irradiation resulted in a 26% increase in the integral capacitance at the semiconductor-dielectric (CZTS-oleylamine) interface of the quantum dot without any change in its core size suggesting that the cause be photocapacitive. The increasing charge separation at the semiconductor-dielectric interface due to highly stable and mobile photogenerated carriers cause larger electrostatic forces between the quantum dot and electrolyte leading to an enhanced double layer. This idea was supported by a decrease in the differential capacitance possible due to an enhanced double layer. Furthermore the UV illumination enhanced double layer gives us an AC excitation dependent differential double layer capacitance which confirms that the charging process is non-linear. This ultimately illustrates the utility of a colloidal quantum dot-electrolyte interface as a non-linear photocapacitor. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Opposites Attract: Organic Charge Transfer Salts

    ERIC Educational Resources Information Center

    van de Wouw, Heidi L.; Chamorro, Juan; Quintero, Michael; Klausen, Rebekka S.

    2015-01-01

    A laboratory experiment is described that introduces second-year undergraduate organic chemistry students to organic electronic materials. The discovery of metallic conductivity in the charge transfer salt tetrathiafulvalene tetracyanoquinodimethane (TTF-TCNQ) is a landmark result in the history of organic electronics. The charge transfer…

  20. Influence of the charge double layer on solid oxide fuel cell stack behavior

    NASA Astrophysics Data System (ADS)

    Whiston, Michael M.; Bilec, Melissa M.; Schaefer, Laura A.

    2015-10-01

    While the charge double layer effect has traditionally been characterized as a millisecond phenomenon, longer timescales may be possible under certain operating conditions. This study simulates the dynamic response of a previously developed solid oxide fuel cell (SOFC) stack model that incorporates the charge double layer via an equivalent circuit. The model is simulated under step load changes. Baseline conditions are first defined, followed by consideration of minor and major deviations from the baseline case. This study also investigates the behavior of the SOFC stack with a relatively large double layer capacitance value, as well as operation of the SOFC stack under proportional-integral (PI) control. Results indicate that the presence of the charge double layer influences the SOFC stack's settling time significantly under the following conditions: (i) activation and concentration polarizations are significantly increased, or (ii) a large value of the double layer capacitance is assumed. Under normal (baseline) operation, on the other hand, the charge double layer effect diminishes within milliseconds, as expected. It seems reasonable, then, to neglect the charge double layer under normal operation. However, careful consideration should be given to potential variations in operation or material properties that may give rise to longer electrochemical settling times.

  1. Pion single and double charge exchange in the resonance region: Dynamical corrections

    NASA Astrophysics Data System (ADS)

    Johnson, Mikkel B.; Siciliano, E. R.

    1983-04-01

    We consider pion-nucleus elastic scattering and single- and double-charge-exchange scattering to isobaric analog states near the (3,3) resonance within an isospin invariant framework. We extend previous theories by introducing terms into the optical potential U that are quadratic in density and consistent with isospin invariance of the strong interaction. We study the sensitivity of single and double charge exchange angular distributions to parameters of the second-order potential both numerically, by integrating the Klein-Gordon equation, and analytically, by using semiclassical approximations that explicate the dependence of the exact numerical results to the parameters of U. The magnitude and shape of double charge exchange angular distributions are more sensitive to the isotensor term in U than has been hitherto appreciated. An examination of recent experimental data shows that puzzles in the shape of the 18O(π+, π-)18Ne angular distribution at 164 MeV and in the A dependence of the forward double charge exchange scattering on 18O, 26Mg, 42Ca, and 48Ca at the same energy may be resolved by adding an isotensor term in U. NUCLEAR REACTIONS Scattering theory for elastic, single-, and double-charge-exchange scattering to IAS in the region of the P33 resonance. Second-order effects on charge-exchange calculations of σ(A, θ).

  2. What Controls the Rate of Ultrafast Charge Transfer and Charge Separation Efficiency in Organic Photovoltaic Blends.

    PubMed

    Jakowetz, Andreas C; Böhm, Marcus L; Zhang, Jiangbin; Sadhanala, Aditya; Huettner, Sven; Bakulin, Artem A; Rao, Akshay; Friend, Richard H

    2016-09-14

    In solar energy harvesting devices based on molecular semiconductors, such as organic photovoltaics (OPVs) and artificial photosynthetic systems, Frenkel excitons must be dissociated via charge transfer at heterojunctions to yield free charges. What controls the rate and efficiency of charge transfer and charge separation is an important question, as it determines the overall power conversion efficiency (PCE) of these systems. In bulk heterojunctions between polymer donor and fullerene acceptors, which provide a model system to understand the fundamental dynamics of electron transfer in molecular systems, it has been established that the first step of photoinduced electron transfer can be fast, of order 100 fs. But here we report the first study which correlates differences in the electron transfer rate with electronic structure and morphology, achieved with sub-20 fs time resolution pump-probe spectroscopy. We vary both the fullerene substitution and donor/fullerene ratio which allow us to control both aggregate size and the energetic driving force for charge transfer. We observe a range of electron transfer times from polymer to fullerene, from 240 fs to as short as 37 fs. Using ultrafast electro-optical pump-push-photocurrent spectroscopy, we find the yield of free versus bound charges to be weakly dependent on the energetic driving force, but to be very strongly dependent on fullerene aggregate size and packing. Our results point toward the importance of state accessibility and charge delocalization and suggest that energetic offsets between donor and acceptor levels are not an important criterion for efficient charge generation. This provides design rules for next-generation materials to minimize losses related to driving energy and boost PCE.

  3. Variationally consistent approximation scheme for charge transfer

    NASA Technical Reports Server (NTRS)

    Halpern, A. M.

    1978-01-01

    The author has developed a technique for testing various charge-transfer approximation schemes for consistency with the requirements of the Kohn variational principle for the amplitude to guarantee that the amplitude is correct to second order in the scattering wave functions. Applied to Born-type approximations for charge transfer it allows the selection of particular groups of first-, second-, and higher-Born-type terms that obey the consistency requirement, and hence yield more reliable approximation to the amplitude.

  4. Organic doping of rotated double layer graphene

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

    George, Lijin; Jaiswal, Manu, E-mail: manu.jaiswal@iitm.ac.in

    2016-05-06

    Charge transfer techniques have been extensively used as knobs to tune electronic properties of two- dimensional systems, such as, for the modulation of conductivity \\ mobility of single layer graphene and for opening the bandgap in bilayer graphene. The charge injected into the graphene layer shifts the Fermi level away from the minimum density of states point (Dirac point). In this work, we study charge transfer in rotated double-layer graphene achieved by the use of organic dopant, Tetracyanoquinodimethane. Naturally occurring bilayer graphene has a well-defined A-B stacking whereas in rotated double-layer the two graphene layers are randomly stacked with differentmore » rotational angles. This rotation is expected to significantly alter the interlayer interaction. Double-layer samples are prepared using layer-by-layer assembly of chemical vapor deposited single-layer graphene and they are identified by characteristic resonance in the Raman spectrum. The charge transfer and distribution of charges between the two graphene layers is studied using Raman spectroscopy and the results are compared with that for single-layer and A-B stacked bilayer graphene doped under identical conditions.« less

  5. Pressure-induced emission band separation of the hybridized local and charge transfer excited state in a TPE-based crystal.

    PubMed

    Liu, Xuedan; Li, Aisen; Xu, Weiqing; Ma, Zhiyong; Jia, Xinru

    2018-05-08

    We herein report a newly synthesized simple molecule, named TPE[double bond, length as m-dash]C4, with twisted D-A structure. TPE[double bond, length as m-dash]C4 showed two intrinsic emission bands ascribed to the locally excited (LE) state and the intramolecular charge transfer (ICT) state, respectively. In the crystal state, the LE emission band is usually observed. However, by applying hydrostatic pressure to the powder sample and the single crystal sample of TPE[double bond, length as m-dash]C4, dual-fluorescence (445 nm and 532 nm) was emerged under high pressure, owing to the pressure-induced emission band separation of the hybridized local and charge transfer excited state (HLCT). It is found that the emission of TPE[double bond, length as m-dash]C4 is generally determined by the ratio of the LE state to the ICT state. The ICT emission band is much more sensitive to the external pressure than the LE emission band. The HLCT state leads to a sample with different responsiveness to grinding and hydrostatic pressure. This study is of significance in the molecular design of such D-A type molecules and in the control of photoluminescence features by molecular structure. Such results are expected to pave a new way to further understand the relationship between the D-A molecular structure and stimuli-responsive properties.

  6. Interfacial charge transfer absorption: Application to metal molecule assemblies

    NASA Astrophysics Data System (ADS)

    Creutz, Carol; Brunschwig, Bruce S.; Sutin, Norman

    2006-05-01

    Optically induced charge transfer between adsorbed molecules and a metal electrode was predicted by Hush to lead to new electronic absorption features, but has been only rarely observed experimentally. Interfacial charge transfer absorption (IFCTA) provides information concerning the barriers to charge transfer between molecules and the metal/semiconductor and the magnitude of the electronic coupling and could thus provide a powerful tool for understanding interfacial charge-transfer kinetics. Here, we utilize a previously published model [C. Creutz, B.S. Brunschwig, N. Sutin, J. Phys. Chem. B 109 (2005) 10251] to predict IFCTA spectra of metal-molecule assemblies and compare the literature observations to these predictions. We conclude that, in general, the electronic coupling between molecular adsorbates and the metal levels is so small that IFCTA is not detectable. However, few experiments designed to detect IFCTA have been done. We suggest approaches to optimizing the conditions for observing the process.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Charge-transfer channel in quantum dot-graphene hybrid materials

    NASA Astrophysics Data System (ADS)

    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.

  9. Charge-transfer channel in quantum dot-graphene hybrid materials.

    PubMed

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

    2018-04-06

    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 Cd 13 Se 13 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.

  10. Voltage and frequency dependence of prestin-associated charge transfer

    PubMed Central

    Sun, Sean X.; Farrell, Brenda; Chana, Matthew S.; Oster, George; Brownell, William E.; Spector, Alexander A.

    2009-01-01

    Membrane protein prestin is a critical component of the motor complex that generates forces and dimensional changes in cells in response to changes in the cell membrane potential. In its native cochlear outer hair cell, prestin is crucial to the amplification and frequency selectivity of the mammalian ear up to frequencies of tens of kHz. Other cells transfected with prestin acquire voltage-dependent properties similar to those of the native cell. The protein performance is critically dependent on chloride ions, and intrinsic protein charges also play a role. We propose an electro-diffusion model to reveal the frequency and voltage dependence of electric charge transfer by prestin. The movement of the combined charge (i.e., anion and protein charges) across the membrane is described with a Fokker-Planck equation coupled to a kinetic equation that describes the binding of chloride ions to prestin. We found a voltage-and frequency-dependent phase shift between the transferred charge and the applied electric field that determines capacitive and resistive components of the transferred charge. The phase shift monotonically decreases from zero to -90 degree as a function of frequency. The capacitive component as a function of voltage is bell-shaped, and decreases with frequency. The resistive component is bell-shaped for both voltage and frequency. The capacitive and resistive components are similar to experimental measurements of charge transfer at high frequencies. The revealed nature of the transferred charge can help reconcile the high-frequency electrical and mechanical observations associated with prestin, and it is important for further analysis of the structure and function of this protein. PMID:19490917

  11. Through-Space Intervalence Charge Transfer as a Mechanism for Charge Delocalisation in Metal-Organic Frameworks.

    PubMed

    Hua, Carol; Doheny, Patrick William; Ding, Bowen; Chan, Bun; Yu, Michelle; Kepert, Cameron J; D'Alessandro, Deanna M

    2018-05-04

    Understanding the nature of charge transfer mechanisms in 3-dimensional Metal-Organic Frameworks (MOFs) is an important goal owing to the possibility of harnessing this knowledge to design conductive frameworks. These materials have been implicated as the basis for the next generation of technological devices for applications in energy storage and conversion, including electrochromic devices, electrocatalysts, and battery materials. After nearly two decades of intense research into MOFs, the mechanisms of charge transfer remain relatively poorly understood, and new strategies to achieve charge mobility remain elusive and challenging to experimentally explore, validate and model. We now demonstrate that aromatic stacking interactions in Zn(II) frameworks containing cofacial thiazolo[5,4-d]thiazole units lead to a mixed-valence state upon electrochemical or chemical reduction. This through-space Intervalence Charge Transfer (IVCT) phenomenon represents a new mechanism for charge delocalisation in MOFs. Computational modelling of the optical data combined with application of Marcus-Hush theory to the IVCT bands for the mixed-valence framework has enabled quantification of the degree of delocalisation using both in situ and ex situ electro- and spectro-electrochemical methods. A distance dependence for the through-space electron transfer has also been identified on the basis of experimental studies and computational calculations. This work provides a new window into electron transfer phenomena in 3-dimensional coordination space, of relevance to electroactive MOFs where new mechanisms for charge transfer are highly sought after, and to understanding biological light harvesting systems where through-space mixed-valence interactions are operative.

  12. Spacecraft Charging in Geostationary Transfer Orbit

    NASA Technical Reports Server (NTRS)

    Parker, Linda Neergaard; Minow, Joseph I.

    2014-01-01

    The 700 km x 5.8 Re orbit of the two Van Allen Probes spacecraft provide a unique opportunity to investigate spacecraft charging in geostationary transfer orbits. We use records from the Helium Oxygen Proton Electron (HOPE) plasma spectrometer to identify candidate surface charging events based on the "ion line" charging signature in the ion records. We summarize the energetic particle environment and the conditions necessary for charging to occur in this environment. We discuss the altitude, duration, and magnitude of events observed in the Van Allen Probes from the beginning of the mission to present time. In addition, we explore what information the dual satellites provide on the spatial and temporal variations in the charging environments.

  13. Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

    PubMed

    Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

    2012-10-04

    Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

  14. Manipulating quantum coherence of charge states in interacting double-dot Aharonov–Bohm interferometers

    NASA Astrophysics Data System (ADS)

    Jin, Jinshuang; Wang, Shikuan; Zhou, Jiahuan; Zhang, Wei-Min; Yan, YiJing

    2018-04-01

    We investigate the dynamics of charge-state coherence in a degenerate double-dot Aharonov–Bohm interferometer with finite inter-dot Coulomb interactions. The quantum coherence of the charge states is found to be sensitive to the transport setup configurations, involving both the single-electron impurity channels and the Coulomb-assisted ones. We numerically demonstrate the emergence of a complete coherence between the two charge states, with the relative phase being continuously controllable through the magnetic flux. Interestingly, a fully coherent charge qubit arises at the double-dots electron pair tunneling resonance condition, where the chemical potential of one electrode is tuned at the center between a single-electron impurity channel and the related Coulomb-assisted channel. This pure quantum state of charge qubit could be experimentally realized at the current–voltage characteristic turnover position, where differential conductance sign changes. We further elaborate the underlying mechanism for both the real-time and the stationary charge-states coherence in the double-dot systems of study.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Effects of Charge-Transfer Excitons on the Photophysics of Organic Semiconductors

    NASA Astrophysics Data System (ADS)

    Hestand, Nicholas J.

    The field of organic electronics has received considerable attention over the past several years due to the promise of novel electronic materials that are cheap, flexible and light weight. While some devices based on organic materials have already emerged on the market (e.g. organic light emitting diodes), a deeper understanding of the excited states within the condensed phase is necessary both to improve current commercial products and to develop new materials for applications that are currently in the commercial pipeline (e.g. organic photovoltaics, wearable displays, and field effect transistors). To this end, a model for pi-conjugated molecular aggregates and crystals is developed and analyzed. The model considers two types of electronic excitations, namely Frenkel and charge-transfer excitons, both of which play a prominent role in determining the nature of the excited states within tightly-packed organic systems. The former consist of an electron-hole pair bound to the same molecule while in the later the electron and hole are located on different molecules. The model also considers the important nuclear reorganization that occurs when the system switches between electronic states. This is achieved using a Holstein-style Hamiltonian that includes linear vibronic coupling of the electronic states to the nuclear motion associated with the high frequency vinyl-stretching and ring-breathing modes. Analysis of the model reveals spectroscopic signatures of charge-transfer mediated J- and H-aggregation in systems where the photophysical properties are determined primarily by charge-transfer interactions. Importantly, such signatures are found to be sensitive to the relative phase of the intermolecular electron and hole transfer integrals, and the relative energy of the Frenkel and charge-transfer states. When the charge-transfer integrals are in phase and the energy of the charge-transfer state is higher than the Frenkel state, the system exhibits J

  17. Charge Transfer and Catalysis at the Metal Support Interface

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

    Baker, Lawrence Robert

    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 catalyticmore » reaction kinetics.« less

  18. Effects of image charges, interfacial charge discreteness, and surface roughness on the zeta potential of spherical electric double layers.

    PubMed

    Gan, Zecheng; Xing, Xiangjun; Xu, Zhenli

    2012-07-21

    We investigate the effects of image charges, interfacial charge discreteness, and surface roughness on spherical electric double layer structures in electrolyte solutions with divalent counterions in the setting of the primitive model. By using Monte Carlo simulations and the image charge method, the zeta potential profile and the integrated charge distribution function are computed for varying surface charge strengths and salt concentrations. Systematic comparisons were carried out between three distinct models for interfacial charges: (1) SURF1 with uniform surface charges, (2) SURF2 with discrete point charges on the interface, and (3) SURF3 with discrete interfacial charges and finite excluded volume. By comparing the integrated charge distribution function and the zeta potential profile, we argue that the potential at the distance of one ion diameter from the macroion surface is a suitable location to define the zeta potential. In SURF2 model, we find that image charge effects strongly enhance charge inversion for monovalent interfacial charges, and strongly suppress charge inversion for multivalent interfacial charges. For SURF3, the image charge effect becomes much smaller. Finally, with image charges in action, we find that excluded volumes (in SURF3) suppress charge inversion for monovalent interfacial charges and enhance charge inversion for multivalent interfacial charges. Overall, our results demonstrate that all these aspects, i.e., image charges, interfacial charge discreteness, their excluding volumes, have significant impacts on zeta potentials of electric double layers.

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

    NASA Astrophysics Data System (ADS)

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

    2017-11-01

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

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

    PubMed

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

    2017-11-29

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

  1. Charge Transfer Rate in Collisions of H + Ions with Si Atoms

    NASA Astrophysics Data System (ADS)

    Kimura, M.; Sannigrahi, A. B.; Gu, J. P.; Hirsch, G.; Buenker, R. J.; Shimamura, I.

    1996-12-01

    Charge transfer in Si(3P, 1D) + H+ collisions is studied theoretically by using a semiclassical molecular representation with six molecular channels for the triplet manifold and four channels for the singlet manifold at collision energies above 30 eV, and by using a fully quantum mechanical approach with two molecular channels for both triplet and singlet manifolds below 30 eV. The ab initio potential curves and nonadiabatic coupling matrix elements for the HSi+ system are obtained from multireference single- and double-excitation configuration interaction (MRD-CI) calculations employing a relatively large basis set. The present rate coefficients for charge transfer to Si+(4P) formation resulting from H+ + Si(3P) collisions are found to be large with values from 1 x 10-10 cm-3 s-1 at 1000 K to 1 x 10-8 cm-3 s-1 at 100,000 K. The rate coefficient for Si+(2P) formation, resulting from H+ + Si(3P) collisions, is found to be much smaller because of a larger energy defect from the initial state. These calculated rates are much larger than those reported by Baliunas & Butler, who estimated a value of 10-11 cm-3 s-1 in their coronal plasma study. The present result may be relevant to the description of the silicon ionization equilibrium.

  2. DDT: participation in ultraviolet-detectable, charge-transfer complexation.

    PubMed

    Wilson, W E; Fishbein, L; Clements, S T

    1971-01-15

    The chlorophenyl groups of DDT and several of its metabolites are capable of participating in a charge-transfer interaction with tetracyanoethylene detectable in the ultraviolet region of the spectrum. In addition, during a change of state DDT undergoes ultraviolet spectral alterations that closely resemble those previously claimed to support the hypothesis suggesting charge-transfer interaction between this pesticide and a component of insect nerve tissue. The pesticide DDT possesses structural characteristics that would permit it to participate in several types of molecular association.

  3. Dielectric spectroscopy on organic charge-transfer salts

    NASA Astrophysics Data System (ADS)

    Lunkenheimer, P.; Loidl, A.

    2015-09-01

    This topical review provides an overview of the dielectric properties of a variety of organic charge-transfer salts, based on both, data reported in literature and our own experimental results. Moreover, we discuss in detail the different processes that can contribute to the dielectric response of these materials. We concentrate on the family of the 1D (TMTTF)2 X systems and the 2D BEDT-TTF-based charge-transfer salts, which in recent years have attracted considerable interest due to their often intriguing dielectric properties. We will mainly focus on the occurrence of electronic ferroelectricity in these systems, which also includes examples of multiferroicity.

  4. Dielectric spectroscopy on organic charge-transfer salts.

    PubMed

    Lunkenheimer, P; Loidl, A

    2015-09-23

    This topical review provides an overview of the dielectric properties of a variety of organic charge-transfer salts, based on both, data reported in literature and our own experimental results. Moreover, we discuss in detail the different processes that can contribute to the dielectric response of these materials. We concentrate on the family of the 1D (TMTTF)2 X systems and the 2D BEDT-TTF-based charge-transfer salts, which in recent years have attracted considerable interest due to their often intriguing dielectric properties. We will mainly focus on the occurrence of electronic ferroelectricity in these systems, which also includes examples of multiferroicity.

  5. Frenkel versus charge-transfer exciton dispersion in molecular crystals

    NASA Astrophysics Data System (ADS)

    Cudazzo, Pierluigi; Gatti, Matteo; Rubio, Angel; Sottile, Francesco

    2013-11-01

    By solving the many-body Bethe-Salpeter equation at finite momentum transfer, we characterize the exciton dispersion in two prototypical molecular crystals, picene and pentacene, in which localized Frenkel excitons compete with delocalized charge-transfer excitons. We explain the exciton dispersion on the basis of the interplay between electron and hole hopping and electron-hole exchange interaction, unraveling a simple microscopic description to distinguish Frenkel and charge-transfer excitons. This analysis is general and can be applied to other systems in which the electron wave functions are strongly localized, as in strongly correlated insulators.

  6. DNA Damage by Ionizing Radiation: Tandem Double Lesions by Charged Particles

    NASA Technical Reports Server (NTRS)

    Huo, Winifred M.; Chaban, Galina M.; Wang, Dunyou; Dateo, Christopher E.

    2005-01-01

    Oxidative damages by ionizing radiation are the source of radiation-induced carcinogenesis, damage to the central nervous system, lowering of the immune response, as well as other radiation-induced damages to human health. Monte Carlo track simulations and kinetic modeling of radiation damages to the DNA employ available molecular and cellular data to simulate the biological effect of high and low LET radiation io the DNA. While the simulations predict single and double strand breaks and base damages, so far all complex lesions are the result of stochastic coincidence from independent processes. Tandem double lesions have not yet been taken into account. Unlike the standard double lesions that are produced by two separate attacks by charged particles or radicals, tandem double lesions are produced by one single attack. The standard double lesions dominate at the high dosage regime. On the other hand, tandem double lesions do not depend on stochastic coincidences and become important at the low dosage regime of particular interest to NASA. Tandem double lesions by hydroxyl radical attack of guanine in isolated DNA have been reported at a dosage of radiation as low as 10 Gy. The formation of two tandem base lesions was found to be linear with the applied doses, a characteristic of tandem lesions. However, tandem double lesions from attack by a charged particle have not been reported.

  7. Laboratory Studies of Thermal Energy Charge Transfer of Multiply Charged Ions in Astrophysical Plasmas

    NASA Technical Reports Server (NTRS)

    Kwong, Victor H. S.

    2003-01-01

    The laser ablation/ion storage facility at the UNLV Physics Department has been dedicated to the study of atomic and molecular processes in low temperature plasmas. Our program focuses on the charge transfer (electron capture) of multiply charged ions and neutrals important in astrophysics. The electron transfer reactions with atoms and molecules is crucial to the ionization condition of neutral rich photoionized plasmas. With the successful deployment of the Far Ultraviolet Spectroscopic Explorer (FUSE) and the Chandra X-ray Observatory by NASA high resolution VUV and X-ray emission spectra fiom various astrophysical objects have been collected. These spectra will be analyzed to determine the source of the emission and the chemical and physical environment of the source. The proper interpretation of these spectra will require complete knowledge of all the atomic processes in these plasmas. In a neutral rich environment, charge transfer can be the dominant process. The rate coefficients need to be known accurately. We have also extended our charge transfer measurements to KeV region with a pulsed ion beam. The inclusion of this facility into our current program provides flexibility in extending the measurement to higher energies (KeV) if needed. This flexibility enables us to address issues of immediate interest to the astrophysical community as new observations are made by high resolution space based observatories.

  8. Intramolecular Charge Transfer States in the Condensed Phase

    NASA Astrophysics Data System (ADS)

    Williams, C. F.; Herbert, J. M.

    2009-06-01

    Time-Dependent Density Functional Theory (TDDFT) with long range corrected functionals can give accurate results for the energies of electronically excited states involving Intramolecular Charge Transfer (ICT) in large molecules. If this is combined with a Molecular Mechanics (MM) representation of the surrounding solvent this technique can be used to interpret the results of condensed phase UV-Vis Spectroscopy. Often the MM region is represented by a set of point charges, however this means that the solvent cannot repolarize to adapt to the new charge distribution as a result of ICT and so the excitation energies to ICT states are overestimated. To solve this problem an algorithm that interfaces TDDFT with the polarizable force-field AMOEBA is presented; the effect of solvation on charge transfer in species such as 4,4'dimethylaminobenzonitrile (DMABN) is discussed. M.A. Rohrdanz, K.M. Martins, and J.M. Herbert, J. Chem. Phys. 130 034107 (2008).

  9. Enhancing SERS by Means of Supramolecular Charge Transfer

    NASA Technical Reports Server (NTRS)

    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.

  10. CCD charge collection efficiency and the photon transfer technique

    NASA Technical Reports Server (NTRS)

    Janesick, J.; Klaasen, K.; Elliott, T.

    1985-01-01

    The charge-coupled device (CCD) has shown unprecendented performance as a photon detector in the areas of spectral response, charge transfer, and readout noise. Recent experience indicates, however, that the full potential for the CCD's charge collection efficiency (CCE) lies well beyond that which is realized in currently available devices. A definition of CCE performance is presented and a standard test tool (the photon transfer technique) for measuring and optimizing this important CCD parameter is introduced. CCE characteristics for different types of CCDs are compared; the primary limitations in achieving high CCE performance are discussed, and the prospects for future improvement are outlined.

  11. Charge transfer in model peptides: obtaining Marcus parameters from molecular simulation.

    PubMed

    Heck, Alexander; Woiczikowski, P Benjamin; Kubař, Tomáš; Giese, Bernd; Elstner, Marcus; Steinbrecher, Thomas B

    2012-02-23

    Charge transfer within and between biomolecules remains a highly active field of biophysics. Due to the complexities of real systems, model compounds are a useful alternative to study the mechanistic fundamentals of charge transfer. In recent years, such model experiments have been underpinned by molecular simulation methods as well. In this work, we study electron hole transfer in helical model peptides by means of molecular dynamics simulations. A theoretical framework to extract Marcus parameters of charge transfer from simulations is presented. We find that the peptides form stable helical structures with sequence dependent small deviations from ideal PPII helices. We identify direct exposure of charged side chains to solvent as a cause of high reorganization energies, significantly larger than typical for electron transfer in proteins. This, together with small direct couplings, makes long-range superexchange electron transport in this system very slow. In good agreement with experiment, direct transfer between the terminal amino acid side chains can be dicounted in favor of a two-step hopping process if appropriate bridging groups exist. © 2012 American Chemical Society

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

    PubMed

    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.

  13. Energy and charge transfer in nanoscale hybrid materials.

    PubMed

    Basché, Thomas; Bottin, Anne; Li, Chen; Müllen, Klaus; Kim, Jeong-Hee; Sohn, Byeong-Hyeok; Prabhakaran, Prem; Lee, Kwang-Sup

    2015-06-01

    Hybrid materials composed of colloidal semiconductor quantum dots and π-conjugated organic molecules and polymers have attracted continuous interest in recent years, because they may find applications in bio-sensing, photodetection, and photovoltaics. Fundamental processes occurring in these nanohybrids are light absorption and emission as well as energy and/or charge transfer between the components. For future applications it is mandatory to understand, control, and optimize the wide parameter space with respect to chemical assembly and the desired photophysical properties. Accordingly, different approaches to tackle this issue are described here. Simple organic dye molecules (Dye)/quantum dot (QD) conjugates are studied with stationary and time-resolved spectroscopy to address the dynamics of energy and ultra-fast charge transfer. Micellar as well as lamellar nanostructures derived from diblock copolymers are employed to fine-tune the energy transfer efficiency of QD donor/dye acceptor couples. Finally, the transport of charges through organic components coupled to the quantum dot surface is discussed with an emphasis on functional devices. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product

    NASA Astrophysics Data System (ADS)

    Zhang, Song; Sun, Simei; Zhou, Miaomiao; Wang, Lian; Zhang, Bing

    2017-02-01

    We investigated the mechanism of intramolecular charge transfer and the following radiationless dynamics of the excited states of 1-aminoanthraquinone using steady state and time-resolved absorption spectroscopy combined with quantum chemical calculations. Following photoexcitation with 460 nm, conformational relaxation via twisting of the amino group, charge transfer and the intersystem crossing (ISC) processes have been established to be the major relaxation pathways responsible for the ultrafast nonradiative of the excited S1 state. Intramolecular proton transfer, which could be induced by intramolecular hydrogen bonding is inspected and excluded. Time-dependent density functional theory (TDDFT) calculations reveal the change of the dipole moments of the S0 and S1 states along the twisted coordinate of the amino group, indicating the mechanism of twisted intra-molecular charge transfer (TICT). The timescale of TICT is measured to be 5 ps due to the conformational relaxation and a barrier on the S1 potential surface. The ISC from the S1 state to the triplet manifold is a main deactivation pathway with the decay time of 28 ps. Our results observed here have yield a physically intuitive and complete picture of the photoinduced charge transfer and radiationless dynamics in anthraquinone pharmaceutial products.

  15. Coupled electron-nuclear dynamics: Charge migration and charge transfer initiated near a conical intersection

    NASA Astrophysics Data System (ADS)

    Mendive-Tapia, David; Vacher, Morgane; Bearpark, Michael J.; Robb, Michael A.

    2013-07-01

    Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conical intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D6h Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D2 eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D1, D2 (N+-Phenyl, N-Phenyl+). If the Ehrenfest propagation is started near this point, using the sudden approximation without coupled nuclear motion, one observes an

  16. Large Ice Crystal Charge Transfer Studies

    DTIC Science & Technology

    1988-10-28

    electrification. However, the extra- polation using qcd 4 was completely unjustified. With corrected values of the separation probability of ice crystals...contact to leak away from the local area or become trapped in the crystal lattice . Obviously, larger initial charge transfers, with larger 6 crystals

  17. On the calculation of charge transfer transitions with standard density functionals using constrained variational density functional theory.

    PubMed

    Ziegler, Tom; Krykunov, Mykhaylo

    2010-08-21

    It is well known that time-dependent density functional theory (TD-DFT) based on standard gradient corrected functionals affords both a quantitative and qualitative incorrect picture of charge transfer transitions between two spatially separated regions. It is shown here that the well known failure can be traced back to the use of linear response theory. Further, it is demonstrated that the inclusion of higher order terms readily affords a qualitatively correct picture even for simple functionals based on the local density approximation. The inclusion of these terms is done within the framework of a newly developed variational approach to excitation energies called constrained variational density functional theory (CV-DFT). To second order [CV(2)-DFT] this theory is identical to adiabatic TD-DFT within the Tamm-Dancoff approximation. With inclusion of fourth order corrections [CV(4)-DFT] it affords a qualitative correct description of charge transfer transitions. It is finally demonstrated that the relaxation of the ground state Kohn-Sham orbitals to first order in response to the change in density on excitation together with CV(4)-DFT affords charge transfer excitations in good agreement with experiment. The new relaxed theory is termed R-CV(4)-DFT. The relaxed scheme represents an effective way in which to introduce double replacements into the description of single electron excitations, something that would otherwise require a frequency dependent kernel.

  18. Optimisation of stability and charge transferability of ferrocene-encapsulated carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Prajongtat, Pongthep; Sriyab, Suwannee; Zentgraf, Thomas; Hannongbua, Supa

    2018-01-01

    Ferrocene-encapsulated carbon nanotubes (Fc@CNTs) became promising nanocomposite materials for a wide range of applications due to their superior catalytic, mechanical and electronic properties. To open up new windows of applications, the highly stable and charge transferable encapsulation complexes are required. In this work, we designed the new encapsulation complexes formed from ferrocene derivatives (FcR, where R = -CHO, -CH2OH, -CON3 and -PCl2) and single-walled carbon nanotubes (SWCNTs). The influence of diameter and chirality of the nanotubes on the stability, charge transferability and electronic properties of such complexes has been investigated using density functional theory. The calculations suggest that the encapsulation stability and charge transferability of the encapsulation complexes depend on the size and chirality of the nanotubes. FcR@SWCNTs are more stable than Fc@SWCNTs at the optimum tube diameter. The greatest charge transfer was observed for FcCH2OH@SWCNTs and Fc@SWCNTs since the Fe d levels of FcCH2OH and Fc are nearly equal and close to the Fermi energy level of the nanotubes. The obtained results pave the way to the design of new encapsulated ferrocene derivatives which can give rise to higher stability and charge transferability of the encapsulation complexes.

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

    USGS Publications Warehouse

    Sherman, David M.

    1987-01-01

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

  20. Charge Transfer from n-Doped Nanocrystals: Mimicking Intermediate Events in Multielectron Photocatalysis.

    PubMed

    Wang, Junhui; Ding, Tao; Wu, Kaifeng

    2018-06-12

    In multielectron photocatalytic reactions, an absorbed photon triggers charge transfer from the light-harvester to the attached catalyst, leaving behind a charge of the opposite sign in the light-harvester. If this charge is not scavenged before the absorption of the following photons, photoexcitation generates not neutral but charged excitons from which the extraction of charges should become more difficult. This is potentially an efficiency-limiting intermediate event in multielectron photocatalysis. To study the charge dynamics in this event, we doped CdS nanocrystal quantum dots (QDs) with an extra electron and measured hole transfer from n-doped QDs to attached acceptors. We find that the Auger decay of charged excitons lowers the charge separation yield to 68.6% from 98.4% for neutral excitons. In addition, the hole transfer rate in the presence of two electrons (1290 ps) is slower than that in the presence one electron (776 ps), and the recombination rate of charge separated states is about 2 times faster in the former case. This model study provides important insights into possible efficiency-limiting intermediate events involved in photocatalysis.

  1. Charge transfer transitions in optical spectra of NicMg1-cO oxides

    NASA Astrophysics Data System (ADS)

    Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Uimin, M. A.; Byzov, I. V.; Druzhinin, A. V.; Korolyov, A. V.; Kim, G. A.; Zatsepin, A. F.; Kuznetsova, J. A.

    2017-04-01

    Radiative recombination with charge transfer was observed in NicMg1-cO (c = 0.008) oxides over the 8-300 K temperature range. This recombination occurs as a result of strong hybridization of the Ni2+ ion 3d-states and the band states. The charge transfer radiation excitation spectrum shows vibrational LO repeats of two exciton lines having charge transfer energy intervals of about 35 meV. The NiO nanocrystal absorption spectrum shows two weak peaks with energies of 3.510 and 3.543 eV, which are highly dependent on temperature. They are interpreted as charge transfer excitons at the edge of NiO fundamental absorption. The distance between the charge transfer exciton lines in the NicMg1-cO oxide spectra are caused by spin-orbit splitting of the valence band peak that was formed by the p-states of the oxygen ion.

  2. Charge transfer efficiency improvement of 4T pixel for high speed CMOS image sensor

    NASA Astrophysics Data System (ADS)

    Jin, Xiangliang; Liu, Weihui; Yang, Hongjiao; Tang, Lizhen; Yang, Jia

    2015-03-01

    The charge transfer efficiency improvement method is proposed by optimizing the electrical potential distribution along the transfer path from the PPD to the FD. In this work, we present a non-uniform doped transfer transistor channel, with the adjustments to the overlap length between the CPIA layer and the transfer gate, and the overlap length between the SEN layer and transfer gate. Theory analysis and TCAD simulation results show that the density of the residual charge reduces from 1e11 /cm3 to 1e9 /cm3, and the transfer time reduces from 500 ns to 143 ns, and the charge transfer efficiency is about 77 e-/ns. This optimizing design effectively improves the charge transfer efficiency of 4T pixel and the performance of 4T high speed CMOS image sensor.

  3. Creating and optimizing interfaces for electric-field and photon-induced charge transfer.

    PubMed

    Park, Byoungnam; Whitham, Kevin; Cho, Jiung; Reichmanis, Elsa

    2012-11-27

    We create and optimize a structurally well-defined electron donor-acceptor planar heterojunction interface in which electric-field and/or photon-induced charge transfer occurs. Electric-field-induced charge transfer in the dark and exciton dissociation at a pentacene/PCBM interface were probed by in situ thickness-dependent threshold voltage shift measurements in field-effect transistor devices during the formation of the interface. Electric-field-induced charge transfer at the interface in the dark is correlated with development of the pentacene accumulation layer close to PCBM, that is, including interface area, and dielectric relaxation time in PCBM. Further, we demonstrate an in situ test structure that allows probing of both exciton diffusion length and charge transport properties, crucial for optimizing optoelectronic devices. Competition between the optical absorption length and the exciton diffusion length in pentacene governs exciton dissociation at the interface. Charge transfer mechanisms in the dark and under illumination are detailed.

  4. Charge transfer properties of pentacene adsorbed on silver: DFT study

    NASA Astrophysics Data System (ADS)

    N, Rekha T.; Rajkumar, Beulah J. M.

    2015-06-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Jurgensen, Charles Willard

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

  6. The mechanisms of delayed fluorescence in charge-transfer crystal of tetracyanobenzene-hexamethylbenzene

    NASA Astrophysics Data System (ADS)

    Kozankiewicz, B.; Prochorow, J.

    1989-08-01

    Fluorescence, phosphorescence and delayed fluorescence emission characteristics of tetracyanobenzene-hexamethylbenzene (TCNB-HMB) charge-transfer crystal have been studied in the 1.7-340 K temperature range. Delayed fluorescence, originating from heterogeneous triplet-triplet annihilation indicates the presence of mobile charge-transfer triplet excitons at a temperature as low as 1.7 K. However, the behaviour of triplet excitons in TCNB-HMB crystal is strongly controlled by a very efficient trapping process in the whole temperature range investigated. It was found that thermally activated delayed fluorescence, which is a dominating emission of the crystal at elevated temperatures (>60 K), has a different origin (a different initial state) at different temperatures. These observations were analysed and interpreted in terms of a photokinetic model, which is considered to be typical for charge-transfer crystals with high charge-transfer character of triplet excitons.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. Coupled electron-nuclear dynamics: Charge migration and charge transfer initiated near a conical intersection

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

    Mendive-Tapia, David; Vacher, Morgane; Bearpark, Michael J.

    Coupled electron-nuclear dynamics, implemented using the Ehrenfest method, has been used to study charge migration with fixed nuclei, together with charge transfer when nuclei are allowed to move. Simulations were initiated at reference geometries of neutral benzene and 2-phenylethylamine (PEA), and at geometries close to potential energy surface crossings in the cations. Cationic eigenstates, and the so-called sudden approximation, involving removal of an electron from a correlated ground-state wavefunction for the neutral species, were used as initial conditions. Charge migration without coupled nuclear motion could be observed if the Ehrenfest simulation, using the sudden approximation, was started near a conicalmore » intersection where the states were both strongly coupled and quasi-degenerate. Further, the main features associated with charge migration were still recognizable when the nuclear motion was allowed to couple. In the benzene radical cation, starting from the reference neutral geometry with the sudden approximation, one could observe sub-femtosecond charge migration with a small amplitude, which results from weak interaction with higher electronic states. However, we were able to engineer large amplitude charge migration, with a period between 10 and 100 fs, corresponding to oscillation of the electronic structure between the quinoid and anti-quinoid cationic electronic configurations, by distorting the geometry along the derivative coupling vector from the D{sub 6h} Jahn-Teller crossing to lower symmetry where the states are not degenerate. When the nuclear motion becomes coupled, the period changes only slightly. In PEA, in an Ehrenfest trajectory starting from the D{sub 2} eigenstate and reference geometry, a partial charge transfer occurs after about 12 fs near the first crossing between D{sub 1}, D{sub 2} (N{sup +}-Phenyl, N-Phenyl{sup +}). If the Ehrenfest propagation is started near this point, using the sudden approximation without

  10. Simulation of diffuse-charge capacitance in electric double layer capacitors

    NASA Astrophysics Data System (ADS)

    Sun, Ning; Gersappe, Dilip

    2017-01-01

    We use a Lattice Boltzmann Model (LBM) in order to simulate diffuse-charge dynamics in Electric Double Layer Capacitors (EDLCs). Simulations are carried out for both the charge and the discharge processes on 2D systems of complex random electrode geometries (pure random, random spheres and random fibers). The steric effect of concentrated solutions is considered by using a Modified Poisson-Nernst-Planck (MPNP) equations and compared with regular Poisson-Nernst-Planck (PNP) systems. The effects of electrode microstructures (electrode density, electrode filler morphology, filler size, etc.) on the net charge distribution and charge/discharge time are studied in detail. The influence of applied potential during discharging process is also discussed. Our studies show how electrode morphology can be used to tailor the properties of supercapacitors.

  11. Double-Resonance Facilitated Decomposion of Emission Spectra

    NASA Astrophysics Data System (ADS)

    Kato, Ryota; Ishikawa, Haruki

    2016-06-01

    Emission spectra provide us with rich information about the excited-state processes such as proton-transfer, charge-transfer and so on. In the cases that more than one excited states are involved, emission spectra from different excited states sometimes overlap and a decomposition of the overlapped spectra is desired. One of the methods to perform a decomposition is a time-resolved fluorescence technique. It uses a difference in time evolutions of components involved. However, in the gas-phase, a concentration of the sample is frequently too small to carry out this method. On the other hand, double-resonance technique is a very powerful tool to discriminate or identify a common species in the spectra in the gas-phase. Thus, in the present study, we applied the double-resonance technique to resolve the overlapped emission spectra. When transient IR absorption spectra of the excited state are available, we can label the population of the certain species by the IR excitation with a proper selection of the IR wavenumbers. Thus, we can obtain the emission spectra of labeled species by subtracting the emission spectra with IR labeling from that without IR. In the present study, we chose the charge-transfer emission spectra of cyanophenyldisilane (CPDS) as a test system. One of us reported that two charge-transfer (CT) states are involved in the intramolecular charge-transfer (ICT) process of CPDS-water cluster and recorded the transient IR spectra. As expected, we have succeeded in resolving the CT emission spectra of CPDS-water cluster by the double resonance facilitated decomposion technique. In the present paper, we will report the details of the experimental scheme and the results of the decomposition of the emission spectra. H. Ishikawa, et al., Chem. Phys. Phys. Chem., 9, 117 (2007).

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

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  13. Femtochemistry of Intramolecular Charge and Proton Transfer Reactions in Solution

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

    Douhal, Abderrazzak; Sanz, Mikel; Carranza, Maria Angeles

    2005-03-17

    We report on the first observation of ultrafast intramolecular charge- and proton-transfer reactions in 4'-dimethylaminoflavonol (DAMF) in solution. Upon femtosecond excitation of a non-planar structure of DMAF in apolar medium, the intramolecular charge transfer (ICT) does not occur, and a slow (2 ps) proton motion takes place. However, in polar solvents, the ICT is very fast (100-200 fs) and the produced structure is stabilized that proton motion takes place in few or tens of ps.

  14. Measurement techniques and applications of charge transfer to aerospace research

    NASA Technical Reports Server (NTRS)

    Smith, A.

    1978-01-01

    A technique of developing high-velocity low-intensity neutral gas beams for use in aerospace research problems is described. This technique involves ionization of gaseous species with a mass spectrometer and focusing the resulting primary ion beam into a collision chamber containing a static gas at a known pressure and temperature. Equations are given to show how charge-transfer cross sections are obtained from a total-current measurement technique. Important parameters are defined for the charge-transfer process.

  15. Efficient Auger Charge-Transfer Processes in ZnO

    NASA Astrophysics Data System (ADS)

    Stehr, J. E.; Chen, S. L.; Svensson, B. G.; Buyanova, I. A.; Chen, W. M.

    2018-05-01

    Photoluminescence and magneto-optical measurements are performed on a line peaking at 3.354 eV (labeled as NBX) in electron-irradiated ZnO. Even though the energy position of the NBX line is close to that for bound excitons in ZnO, it has distinctively different magneto-optical properties. Photoelectron paramagnetic resonance measurements reveal a connection and a charge-transfer process involving NBX and Fe and Al centers. The experimental results are explained within a model which assumes that the NBX is a neutral donor bound exciton at a defect center located near a Fe impurity and an Auger-type charge-transfer process occurs between NBX and Fe3 + . While the NBX dissociates, its hole is captured by an excited state of Fe3 + and the released energy is transferred to the NBX electron, which is excited to the conduction band and subsequently trapped by a substitutional AlZn shallow donor.

  16. Polyoxometalate active charge-transfer material for mediated redox flow battery

    DOEpatents

    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.

  17. Site energies and charge transfer rates near pentacene grain boundaries from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Kobayashi, Hajime; Tokita, Yuichi

    2015-03-01

    Charge transfer rates near pentacene grain boundaries are derived by calculating the site energies and transfer integrals of 37 pentacene molecules using first-principles calculations. The site energies decrease considerably near the grain boundaries, and electron traps of up to 300 meV and hole barriers of up to 400 meV are generated. The charge transfer rates across the grain boundaries are found to be reduced by three to five orders of magnitude with a grain boundary gap of 4 Å because of the reduction in the transfer integrals. The electron traps and hole barriers also reduce the electron and hole transfer rates by factors of up to 10 and 50, respectively. It is essential to take the site energies into consideration to determine charge transport near the grain boundaries. We show that the complex site energy distributions near the grain boundaries can be represented by an equivalent site energy difference, which is a constant for any charge transfer pass. When equivalent site energy differences are obtained for various grain boundary structures by first-principles calculations, the effects of the grain boundaries on the charge transfer rates are introduced exactly into charge transport simulations, such as the kinetic Monte Carlo method.

  18. The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

    DOE PAGES

    Wang, Han; Bang, Junhyeok; Sun, Yiyang; ...

    2016-05-10

    Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the

  19. The role of collective motion in the ultrafast charge transfer in van der Waals heterostructures

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

    Wang, Han; Bang, Junhyeok; Sun, Yiyang

    Here, the success of van der Waals (vdW) heterostructures, made of graphene, metal dichalcogenides, and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that vdW heterostructues can exhibit ultra-fast charge transfer despite the weak binding of the heterostructure. Using time-dependent density functional theory molecular dynamics, we identify a strong dynamic coupling between the vdW layers associated with charge transfer. This dynamic coupling results in rapid nonlinear coherentmore » charge oscillations which constitute a purely electronic phenomenon and are shown to be a general feature of vdW heterostructures provided they have a critical minimum dipole coupling. Application to MoS2/WS2 heterostructure yields good agreement with experiment, indicating near complete charge transfer within a timescale of 100 fs.The success of van der Waals heterostructures made of graphene, metal dichalcogenides and other layered materials, hinges on the understanding of charge transfer across the interface as the foundation for new device concepts and applications. In contrast to conventional heterostructures, where a strong interfacial coupling is essential to charge transfer, recent experimental findings indicate that van der Waals heterostructues can exhibit ultrafast charge transfer despite the weak binding of these heterostructures. Here we find, using time-dependent density functional theory molecular dynamics, that the collective motion of excitons at the interface leads to plasma oscillations associated with optical excitation. By constructing a simple model of the van der Waals heterostructure, we show that there exists an unexpected criticality of the oscillations, yielding rapid charge transfer across the

  20. The effect of charge transfer fluctuation on superconductivity in high temperature superconductors

    NASA Astrophysics Data System (ADS)

    Liu, Yihsuan; Wu, Huan-Kuang; Lee, Ting-Kuo

    H i g h - Tc Cuprates have been studied quite often as an effective one band t - J model that neglects charge fluctuation between oxygen 2p6 band and copper 3d10 band, and Zhang-Rice singlet is just a hole in the model. However, recent Scanning Tunneling Spectra(STS) measurement on underdoped Cuprate shows that charge transfer gap is only of order 12 eV. This small gap necessitates a re-examination of the charge transfer fluctuation. Here we modify the t-J model by including charge transfer fluctuation allowing the formation of doubly occupied sites. For certain parameters it is similar with the t-J-U model. This model is studied via variational Monte Carlo method(VMC). Our result shows that this model can give a unified behavior of superconducting dome with different long rang hopping parameters. The anti-correlation between charge transfer gap and pairing is also confirmed. More interestingly the charge fluctuation is found to affect pairing order parameter in different ways in underdoped and overdoped regions. This work is partially supported by Taiwan Ministry of Science and Technology with Grant. MOST 105-2112-M-001-008 and calculation was supported by a National Center of High Performance Computing in Taiwan.

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

    PubMed

    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.

  2. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

    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.

  3. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

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

  4. Active pixel sensor with intra-pixel charge transfer

    NASA Technical Reports Server (NTRS)

    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.

  5. Optical and thermal charge-transfer processes occurring in a series of three-centered, cyanide-bridged intervalent charge-transfer complexes

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

    Pfennig, B.W.; Bocarsly, A.B.

    1992-01-09

    The mixed-valent compound (Pt(NH{sub 3}){sub 4}){sub 2}((NC){sub 5}Fe-CN-Pt(NH{sub 3}){sub 4}-NC-Fe(CN){sub 5} was used as the starting point for the synthesis and characterization of two series of trinuclear {open_quotes}M-Pt-M{close_quotes} compounds. The first group of complexes have the general formula Na{sub 2}(L(NC){sub 4}Fe-CN-Pt(NH{sub 3}){sub 4}-NC-Fe(CN){sub 4}L) (where the sixth coordination site on the terminal iron units has been varied using six different substituted pyridine or pyrazine ligands, L), and the secondary group of compounds have the general formula (Pt(NH){sub 3}){sub 4}){sub 2}((NC){sub 5}M-CN-Pt(NH{sub 3}){sub 4}-NC-M(CN){sub 5}) (where M = Fe, Ru, and Os). All of the compounds yielded an absorption spectrum containingmore » an intervalent charge-transfer (IT) band in the visible. Both series of complexes were modeled using Marcus-Hush theory to estimate the reorganization energies for the optical electron-transfer processes, electron-transfer rate constants, thermal-activation barriers, and the degrees of delocalization of these species. In addition, the kinetics of formation, photochemical decomposition, and a novel solvent-gated charge-transfer process are discussed. 26 refs., 10 figs., 4 tabs.« less

  6. Quantum effects in energy and charge transfer in an artificial photosynthetic complex

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

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu.; Nori, Franco

    2011-06-28

    We investigate the quantum dynamics of energy and charge transfer in a wheel-shaped artificial photosynthetic antenna-reaction center complex. This complex consists of six light-harvesting chromophores and an electron-acceptor fullerene. To describe quantum effects on a femtosecond time scale, we derive the set of exact non-Markovian equations for the Heisenberg operators of this photosynthetic complex in contact with a Gaussian heat bath. With these equations we can analyze the regime of strong system-bath interactions, where reorganization energies are of the order of the intersite exciton couplings. We show that the energy of the initially excited antenna chromophores is efficiently funneled tomore » the porphyrin-fullerene reaction center, where a charge-separated state is set up in a few picoseconds, with a quantum yield of the order of 95%. In the single-exciton regime, with one antenna chromophore being initially excited, we observe quantum beatings of energy between two resonant antenna chromophores with a decoherence time of {approx}100 fs. We also analyze the double-exciton regime, when two porphyrin molecules involved in the reaction center are initially excited. In this regime we obtain pronounced quantum oscillations of the charge on the fullerene molecule with a decoherence time of about 20 fs (at liquid nitrogen temperatures). These results show a way to directly detect quantum effects in artificial photosynthetic systems.« less

  7. Competing charge transfer pathways at the photosystem II-electrode interface

    PubMed Central

    Zhang, Jenny Z.; Sokol, Katarzyna P.; Paul, Nicholas; Romero, Elisabet; van Grondelle, Rienk; Reisner, Erwin

    2016-01-01

    The integration of the water-oxidation enzyme, photosystem II (PSII), into electrodes allows the electrons extracted from water-oxidation to be harnessed for enzyme characterization and driving novel endergonic reactions. However, PSII continues to underperform in integrated photoelectrochemical systems despite extensive optimization efforts. Here, we performed protein-film photoelectrochemistry on spinach and Thermosynechococcus elongatus PSII, and identified a competing charge transfer pathway at the enzyme-electrode interface that short-circuits the known water-oxidation pathway: photo-induced O2 reduction occurring at the chlorophyll pigments. This undesirable pathway is promoted by the embedment of PSII in an electron-conducting matrix, a common strategy of enzyme immobilization. Anaerobicity helps to recover the PSII photoresponses, and unmasked the onset potentials relating to the QA/QB charge transfer process. These findings have imparted a fuller understanding of the charge transfer pathways within PSII and at photosystem-electrode interfaces, which will lead to more rational design of pigment-containing photoelectrodes in general. PMID:27723748

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    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.

  9. Transfer in motion discrimination learning was no greater in double training than in single training.

    PubMed

    Huang, Jinfeng; Liang, Ju; Zhou, Yifeng; Liu, Zili

    2017-06-01

    We investigated the controversy regarding double training in motion discrimination learning. We collected data from 43 participants in a motion direction discrimination learning task with either double training (i.e., training plus exposure) or single training (i.e., no exposure). By pooling these data with those in the literature, we had data in double training from 28 participants and in single training from 36 participants. We found that, in double training, the transfer along the exposed direction was less than that along the trained direction, indicating incomplete transfer. Importantly, the transfer in double training was not reliably greater than that in single training.

  10. Charge transfer in photorefractive CdTe:Ge at different wavelengths

    NASA Astrophysics Data System (ADS)

    Shcherbin, K.; Odoulov, S.; Ramaz, F.; Farid, B.; Briat, B.; von Bardeleben, H. J.; Delaye, P.; Roosen, G.

    2001-10-01

    The charge transfer processes in photorefractive CdTe:Ge were modeled using the data of optical absorption, magnetic circular dichroism (MCD) and electron paramagnetic resonance (EPR) spectroscopies. Within the developed model the variations in the photorefractive properties of different CdTe:Ge samples are explained by differences in the relative concentrations of donor and trap centers. The existence of two different centers of comparable concentrations, each in two charge states, allows charge redistribution between them and gives rise to optical sensitization of some CdTe:Ge samples for photorefractive recording under an auxiliary illumination. In the present article we follow the proposal of pseudo-3D presentation of light-induced absorption to distinguish the main charge transfer processes at different excitation energies and explain the sensitization of CdTe:Ge for photorefractive recording at 1.06, 1.32 and 1.55 μm by light with appropriate wavelength.

  11. Double layer of platinum electrodes: Non-monotonic surface charging phenomena and negative double layer capacitance

    NASA Astrophysics Data System (ADS)

    Huang, Jun; Zhou, Tao; Zhang, Jianbo; Eikerling, Michael

    2018-01-01

    In this study, a refined double layer model of platinum electrodes accounting for chemisorbed oxygen species, oriented interfacial water molecules, and ion size effects in solution is presented. It results in a non-monotonic surface charging relation and a peculiar capacitance vs. potential curve with a maximum and possibly negative values in the potential regime of oxide-formation.

  12. Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

    NASA Technical Reports Server (NTRS)

    Kwong, Victor H. S.

    1996-01-01

    Charge transfer at electron-volt energies between multiply charged atomic ions and neutral atoms and molecules is of considerable importance in astrophysics, plasma physics, and in particular, fusion plasmas. In the year covered by this report, several major tasks were completed. These include: (1) the re-calibration of the ion gauge to measure the absolute particle densities of H2, He, N2, and CO for our current measurements; (2) the analysis of data for charge transfer reactions of N(exp 2 plus) ion and He, H2, N2, and CO; (3) measurement and data analysis of the charge transfer reaction of (Fe(exp 2 plus) ion and H2; (4) charge transfer measurement of Fe(exp 2 plus) ion and H2; and (5) redesign and modification of the ion detection and data acquisition system for the low energy beam facility (reflection time of flight mass spectrometer) dedicated to the study of state select charge transfer.

  13. The study of surface acoustic wave charge transfer device

    NASA Technical Reports Server (NTRS)

    Papanicolaou, N.; Lin, H. C.

    1978-01-01

    A surface acoustic wave-charge transfer device, consisting of an n-type silicon substrate, a thermally grown silicon dioxide layer, and a sputtered film of piezoelectric zinc oxide is proposed as a means of circumventing problems associated with charge-coupled device (CCD) applications in memory, signal processing, and imaging. The proposed device creates traveling longitudinal electric fields in the silicon and replaces the multiphase clocks in CCD's. The traveling electric fields create potential wells which carry along charges stored there. These charges may be injected into the wells by light or by using a p-n junction as in conventional CCD's.

  14. Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

    DOE PAGES

    Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...

    2016-12-19

    Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less

  15. Review on charge transfer and chemical activity of TiO2: Mechanism and applications

    NASA Astrophysics Data System (ADS)

    Cai, Yongqing; Feng, Yuan Ping

    2016-12-01

    Charge separation and transfer at the interface between two materials play a significant role in various atomic-scale processes and energy conversion systems. In this review, we present the mechanism and outcome of charge transfer in TiO2, which is extensively explored for photocatalytic applications in the field of environmental science. We list several experimental and computational methods to estimate the amount of charge transfer. The effects of the work function, defects and doping, and employment of external electric field on modulating the charge transfer are presented. The interplay between the band bending and carrier transport across the surface and interface consisting of TiO2 is discussed. We show that the charge transfer can also strongly affect the behavior of deposited nanoparticles on TiO2 through built-in electric field that it creates. This review encompasses several advances of composite materials where TiO2 is combined with two-dimensional materials like graphene, MoS2, phosphorene, etc. The charge transport in the TiO2-organohalide perovskite with respect to the electron-hole separation at the interface is also discussed.

  16. Chemically assembled double-dot single-electron transistor analyzed by the orthodox model considering offset charge

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

    Kano, Shinya; Maeda, Kosuke; Majima, Yutaka, E-mail: majima@msl.titech.ac.jp

    2015-10-07

    We present the analysis of chemically assembled double-dot single-electron transistors using orthodox model considering offset charges. First, we fabricate chemically assembled single-electron transistors (SETs) consisting of two Au nanoparticles between electroless Au-plated nanogap electrodes. Then, extraordinary stable Coulomb diamonds in the double-dot SETs are analyzed using the orthodox model, by considering offset charges on the respective quantum dots. We determine the equivalent circuit parameters from Coulomb diamonds and drain current vs. drain voltage curves of the SETs. The accuracies of the capacitances and offset charges on the quantum dots are within ±10%, and ±0.04e (where e is the elementary charge),more » respectively. The parameters can be explained by the geometrical structures of the SETs observed using scanning electron microscopy images. Using this approach, we are able to understand the spatial characteristics of the double quantum dots, such as the relative distance from the gate electrode and the conditions for adsorption between the nanogap electrodes.« less

  17. Electron Transfer Dissociation: Effects of Cation Charge State on Product Partitioning in Ion/Ion Electron Transfer to Multiply Protonated Polypeptides

    PubMed Central

    Liu, Jian; McLuckey, Scott A.

    2012-01-01

    The effect of cation charge state on product partitioning in the gas-phase ion/ion electron transfer reactions of multiply protonated tryptic peptides, model peptides, and relatively large peptides with singly charged radical anions has been examined. In particular, partitioning into various competing channels, such as proton transfer (PT) versus electron transfer (ET), electron transfer with subsequent dissociation (ETD) versus electron transfer with no dissociation (ET,noD), and fragmentation of backbone bonds versus fragmentation of side chains, was measured quantitatively as a function of peptide charge state to allow insights to be drawn about the fundamental aspects of ion/ion reactions that lead to ETD. The ET channel increases relative to the PT channel, ETD increases relative to ET,noD, and fragmentation at backbone bonds increases relative to side-chain cleavages as cation charge state increases. The increase in ET versus PT with charge state is consistent with a Landau-Zener based curve-crossing model. An optimum charge state for ET is predicted by the model for the ground state-to-ground state reaction. However, when the population of excited product ion states is considered, it is possible that a decrease in ET efficiency as charge state increases will not be observed due to the possibility of the population of excited electronic states of the products. Several factors can contribute to the increase in ETD versus ET,noD and backbone cleavage versus side-chain losses. These factors include an increase in reaction exothermicity and charge state dependent differences in precursor and product ion structures, stabilities, and sites of protonation. PMID:23264749

  18. Interlayer‐State‐Coupling Dependent Ultrafast Charge Transfer in MoS2/WS2 Bilayers

    PubMed Central

    Zhang, Jin; Hong, Hao; Lian, Chao; Ma, Wei; Xu, Xiaozhi; Zhou, Xu; Fu, Huixia

    2017-01-01

    Light‐induced interlayer ultrafast charge transfer in 2D heterostructures provides a new platform for optoelectronic and photovoltaic applications. The charge separation process is generally hypothesized to be dependent on the interlayer stackings and interactions, however, the quantitative characteristic and detailed mechanism remain elusive. Here, a systematical study on the interlayer charge transfer in model MoS2/WS2 bilayer system with variable stacking configurations by time‐dependent density functional theory methods is demonstrated. The results show that the slight change of interlayer geometry can significantly modulate the charge transfer time from 100 fs to 1 ps scale. Detailed analysis further reveals that the transfer rate in MoS2/WS2 bilayers is governed by the electronic coupling between specific interlayer states, rather than the interlayer distances, and follows a universal dependence on the state‐coupling strength. The results establish the interlayer stacking as an effective freedom to control ultrafast charge transfer dynamics in 2D heterostructures and facilitate their future applications in optoelectronics and light harvesting. PMID:28932669

  19. Charge Transfer and Orbital Level Alignment at Inorganic/Organic Interfaces: The Role of Dielectric Interlayers.

    PubMed

    Hollerer, Michael; Lüftner, Daniel; Hurdax, Philipp; Ules, Thomas; Soubatch, Serguei; Tautz, Frank Stefan; Koller, Georg; Puschnig, Peter; Sterrer, Martin; Ramsey, Michael G

    2017-06-27

    It is becoming accepted that ultrathin dielectric layers on metals are not merely passive decoupling layers, but can actively influence orbital energy level alignment and charge transfer at interfaces. As such, they can be important in applications ranging from catalysis to organic electronics. However, the details at the molecular level are still under debate. In this study, we present a comprehensive analysis of the phenomenon of charge transfer promoted by a dielectric interlayer with a comparative study of pentacene adsorbed on Ag(001) with and without an ultrathin MgO interlayer. Using scanning tunneling microscopy and photoemission tomography supported by density functional theory, we are able to identify the orbitals involved and quantify the degree of charge transfer in both cases. Fractional charge transfer occurs for pentacene adsorbed on Ag(001), while the presence of the ultrathin MgO interlayer promotes integer charge transfer with the lowest unoccupied molecular orbital transforming into a singly occupied and singly unoccupied state separated by a large gap around the Fermi energy. Our experimental approach allows a direct access to the individual factors governing the energy level alignment and charge-transfer processes for molecular adsorbates on inorganic substrates.

  20. Analysis of the heat transfer in double and triple concentric tube heat exchangers

    NASA Astrophysics Data System (ADS)

    Rădulescu, S.; Negoiţă, L. I.; Onuţu, I.

    2016-08-01

    The tubular heat exchangers (shell and tube heat exchangers and concentric tube heat exchangers) represent an important category of equipment in the petroleum refineries and are used for heating, pre-heating, cooling, condensation and evaporation purposes. The paper presents results of analysis of the heat transfer to cool a petroleum product in two types of concentric tube heat exchangers: double and triple concentric tube heat exchangers. The cooling agent is water. The triple concentric tube heat exchanger is a modified constructive version of double concentric tube heat exchanger by adding an intermediate tube. This intermediate tube improves the heat transfer by increasing the heat area per unit length. The analysis of the heat transfer is made using experimental data obtained during the tests in a double and triple concentric tube heat exchanger. The flow rates of fluids, inlet and outlet temperatures of water and petroleum product are used in determining the performance of both heat exchangers. Principally, for both apparatus are calculated the overall heat transfer coefficients and the heat exchange surfaces. The presented results shows that triple concentric tube heat exchangers provide better heat transfer efficiencies compared to the double concentric tube heat exchangers.

  1. CHARGE-TRANSFER ASSOCIATION AND PARAMAGNETISM OF SOME ORGANIC SYSTEMS

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

    Eastman, J W

    When p-xylene was combined with chloranil in n-heptane, charge-transfer optical absorption was observed. The magnitude of this absorption was used to calculate an equilibrium constant for the formation of a donor-acceptor complex containing one p-xylene was combined with carbon tetrabromide and with carbon tetrachloride in n-heptane, no charge-transfer absorption was observed. Reactions of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) with chloranil (pQCl/ sub 4/) were observed in ethylene dichloride and acetonitrile. In both solvents adduct formation occurred initially, as observed by its charge-transfer absorption. In acetonitrile time-dependent electron spin resonance (ESR) absorption was observed, and it was identified with the positive and negative radicalmore » ions of TMPD and pQCl/sub 4/, respectively. In this case a completely ionized electron transfer had occurred. Chloranil and other quinones were found to react with N,N-dimethylaniline forming a crystal violet salt. The diamagnetic donor-acceptor complexes and also semiquinone radicals are intermediates which were observed. Some physical measurements of the kinetics of this reaction are described and correlated. When fluoranil was allowed to react with dimethylaniline, the hyperfine splitting by the fluorine atoms of the fluoranil radical was not resolved. Characteristics of the ESR absorption by this radical in dimethylaniline are discussed in terms of an electron transfer between the semiquinone and quinone, and between the semiquinone and hydroquinone ion. Paramagnetism was discovered in hydrocarbon-quinone solids. ESR absorption was assigned to imperfections in the solid which was normally diamagnetic. The preparation of these solids and some of their physical characteristics are described. (auth)« less

  2. The double-layer of penetrable ions: an alternative route to charge reversal.

    PubMed

    Frydel, Derek; Levin, Yan

    2013-05-07

    We investigate a double-layer of penetrable ions near a charged wall. We find a new mechanism for charge reversal that occurs in the weak-coupling regime and, accordingly, the system is suitable for the mean-field analysis. The penetrability is achieved by smearing-out the ionic charge inside a sphere, so there is no need to introduce non-electrostatic forces and the system in the low coupling limit can be described by a modified version of the Poisson-Boltzmann equation. The predictions of the theory are compared with the Monte Carlo simulations.

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

    PubMed

    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.

  4. Theoretical Investigation of Charge Transfer in Metal Organic Frameworks for Electrochemical Device Applications

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

    Patwardhan, Sameer; Schatz, George C.

    For electrochemical device applications metal organic frameworks (MOFs) must exhibit suitable conduction properties. To this end, we have performed computational studies of intermolecular charge transfer in MOFs consisting of hexa-ZrIV nodes and tetratopic carboxylate linkers. This includes an examination of the electronic structure of linkers that are derived from tetraphenyl benzene 1, tetraphenyl pyrene 2, and tetraphenyl porphyrin 3 molecules. These results are used to determine charge transfer propensities in MOFs, within the framework of Marcus theory, including an analysis of the key parameters (charge transfer integral t, reorganization energy λ, and free energy change ΔG0) and evaluation of figuresmore » of merit for charge transfer based on the chemical structures of the linkers. This qualitative analysis indicates that delocalization of the HOMO/LUMO on terminal substituents increases t and decreases λ, while weaker binding to counterions decreases ΔG0, leading to better charge transfer propensity. Subsequently, we study hole transfer in the linker 2 containing MOFs, NU-901 and NU-1000, in detail and describe mechanisms (hopping and superexchange) that may be operative under different electrochemical conditions. Comparisons with experiment are provided where available. On the basis of the redox and catalytic activity of nodes and linkers, we propose three possible schemes for constructing electrochemical devices for catalysis. We believe that the results of this study will lay the foundation for future experimental work on this topic.« less

  5. Tuning Topological Surface States by Charge Transfer

    NASA Astrophysics Data System (ADS)

    Chen, Zhiyi

    Three-dimensional (3D) topological insulators (TIs), Bi2Se 3, Bi2Te3, Sb2Te3, are a class of materials that has non-trivial bulk band structure and metallic surface states. Access to charge transport through Dirac surface states in TIs can be challenging due to their intermixing with bulk states or non-topological two-dimensional electron gas quantum well states caused by bending of electronic bands near the surface. The band bending arises via charge transfer from surface adatoms or interfaces and, therefore, the choice of layers abutting topological surfaces is critical. Surfaces of these 3D TIs have also been proposed to host new quantum phases at the interfaces with other types of materials, provided that the topological properties of interfacial regions remain unperturbed. This thesis presents a systematic experimental study of both bulk conducting and surface charge transfer problems. We started with optimizing growth condition of Bi2Se3 on various substrates, to achieve best quality of Bi2Se3 single layers we can get. We then move on to growth of Bi2Se3/ZnxCd1-xSe bilayers. Here we improved lattice mismatch between Bi2Se 3 and ZnxCd1-xSe layers by tuning lattice parameter of ZnxCd1-xSe. After that, we achieved molecular beam epitaxial growth of Bi2Se3/ZnxCd1-x Se superlattices that hold only one topological surface channel per TI layer. The topological nature of conducting channels is supported by pi-Berry phase evident from observed Shubnikov de Haas quantum oscillations and by the associated two-dimensional weak antilocalization quantum interference correction to magnetoresistance. Both density functional theory calculations and transport measurements suggest that a single topological Dirac cone per TI layer can be realized by asymmetric interfaces: Se-terminated Znx Cd1-xSe interface with the TI remains 'electronically intact', while charge transfer occurs at the Zn-terminated interface. Our findings indicate that topological transport could be controlled

  6. Quantum state transfer in double-quantum-well devices

    NASA Technical Reports Server (NTRS)

    Jakumeit, Jurgen; Tutt, Marcel; Pavlidis, Dimitris

    1994-01-01

    A Monte Carlo simulation of double-quantum-well (DQW) devices is presented in view of analyzing the quantum state transfer (QST) effect. Different structures, based on the AlGaAs/GaAs system, were simulated at 77 and 300 K and optimized in terms of electron transfer and device speed. The analysis revealed the dominant role of the impurity scattering for the QST. Different approaches were used for the optimization of QST devices and basic physical limitations were found in the electron transfer between the QWs. The maximum transfer of electrons from a high to a low mobility well was at best 20%. Negative differential resistance is hampered by the almost linear rather than threshold dependent relation of electron transfer on electric field. By optimizing the doping profile the operation frequency limit could be extended to 260 GHz.

  7. Interfacial Charge Transfer States in Condensed Phase Systems

    NASA Astrophysics Data System (ADS)

    Vandewal, Koen

    2016-05-01

    Intermolecular charge transfer (CT) states at the interface between electron-donating (D) and electron-accepting (A) materials in organic thin films are characterized by absorption and emission bands within the optical gap of the interfacing materials. CT states efficiently generate charge carriers for some D-A combinations, and others show high fluorescence quantum efficiencies. These properties are exploited in organic solar cells, photodetectors, and light-emitting diodes. This review summarizes experimental and theoretical work on the electronic structure and interfacial energy landscape at condensed matter D-A interfaces. Recent findings on photogeneration and recombination of free charge carriers via CT states are discussed, and relations between CT state properties and optoelectronic device parameters are clarified.

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

    DOE PAGES

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

    2017-06-23

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

  9. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    NASA Astrophysics Data System (ADS)

    Skourtis, Spiros S.; Prytkova, Tatiana; Beratan, David N.

    2007-12-01

    This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH--containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH-, upon photo-excitation of FADH- with 350-450 nm light. We compute the lowest singlet excited states of FADH- in DNA photolyase using INDO/S configuration interaction, time-dependent density-functional, and time-dependent Hartree-Fock methods. The calculations identify the lowest singlet excited state of FADH- that is populated after photo-excitation and that acts as the electron donor. For this donor state we compute conformationally-averaged tunneling matrix elements to empty electron-acceptor states of a thymine dimer bound to photolyase. The conformational averaging involves different FADH--thymine dimer confromations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. The tunneling matrix element computations use INDO/S-level Green's function, energy splitting, and Generalized Mulliken-Hush methods. These calculations indicate that photo-excitation of FADH- causes a π→π* charge-transfer transition that shifts electron density to the side of the flavin isoalloxazine ring that is adjacent to the docked thymine dimer. This shift in electron density enhances the FADH--to-dimer electronic coupling, thus inducing rapid electron transfer.

  10. Molecular Structures and Momentum Transfer Cross Sections: The Influence of the Analyte Charge Distribution.

    PubMed

    Young, Meggie N; Bleiholder, Christian

    2017-04-01

    Structure elucidation by ion mobility spectrometry-mass spectrometry methods is based on the comparison of an experimentally measured momentum transfer cross-section to cross-sections calculated for model structures. Thus, it is imperative that the calculated cross-section must be accurate. However, it is not fully understood how important it is to accurately model the charge distribution of an analyte ion when calculating momentum transfer cross-sections. Here, we calculate and compare momentum transfer cross-sections for carbon clusters that differ in mass, charge state, and mode of charge distribution, and vary temperature and polarizability of the buffer gas. Our data indicate that the detailed distribution of the ion charge density is intimately linked to the contribution of glancing collisions to the momentum transfer cross-section. The data suggest that analyte ions with molecular mass ~3 kDa or momentum transfer cross-section 400-500 Å 2 would be significantly influenced by the charge distribution in nitrogen buffer gas. Our data further suggest that accurate structure elucidation on the basis of IMS-MS data measured in nitrogen buffer gas must account for the molecular charge distribution even for systems as large as C 960 (~12 kDa) when localized charges are present and/or measurements are conducted under cryogenic temperatures. Finally, our data underscore that accurate structure elucidation is unlikely if ion mobility data recorded in one buffer gas is converted into other buffer gases when electronic properties of the buffer gases differ. Graphical Abstract ᅟ.

  11. Charge-transfer complexes of phenylephrine with nitrobenzene derivatives

    NASA Astrophysics Data System (ADS)

    El-Mossalamy, E. H.

    2004-04-01

    The molecular charge-transfer complexes of phenylephrine with picric acid and m-dinitrobenzene have been studied and investigated by IR, 1H NMR electronic spectra in organic solvents and buffer solutions, respectively. Simple and selective methods are proposed for the determination of phenylephrine hydrochloride in bulk form and in tablets. The two methods are based on the formation of charge-transfer complexes between drug base as a n-donor (D) and picric acid, m-dinitrobenzene as π-acceptor (A). The products exhibit absorption maxima at 497 and 560 nm in acetonitrile for picric acid and m-dinitrobenzene, respectively. The coloured product exhibits an absorption maximum at 650 nm in dioxane. The sensitive kinetic methods for the determination phynylephrine hydrochloride are described. The method is based upon a kinetic investigation of the oxidation reaction of the drug with alkaline potassium permanganate at room temperature for a fixed time at 20 min.

  12. Jet Formation and Penetration Study of Double-Layer Shaped Charge

    NASA Astrophysics Data System (ADS)

    Wang, Zhe; Jiang, Jian-Wei; Wang, Shu-You; Liu, Han

    2018-04-01

    A theoretical analysis on detonation wave propagation in a double-layer shaped charge (DLSC) is performed. Numerical simulations using the AUTODYN software are carried out to compare the distinctions between jet formations in DLSC and ordinary shaped charge (OSC), in particular, the OSC made using a higher detonation velocity explosive, which is treated as the outer layer charge in the DLSC. The results show that the improved detonation velocity ratio and radial charge percentage of outer-to-inner layer charge are conducive to the formation of a convergent detonation wave, which contributes to enhancement of jet tip velocity in DLSC. The thickness and mass percentages of liner flowing into jet in DLSC closely follow the exponential distribution along the radial direction, but the percentages in DLSC and the mass of effective jet, which have significant influence on the penetration depth, are lower than those in OSC with the outer layer charge. This implies that the total charge energy is the major factor controlling the effective jet formation, which is confirmed by the verification tests using flash X-ray system and following penetration tests. The numerical simulation and test results compare well, while penetration test results indicate that the performance of DLSC is not better than that of OSC with the outer layer charge, due to the differences in jet formation.

  13. Transfer RNA: a dancer between charging and mis-charging for protein biosynthesis.

    PubMed

    Zhou, Xiaolong; Wang, Enduo

    2013-10-01

    Transfer RNA plays a fundamental role in the protein biosynthesis as an adaptor molecule by functioning as a biological link between the genetic nucleotide sequence in the mRNA and the amino acid sequence in the protein. To perform its role in protein biosynthesis, it has to be accurately recognized by aminoacyl-tRNA synthetases (aaRSs) to generate aminoacyl-tRNAs (aa-tRNAs). The correct pairing between an amino acid with its cognate tRNA is crucial for translational quality control. Production and utilization of mis-charged tRNAs are usually detrimental for all the species, resulting in cellular dysfunctions. Correct aa-tRNAs formation is collectively controlled by aaRSs with distinct mechanisms and/or other trans-factors. However, in very limited instances, mis-charged tRNAs are intermediate for specific pathways or essential components for the translational machinery. Here, from the point of accuracy in tRNA charging, we review our understanding about the mechanism ensuring correct aa-tRNA generation. In addition, some unique mis-charged tRNA species necessary for the organism are also briefly described.

  14. Double proton transfer behavior and one-electron oxidation effect in double H-bonded glycinamide-formic acid complex.

    PubMed

    Li, Ping; Bu, Yuxiang

    2004-11-22

    The behavior of double proton transfer occurring in a representative glycinamide-formic acid complex has been investigated at the B3LYP/6-311 + + G( * *) level of theory. Thermodynamic and, especially, kinetic parameters, such as tautomeric energy, equilibrium constant, and barrier heights have been discussed, respectively. The relevant quantities involved in the double proton transfer process, such as geometrical changes, interaction energies, and intrinsic reaction coordinate calculations have also been studied. Computational results show that the participation of a formic acid molecule favors the proceeding of the proton transfer for glycinamide compared with that without mediate-assisted case. The double proton transfer process proceeds with a concerted mechanism rather than a stepwise one since no ion-pair complexes have been located during the proton transfer process. The calculated barrier heights are 11.48 and 0.85 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 2.95 and 2.61 kcal/mol to 8.53 and -1.76 kcal/mol if further inclusion of zero-point vibrational energy corrections, where the negative barrier height implies that the reverse reaction should proceed with barrierless spontaneously, analogous to that occurring between glycinamide and formamide. Furthermore, solvent effects on the thermodynamic and kinetic processes have also been predicted qualitatively employing the isodensity surface polarized continuum model within the framework of the self-consistent reaction field theory. Additionally, the oxidation process for the double H-bonded glycinamide-formic acid complex has also been investigated. Contrary to that neutral form possessing a pair of two parallel intermolecular H bonds, only a single H bond with a comparable strength has been found in its ionized form. The vertical and adiabatic ionization potentials for the neutral complex have been determined to be about 9.40 and 8.69 e

  15. Radiation and the classical double copy for color charges

    NASA Astrophysics Data System (ADS)

    Goldberger, Walter D.; Ridgway, Alexander K.

    2017-06-01

    We construct perturbative classical solutions of the Yang-Mills equations coupled to dynamical point particles carrying color charge. By applying a set of color to kinematics replacement rules first introduced by Bern, Carrasco and Johansson, these are shown to generate solutions of d -dimensional dilaton gravity, which we also explicitly construct. Agreement between the gravity result and the gauge theory double copy implies a correspondence between non-Abelian particles and gravitating sources with dilaton charge. When the color sources are highly relativistic, dilaton exchange decouples, and the solutions we obtain match those of pure gravity. We comment on possible implications of our findings to the calculation of gravitational waveforms in astrophysical black hole collisions, directly from computationally simpler gluon radiation in Yang-Mills theory.

  16. Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules - Synthesis and Characterization

    DTIC Science & Technology

    2016-04-12

    AFRL-AFOSR-CL-TR-2016-0012 Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene Macromolecules Ronald Ziolo CIQA Final Report 07/07...3. DATES COVERED (From - To)  15 Aug 2014 to 14 Jan 2016 4. TITLE AND SUBTITLE Intramolecular Charge Transfer of Conjugated Liquid Crystal Ferrocene...characterization of a new series of conjugated macromolecules bearing ferrocene as a highly efficient electron donor material coupled to 2,5-di(alcoxy) benzene

  17. Charge transfer during individual collisions in ice growing by riming

    NASA Technical Reports Server (NTRS)

    Avila, Eldo E.; Caranti, Giorgio M.

    1991-01-01

    The charging of a target by riming in the wind was studied in the temperature range of (-10, -18 C). For each temperature, charge transfers of both signs are observed and, according to the environmental conditions, one of them prevails. The charge is more positive as the liquid water concentration is increased at any particular temperature. It is found that even at the low impact velocities used (5 m/s) there is abundant evidence of fragmentation following the collision.

  18. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    NASA Astrophysics Data System (ADS)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  19. Charge transfer polarisation wave and carrier pairing in the high T(sub c) copper oxides

    NASA Technical Reports Server (NTRS)

    Chakraverty, B. K.

    1990-01-01

    The High T(sub c) oxides are highly polarizable materials and are charge transfer insulators. The charge transfer polarization wave formalism is developed in these oxides. The dispersion relationships due to long range dipole-dipole interaction of a charge transfer dipole lattice are obtained in 3-D and 2-D. These are high frequency bosons and their coupling with carriers is weak and antiadiabatic in nature. As a result, the mass renormalization of the carriers is negligible in complete contrast to conventional electron-phonon interaction, that give polarons and bipolarons. Both bound and superconducting pairing is discussed for a model Hamiltonian valid in the antiadiabatic regime, both in 3-D and 2-D. The stability of the charge transfer dipole lattice has interesting consequences that are discussed.

  20. Charge transfer kinetics at the solid-solid interface in porous electrodes

    NASA Astrophysics Data System (ADS)

    Bai, Peng; Bazant, Martin Z.

    2014-04-01

    Interfacial charge transfer is widely assumed to obey the Butler-Volmer kinetics. For certain liquid-solid interfaces, the Marcus-Hush-Chidsey theory is more accurate and predictive, but it has not been applied to porous electrodes. Here we report a simple method to extract the charge transfer rates in carbon-coated LiFePO4 porous electrodes from chronoamperometry experiments, obtaining curved Tafel plots that contradict the Butler-Volmer equation but fit the Marcus-Hush-Chidsey prediction over a range of temperatures. The fitted reorganization energy matches the Born solvation energy for electron transfer from carbon to the iron redox site. The kinetics are thus limited by electron transfer at the solid-solid (carbon-LixFePO4) interface rather than by ion transfer at the liquid-solid interface, as previously assumed. The proposed experimental method generalizes Chidsey’s method for phase-transforming particles and porous electrodes, and the results show the need to incorporate Marcus kinetics in modelling batteries and other electrochemical systems.

  1. Topologically protected charge transfer along the edge of a chiral p -wave superconductor

    NASA Astrophysics Data System (ADS)

    Gnezdilov, N. V.; van Heck, B.; Diez, M.; Hutasoit, Jimmy A.; Beenakker, C. W. J.

    2015-09-01

    The Majorana fermions propagating along the edge of a topological superconductor with px+i py pairing deliver a shot noise power of 1/2 ×e2/h per eV of voltage bias. We calculate the full counting statistics of the transferred charge and find that it becomes trinomial in the low-temperature limit, distinct from the binomial statistics of charge-e transfer in a single-mode nanowire or charge-2 e transfer through a normal-superconductor interface. All even-order correlators of current fluctuations have a universal quantized value, insensitive to disorder and decoherence. These electrical signatures are experimentally accessible, because they persist for temperatures and voltages large compared to the Thouless energy.

  2. Band Alignment and Charge Transfer in Complex Oxide Interfaces

    NASA Astrophysics Data System (ADS)

    Zhong, Zhicheng; Hansmann, Philipp

    2017-01-01

    The synthesis of transition metal heterostructures is currently one of the most vivid fields in the design of novel functional materials. In this paper, we propose a simple scheme to predict band alignment and charge transfer in complex oxide interfaces. For semiconductor heterostructures, band-alignment rules like the well-known Anderson or Schottky-Mott rule are based on comparison of the work function or electron affinity of the bulk components. This scheme breaks down for oxides because of the invalidity of a single work-function approximation as recently shown in [Phys. Rev. B 93, 235116 (2016), 10.1103/PhysRevB.93.235116; Adv. Funct. Mater. 26, 5471 (2016), 10.1002/adfm.201600243]. Here, we propose a new scheme that is built on a continuity condition of valence states originating in the compounds' shared network of oxygen. It allows for the prediction of sign and relative amplitude of the intrinsic charge transfer, taking as input only information about the bulk properties of the components. We support our claims by numerical density functional theory simulations as well as (where available) experimental evidence. Specific applications include (i) controlled doping of SrTiO3 layers with the use of 4 d and 5 d transition metal oxides and (ii) the control of magnetic ordering in manganites through tuned charge transfer.

  3. Calculation of rates of exciton dissociation into hot charge-transfer states in model organic photovoltaic interfaces

    NASA Astrophysics Data System (ADS)

    Vázquez, Héctor; Troisi, Alessandro

    2013-11-01

    We investigate the process of exciton dissociation in ordered and disordered model donor/acceptor systems and describe a method to calculate exciton dissociation rates. We consider a one-dimensional system with Frenkel states in the donor material and states where charge transfer has taken place between donor and acceptor. We introduce a Green's function approach to calculate the generation rates of charge-transfer states. For disorder in the Frenkel states we find a clear exponential dependence of charge dissociation rates with exciton-interface distance, with a distance decay constant β that increases linearly with the amount of disorder. Disorder in the parameters that describe (final) charge-transfer states has little effect on the rates. Exciton dissociation invariably leads to partially separated charges. In all cases final states are “hot” charge-transfer states, with electron and hole located far from the interface.

  4. Charge Transfer Processes in OPV Materials as Revealed by EPR Spectroscopy

    DOE PAGES

    Niklas, Jens; Poluektov, Oleg

    2017-03-03

    Understanding charge separation and charge transport at a molecular level is crucial for improving the efficiency of organic photovoltaic (OPV) cells. Under illumination of Bulk Heterojunction (BHJ) blends of polymers and fullerenes, various paramagnetic species are formed including polymer and fullerene radicals, radical pairs, and photoexcited triplet states. Light-induced Electron Paramagnetic Resonance (EPR) spectroscopy is ideally suited to study these states in BHJ due to its selectivity in probing the paramagnetic intermediates. Some advanced EPR techniques like light-induced ENDOR spectroscopy and pulsed techniques allow the determination of hyperfine coupling tensors, while high-frequency EPR allows the EPR signals of the individualmore » species to be resolved and their g-tensors to be determined. In these magnetic resonance parameters reveal details about the delocalization of the positive polaron on the various polymer donors which is important for the efficient charge separation in BHJ systems. Time-resolved EPR can contribute to the study of the dynamics of charge separation, charge transfer and recombination in BHJ by probing the unique spectral signatures of charge transfer and triplet states. Furthermore, the potential of the EPR also allows characterization of the intermediates and products of BHJ degradation.« less

  5. Studies on interaction of an intramolecular charge transfer fluorescence probe: 4'-dimethylamino-2,5-dihydroxychalcone with DNA.

    PubMed

    Xu, Zhicheng; Bai, Guan; Dong, Chuan

    2005-10-15

    The interaction of a new intramolecular charge transfer probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC), with calf thymus DNA has been studied. Compared to the spectral characteristics of the free form in aqueous solution, the fluorescence of DMADHC enhanced dramatically accompanying a blueshift of the emission maxima in the presence of DNA. The absorption and fluorescence spectra, salt concentration effect, KI quenching, fluorescence polarization, and DNA denaturation experiments were given. These results give evidence that the DMADHC molecule is inserted into the base-stacking domain of the DNA double helix. The intrinsic binding constant and the binding site number were estimated. The analytical characteristics were also given.

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

    PubMed

    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

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

    PubMed Central

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

    2011-01-01

    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. PMID:21895159

  8. Crystallochromy of perylene pigments: Interference between Frenkel excitons and charge-transfer states

    NASA Astrophysics Data System (ADS)

    Gisslén, Linus; Scholz, Reinhard

    2009-09-01

    The optical properties of perylene-based pigments are arising from the interplay between neutral molecular excitations and charge transfer between adjacent molecules. In the crystalline phase, these excitations are coupled via electron and hole transfer, two quantities relating directly to the width of the conduction and valence band in the crystalline phase. Based on the crystal structure determined by x-ray diffraction, density-functional theory (DFT) and Hartree-Fock are used for the calculation of the electronic states of a dimer of stacked molecules. The resulting transfer parameters for electron and hole are used in an exciton model for the coupling between Frenkel excitons and charge-transfer states. The deformation of the positively or negatively charged molecular ions with respect to the neutral ground state is calculated with DFT and the geometry in the optically excited state is deduced from time-dependent DFT and constrained DFT. All of these deformations are interpreted in terms of the elongation of an effective internal vibration which is used subsequently in the exciton model for the crystalline phase. A comparison between the calculated dielectric function and the observed optical spectra allows to deduce the relative energetic position of Frenkel excitons and the charge-transfer state involving stack neighbors, a key parameter for various electronic and optoelectronic device applications. For five out of six perylene pigments studied in the present work, this exciton model results in excellent agreement between calculated and observed optical properties.

  9. Double second toe transfer in congenital hand anomalies.

    PubMed

    Van Holder, C; Giele, H; Gilbert, A

    1999-08-01

    A series of 14 patients with congenital hand anomalies who received staged double second toe transfers to the same hand for restoration of function or form were reviewed retrospectively. There were three children with constriction ring syndrome, two with symbrachydactyly and nine with transverse absence (failure of formation). There were different indications, technical difficulties and results with the various anomalies. All transferred toes were mobile and sensate, and were reported to be of benefit in both function and appearance. However, secondary surgical procedures were required in all patients.

  10. Lowest energy Frenkel and charge transfer exciton intermixing in one-dimensional copper phthalocyanine molecular lattice

    NASA Astrophysics Data System (ADS)

    Bondarev, I. V.; Popescu, A.; Younts, R. A.; Hoffman, B.; McAfee, T.; Dougherty, D. B.; Gundogdu, K.; Ade, H. W.

    2016-11-01

    We report the results of the combined experimental and theoretical studies of the low-lying exciton states in crystalline copper phthalocyanine. We derive the eigen energy spectrum for the two lowest intramolecular Frenkel excitons coupled to the intermolecular charge transfer exciton state and compare it with temperature dependent optical absorption spectra measured experimentally, to obtain the parameters of the Frenkel-charge-transfer exciton intermixing. The two Frenkel exciton states are spaced apart by 0.26 eV, and the charge transfer exciton state is 50 meV above the lowest Frenkel exciton. Both Frenkel excitons are strongly mixed with the charge transfer exciton, showing the coupling constant 0.17 eV which agrees with earlier experimental measurements. These results can be used for the proper interpretation of the physical properties of crystalline phthalocyanines.

  11. Quasi-four-body treatment of charge transfer in the collision of protons with atomic helium: II. Second-order non-Thomas mechanisms and the cross sections

    NASA Astrophysics Data System (ADS)

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

    2018-05-01

    A fully quantum mechanical four-body treatment of charge transfer collisions between energetic protons and atomic helium is developed here. The Pauli exclusion principle is applied to both the wave function of the initial and final states as well as the operators involved in the interaction. Prior to the collision, the helium atom is assumed as a two-body system composed of the nucleus, He2+, and an electron cloud composed of two electrons. Nonetheless, four particles are assumed in the final state. As the double interactions contribute extensively in single charge transfer collisions, the Faddeev-Lovelace-Watson scattering formalism describes it best physically. The treatment of the charge transfer cross section, under this quasi-four-body treatment within the FWL formalism, showed that other mechanisms leading to an effect similar to the Thomas one occur at the same scattering angle. Here, we study the two-body interactions which are not classically described but which lead to an effect similar to the Thomas mechanism and finally we calculate the total singlet and triplet amplitudes as well as the angular distributions of the charge transfer cross sections. As the incoming projectiles are assumed to be plane waves, the present results are calculated for high energies; specifically a projectile energy of 7.42 MeV was assumed as this is where experimental results are available in the literature for comparison. Finally, when possible we compare the present results with the other available theoretical data.

  12. Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces

    NASA Astrophysics Data System (ADS)

    Grisolia, M. N.; Varignon, J.; Sanchez-Santolino, G.; Arora, A.; Valencia, S.; Varela, M.; Abrudan, R.; Weschke, E.; Schierle, E.; Rault, J. E.; Rueff, J.-P.; Barthélémy, A.; Santamaria, J.; Bibes, M.

    2016-05-01

    At interfaces between conventional materials, band bending and alignment are classically controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from strong Coulomb interactions at and between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence.

  13. Hybridization-controlled charge transfer and induced magnetism at correlated oxide interfaces

    PubMed Central

    Grisolia, M.N.; Arora, A.; Valencia, S.; Varela, M.; Abrudan, R.; Weschke, E.; Schierle, E.; Rault, J.E.; Rueff, J.-P.; Barthélémy, A.; Santamaria, J.; Bibes, M.

    2015-01-01

    At interfaces between conventional materials, band bending and alignment are classically controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from strong Coulomb interactions between transition metal and oxygen ions. Such electronic correlations offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. Here we show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we probe charge reconstruction at interfaces with gadolinium titanate GdTiO3. X-ray absorption spectroscopy shows that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate, exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence. PMID:27158255

  14. Tunable charge transfer properties in metal-phthalocyanine heterojunctions.

    PubMed

    Siles, P F; Hahn, T; Salvan, G; Knupfer, M; Zhu, F; Zahn, D R T; Schmidt, O G

    2016-04-28

    Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

  15. Electrophoresis of a charged soft particle in a charged cavity with arbitrary double-layer thickness.

    PubMed

    Chen, Wei J; Keh, Huan J

    2013-08-22

    An analysis for the quasi-steady electrophoretic motion of a soft particle composed of a charged spherical rigid core and an adsorbed porous layer positioned at the center of a charged spherical cavity filled with an arbitrary electrolyte solution is presented. Within the porous layer, frictional segments with fixed charges are assumed to distribute uniformly. Through the use of the linearized Poisson-Boltzmann equation and the Laplace equation, the equilibrium double-layer potential distribution and its perturbation caused by the applied electric field are separately determined. The modified Stokes and Brinkman equations governing the fluid flow fields outside and inside the porous layer, respectively, are solved subsequently. An explicit formula for the electrokinetic migration velocity of the soft particle in terms of the fixed charge densities on the rigid core surface, in the porous layer, and on the cavity wall is obtained from a balance between its electrostatic and hydrodynamic forces. This formula is valid for arbitrary values of κa, λa, r0/a, and a/b, where κ is the Debye screening parameter, λ is the reciprocal of the length characterizing the extent of flow penetration inside the porous layer, a is the radius of the soft particle, r0 is the radius of the rigid core of the particle, and b is the radius of the cavity. In the limiting cases of r0 = a and r0 = 0, the migration velocity for the charged soft sphere reduces to that for a charged impermeable sphere and that for a charged porous sphere, respectively, in the charged cavity. The effect of the surface charge at the cavity wall on the particle migration can be significant, and the particle may reverse the direction of its migration.

  16. Structure and Electronic Spectra of Purine-Methyl Viologen Charge Transfer Complexes

    PubMed Central

    Jalilov, Almaz S.; Patwardhan, Sameer; Singh, Arunoday; Simeon, Tomekia; Sarjeant, Amy A.; Schatz, George C.; Lewis, Frederick D.

    2014-01-01

    The structure and properties of the electron donor-acceptor complexes formed between methyl viologen (MV) and purine nucleosides and nucleotides in water and the solid state have been investigated using a combination of experimental and theoretical methods. Solution studies were performed using UV-vis and 1H NMR spectroscopy. Theoretical calculations were performed within the framework of density functional theory (DFT). Energy decomposition analysis indicates that dispersion and induction (charge-transfer) interactions dominate the total binding energy, whereas electrostatic interactions are largely repulsive. The appearance of charge transfer bands in the absorption spectra of the complexes are well described by time-dependent (TD) DFT and are further explained in terms of the redox properties of purine monomers and solvation effects. Crystal structures are reported for complexes of methyl viologen with the purines 2′-deoxyguanosine 3′-monophosphate GMP (DAD′DAD′ type) and 7-deazaguanosine zG (DAD′ADAD′ type). Comparison of the structures determined in the solid state and by theoretical methods in solution provides valuable insights into the nature of charge-transfer interactions involving purine bases as electron donors. PMID:24294996

  17. Characteristic Features of Double Layers in Rotating, Magnetized Plasma Contaminated with Dust Grains with Varying Charges

    NASA Astrophysics Data System (ADS)

    Paul, Jaydeep; Nag, Apratim; Devi, Karabi; Das, Himadri Sekhar

    2018-03-01

    The evolution and the characteristic features of double layers in a plasma under slow rotation and contaminated with dust grains with varying charges under the effect of an external magnetic field are studied. The Coriolis force resulting from the slow rotation is responsible for the generation of an equivalent magnetic field. A comparatively new pseudopotential approach has been used to derive the small amplitude double layers. The effect of the relative electron-ion concentration, as well as the temperature ratio, on the formation of the double layers has also been investigated. The study reveals that compressive, as well as rarefactive, double layers can be made to co-exist in plasma by controlling the dust charge fluctuation effect supplemented by variations of the plasma constituents. The effectiveness of slow rotation in causing double layers to exist has also emanated from the study. The results obtained could be of interest because of their possible applications in both laboratories and space.

  18. Modelling charge transfer reactions with the frozen density embedding formalism.

    PubMed

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

    The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two π-stacked nucleobase dimers of B-DNA: 5'-GG-3' and 5'-GT-3'. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionals are used the electronic couplings are grossly overestimated.

  19. Double diffusive conjugate heat transfer: Part II

    NASA Astrophysics Data System (ADS)

    Azeem, Soudagar, Manzoor Elahi M.

    2018-05-01

    Conjugate heat transfer in porous medium is an important study involved in many practical applications. The current study is aimed to investigate the double diffusive flow in a square porous cavity subjected to left vertical surface heating and right vertical surface cooling respectively along with left and right surfaces maintained at high and low concentration. The three governing equations are converted into algebraic form of equations by applying finite element method and solved in iterative manner. The study is focused to investigate the effect of presence of solid inside the cavity with respect to varying buoyancy ratio. It is found that the local heat and mass transfer rate decreases along the height of cavity.

  20. Signature of charge migration in modulations of double ionization

    NASA Astrophysics Data System (ADS)

    Mauger, François; Abanador, Paul M.; Bruner, Adam; Sissay, Adonay; Gaarde, Mette B.; Lopata, Kenneth; Schafer, Kenneth J.

    2018-04-01

    We present a theoretical investigation of charge migration following strong-field ionization in a multielectron system. We study a model homonuclear molecule with two electrons, each restricted to one dimension (1 +1 D ), interacting with a strong, static electric field. We show that in this system charge migration results from the interplay between multiple ionization channels that overlap in space, creating a coherent electron-hole wave packet in the cation. We also find that, in our case, charge migration following the first ionization manifests as a modulation of the subsequent double-ionization signal. We derive a parametrized semiclassical model from the full multielectron system and we discuss the importance of the choice of cation electronic-structure basis for the efficacy of the semiclassical representation. We use the ab initio solution of the full 1 +1 D system as a reference for the qualitative and quantitative results of the parametrized semiclassical model. We discuss the extension of our model to long-wavelength time-dependent fields with full-dimension, many-electron targets.

  1. Surfactant-enhanced singlet energy transfer from the charge-transfer excited state of tris(2,2-bipyridine) ruthenium(II)

    NASA Astrophysics Data System (ADS)

    Mandal, Krishnagopal; Demas, J. N.

    1981-12-01

    Very efficient (45-75%) sodium lauryl sulfate (NaLS) enhanced singlet enengy transfer has been demonstrated from the spin-orbit charge-transfer excited state of [Ru(bpy) 3] 2+ (bpy = 2,2'-bipyridine) to the xxx violet, oxazine 1, and rhodamine 101 at concentrations of 10 -5 M, Energy transfer occurs in xxx.

  2. Improving nanoparticle dispersion and charge transfer in cadmium telluride tetrapod and conjugated polymer blends.

    PubMed

    Monson, Todd C; Hollars, Christopher W; Orme, Christine A; Huser, Thomas

    2011-04-01

    The dispersion of CdTe tetrapods in a conducting polymer and the resulting charge transfer is studied using a combination of confocal fluorescence microscopy and atomic force microscopy (AFM). The results of this work show that both the tetrapod dispersion and charge transfer between the CdTe and conducting polymer (P3HT) are greatly enhanced by exchanging the ligands on the surface of the CdTe and by choosing proper solvent mixtures. The ability to experimentally probe the relationship between particle dispersion and charge transfer through the combination of AFM and fluorescence microscopy provides another avenue to assess the performance of polymer/semiconductor nanoparticle composites. © 2011 American Chemical Society

  3. Effects of convergent diffusion and charge transfer kinetics on the diffusion layer thickness of spherical micro- and nanoelectrodes.

    PubMed

    Molina, A; Laborda, E; González, J; Compton, R G

    2013-05-21

    Nuances of the linear diffusion layer approximation are examined for slow charge transfer reactions at (hemi)spherical micro- and nanoelectrodes. This approximation is widely employed in Electrochemistry to evaluate the extent of electrolyte solution perturbed by the electrode process, which is essential to the understanding of the effects arising from thin-layer diffusion, convergent diffusion, convection, coupled chemical reactions and the double layer. The concept was well established for fast charge transfer processes at macroelectrodes, but remains unclear under other conditions such that a thorough assessment of its meaning was necessary. In a previous publication [A. Molina, J. González, E. Laborda and R. G. Compton, Phys. Chem. Chem. Phys., 2013, 15, 2381-2388] we shed some light on the influence of the reversibility degree. In the present work, the meaning of the diffusion layer thickness is investigated when very small electrodes are employed and so the contribution of convergent diffusion to the mass transport is very important. An analytical expression is given to calculate the linear diffusion layer thickness at (hemi)spherical electrodes and its behaviour is studied for a wide range of conditions of reversibility (from reversible to fully-irreversible processes) and electrode size (from macro- to nano-electrodes). Rigorous analytical solutions are deduced for true concentration profiles, surface concentrations, linear diffusion layer thickness and current densities when a potential pulse is applied at (hemi)spherical electrodes. The expressions for the magnitudes mentioned above are valid for electrodes of any size (including (hemi)spherical nanoelectrodes) and for any degree of reversibility, provided that mass transport occurs exclusively via diffusion. The variation of the above with the electrode size, applied potential and charge transfer kinetics is studied.

  4. Topological Effects of Charge Transfer in Telomere G-Quadruplex Mechanism on Telomerase Activation and Inhibition

    NASA Astrophysics Data System (ADS)

    Wang, Xin; Liang, Shi-Dong

    2013-02-01

    We explore the charge transfer in the telomere G-Quadruplex (TG4) DNA theoretically by the nonequilibrium Green's function method, and reveal the topological effect of the charge transport in TG4 DNA. The consecutive TG4 (CTG4) is semiconducting with 0.2 0.3 eV energy gap. Charges transfer favorably in the CTG4, but are trapped in the nonconsecutive TG4 (NCTG4). The global conductance is inversely proportional to the local conductance for NCTG4. The topological structure transition from NCTG4 to CTG4 induces abruptly 3nA charge current, which provide a microscopic clue to understand the telomerase activated or inhibited by TG4. Our findings reveal the fundamental property of charge transfer in TG4 and its relationship with the topological structure of TG4.

  5. Charge transfer induced by MoO3 at boron subphthalocyanine chloride/α-sexithiophene heterojunction interface

    NASA Astrophysics Data System (ADS)

    Foggiatto, Alexandre L.; Sakurai, Takeaki

    2018-03-01

    The energy-level alignment of boron subphthalocyanine chloride (SubPc)/α-sexithiophene (6T) grown on MoO3 was investigated using ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS). We demonstrated that the p-doping effect generated by the MoO3 layer can induce charge transfer at the organic-organic heterojunction interface. After the deposition of 6T on MoO3, the fermi level becomes pinned close to the 6T highest occupied molecular orbital (HOMO) level and when SubPc is deposited, owing to its tail states, charge transfer occurs in order to achieve thermodynamic equilibrium. We also demonstrated that the charge transfer can be reduced by annealing the film. We suggested that the reduction of the misalignment on the film induces a reduction in the density of gap states, which controls the charge transfer.

  6. Energy and charge transfer in ionized argon coated water clusters.

    PubMed

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

    2013-12-07

    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 (H2O)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 (H2O)(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 (H2O)(n)H2(2+) and (H2O)(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.

  7. Anomalous double-stripe charge ordering in β -NaFe2O3 with double triangular layers consisting of almost perfect regular Fe4 tetrahedra

    NASA Astrophysics Data System (ADS)

    Kobayashi, Shintaro; Ueda, Hiroaki; Michioka, Chishiro; Yoshimura, Kazuyoshi; Nakamura, Shin; Katsufuji, Takuro; Sawa, Hiroshi

    2018-05-01

    The physical properties of the mixed-valent iron oxide β -NaFe2O3 were investigated by means of synchrotron radiation x-ray diffraction, magnetization, electrical resistivity, differential scanning calorimetry, 23Na NMR, and 57FeM o ̈ssbauer measurements. This compound has double triangular layers consisting of almost perfect regular Fe4 tetrahedra, which suggests geometrical frustration. We found that this compound exhibits an electrostatically unstable double-stripe-type charge ordering, which is stabilized by the cooperative compression of Fe3 +O6 octahedra, owing to a valence change and Fe2 +O6 octahedra due to Jahn-Teller distortion. Our results indicate the importance of electron-phonon coupling for charge ordering in the region of strong charge frustration.

  8. Charge transfer in trans-combretastatins

    NASA Astrophysics Data System (ADS)

    Holzmann, Nicole; Bernasconi, Leonardo; Callaghan, Kathrin M.; Bisby, Roger H.; Parker, Anthony W.

    2018-01-01

    The non-toxic trans isomer of combretastatin-A4 can be photoisomerised in physiological conditions to cis-CA4, a potential anticancer drug. Absorption at wavelengths with high tissue penetration can be achieved by functionalization with substituents influencing the degree of charge-transfer (CT) of the S1 state, in which the isomerisation occurs. We present a TDDFT study of the excited state properties of a series of substituted combretastatins with various degrees of CT character. Increasing the CT character determines a redshift of absorption and an intensity enhancement, but it disfavours the isomerisation. An appropriate choice of substituents is therefore required to achieve optimal isomerisation conditions.

  9. Evidences For Charge Transfer-Induced Conformational Changes In Carbon Nanostructure-Protein Corona

    PubMed Central

    Podila, R.; Vedantam, P.; Ke, P. C.; Brown, J. M.; Rao, A. M.

    2012-01-01

    The binding of proteins to a nanostructure often alters protein secondary and tertiary structures. However, the main physical mechanisms that elicit protein conformational changes in the presence of the nanostructure have not yet been fully established. Here we performed a comprehensive spectroscopic study to probe the interactions between bovine serum albumin (BSA) and carbon-based nanostructures of graphene and single-walled carbon nanotubes (SWNTs). Our results showed that the BSA “corona” acted as a weak acceptor to facilitate charge transfer from the carbon nanostructures. Notably, we observed that charge transfer occurred only in the case of SWNTs but not in graphene, resulting from the sharp and discrete electronic density of states of the former. Furthermore, the relaxation of external α–helices in BSA secondary structure increased concomitantly with the charge transfer. These results may help guide controlled nanostructure-biomolecular interactions and prove beneficial for developing novel drug delivery systems, biomedical devices and engineering of safe nanomaterials. PMID:23243478

  10. Engineering the Charge Transfer in all 2D Graphene-Nanoplatelets Heterostructure Photodetectors

    PubMed Central

    Robin, A.; Lhuillier, E.; Xu, X. Z.; Ithurria, S.; Aubin, H.; Ouerghi, A.; Dubertret, B.

    2016-01-01

    Two dimensional layered (i.e. van der Waals) heterostructures open up great prospects, especially in photodetector applications. In this context, the control of the charge transfer between the constituting layers is of crucial importance. Compared to bulk or 0D system, 2D materials are characterized by a large exciton binding energy (0.1–1 eV) which considerably affects the magnitude of the charge transfer. Here we investigate a model system made from colloidal 2D CdSe nanoplatelets and epitaxial graphene in a phototransistor configuration. We demonstrate that using a heterostructured layered material, we can tune the magnitude and the direction (i.e. electron or hole) of the charge transfer. We further evidence that graphene functionalization by nanocrystals only leads to a limited change in the magnitude of the 1/f noise. These results draw some new directions to design van der Waals heterostructures with enhanced optoelectronic properties. PMID:27143413

  11. Enhanced spin-torque in double tunnel junctions using a nonmagnetic-metal spacer

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

    Chen, C. H.; Cheng, Y. H.; Ko, C. W.

    2015-10-12

    This study proposes an enhancement in the spin-transfer torque of a magnetic tunnel junction (MTJ) designed with double-barrier layer structure using a nonmagnetic metal spacer, as a replacement for the ferromagnetic material, which is traditionally used in these double-barrier stacks. Our calculation results show that the spin-transfer torque and charge current density of the proposed double-barrier MTJ can be as much as two orders of magnitude larger than the traditional double-barrier one. In other words, the proposed double-barrier MTJ has a spin-transfer torque that is three orders larger than that of the single-barrier stack. This improvement may be attributed tomore » the quantum-well states that are formed in the nonmagnetic metal spacer and the resonant tunneling mechanism that exists throughout the system.« less

  12. The low-energy, charge-transfer excited states of 4-amino-4-prime-nitrodiphenyl sulfide

    NASA Technical Reports Server (NTRS)

    O'Connor, Donald B.; Scott, Gary W.; Tran, Kim; Coulter, Daniel R.; Miskowski, Vincent M.; Stiegman, Albert E.; Wnek, Gary E.

    1992-01-01

    Absorption and emission spectra of 4-amino-4-prime-nitrodiphenyl sulfide in polar and nonpolar solvents were used to characterize and assign the low-energy excited states of the molecule. Fluorescence-excitation anisotropy spectra and fluorescence quantum yields were also used to characterize the photophysics of these states. The lowest-energy fluorescent singlet state was determined to be an intramolecular charge transfer (ICT) state involving transfer of a full electron charge from the amino to the nitro group yielding a dipole moment of about 50 D. A low-energy, intense absorption band is assigned as a transition to a different ICT state involving a partial electron charge transfer from sulfur to the nitro group.

  13. Modelling charge transfer reactions with the frozen density embedding formalism

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

    Pavanello, Michele; Neugebauer, Johannes

    2011-12-21

    The frozen density embedding (FDE) subsystem formulation of density-functional theory is a useful tool for studying charge transfer reactions. In this work charge-localized, diabatic states are generated directly with FDE and used to calculate electronic couplings of hole transfer reactions in two {pi}-stacked nucleobase dimers of B-DNA: 5{sup '}-GG-3{sup '} and 5{sup '}-GT-3{sup '}. The calculations rely on two assumptions: the two-state model, and a small differential overlap between donor and acceptor subsystem densities. The resulting electronic couplings agree well with benchmark values for those exchange-correlation functionals that contain a high percentage of exact exchange. Instead, when semilocal GGA functionalsmore » are used the electronic couplings are grossly overestimated.« less

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Direct Measurement of Charge Regulation in Metalloprotein Electron Transfer.

    PubMed

    Zahler, Collin T; Zhou, Hongyu; Abdolvahabi, Alireza; Holden, Rebecca L; Rasouli, Sanaz; Tao, Peng; Shaw, Bryan F

    2018-05-04

    Determining whether a protein regulates its net electrostatic charge during electron transfer (ET) will deepen our mechanistic understanding of how polypeptides tune rates and free energies of ET (e.g., by affecting reorganization energy, and/or redox potential). Charge regulation during ET has never been measured for proteins because few tools exist to measure the net charge of a folded protein in solution at different oxidation states. Herein, we used a niche analytical tool (protein charge ladders analyzed with capillary electrophoresis) to determine that the net charges of myoglobin, cytochrome c, and azurin change by 0.62±0.06, 1.19±0.02, and 0.51±0.04 units upon single ET. Computational analysis predicts that these fluctuations in charge arise from changes in the pK a  values of multiple non-coordinating residues (predominantly histidine) that involve between 0.42-0.90 eV. These results suggest that ionizable residues can tune the reactivity of redox centers by regulating the net charge of the entire protein-cofactor-solvent complex. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Charge transfer to ground-state ions produces free electrons

    PubMed Central

    You, D.; Fukuzawa, H.; Sakakibara, Y.; Takanashi, T.; Ito, Y.; Maliyar, G. G.; Motomura, K.; Nagaya, K.; Nishiyama, T.; Asa, K.; Sato, Y.; Saito, N.; Oura, M.; Schöffler, M.; Kastirke, G.; Hergenhahn, U.; Stumpf, V.; Gokhberg, K.; Kuleff, A. I.; Cederbaum, L. S.; Ueda, K

    2017-01-01

    Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne–Kr mixed clusters. PMID:28134238

  18. Using quantum dynamics simulations to follow the competition between charge migration and charge transfer in polyatomic molecules

    NASA Astrophysics Data System (ADS)

    Spinlove, K. E.; Vacher, M.; Bearpark, M.; Robb, M. A.; Worth, G. A.

    2017-01-01

    Recent work, particularly by Cederbaum and co-workers, has identified the phenomenon of charge migration, whereby charge flow occurs over a static molecular framework after the creation of an electronic wavepacket. In a real molecule, this charge migration competes with charge transfer, whereby the nuclear motion also results in the re-distribution of charge. To study this competition, quantum dynamics simulations need to be performed. To break the exponential scaling of standard grid-based algorithms, approximate methods need to be developed that are efficient yet able to follow the coupled electronic-nuclear motion of these systems. Using a simple model Hamiltonian based on the ionisation of the allene molecule, the performance of different methods based on Gaussian Wavepackets is demonstrated.

  19. Double heterojunction nanowire photocatalysts for hydrogen generation.

    PubMed

    Tongying, P; Vietmeyer, F; Aleksiuk, D; Ferraudi, G J; Krylova, G; Kuno, M

    2014-04-21

    Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ∼434.29 ± 27.40 μmol h(-1) g(-1) under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.

  20. Effective pathway of charge transfer in DNA duplex

    NASA Astrophysics Data System (ADS)

    Kim, Seongjin; Yi, Juyeon; Hwang, Sun-Yong

    2009-03-01

    We examine the most efficient route for charge propagation in DNA duplex. We find a direct path along one strand and a detour using the complementary strand compete with each other. Charge tends to take the path along the strand whose energy levels are close to its energy, and yet there exists a crossover length Nc so that for a transfer over a distance shorter than Nc the direct path is always advantageous. We obtain the analytic results for the behavior together with various decay types such as a constant decay, an exponential decay, and a crossover between them, whose validity is confirmed by the numerical calculation.

  1. Substituent and Solvent Effects on Excited State Charge Transfer Behavior of Highly Fluorescent Dyes Containing Thiophenylimidazole-Based Aldehydes

    NASA Technical Reports Server (NTRS)

    Santos, Javier; Bu, Xiu R.; Mintz, Eric A.

    2001-01-01

    The excited state charge transfer for a series of highly fluorescent dyes containing thiophenylimidazole moiety was investigated. These systems follow the Twisted Intramolecular Charge Transfer (TICT) model. Dual fluorescence was observed for each substituted dye. X-ray structures analysis reveals a twisted ground state geometry for the donor substituted aryl on the 4 and 5 position at the imidazole ring. The excited state charge transfer was modeled by a linear solvation energy relationship using Taft's pi and Dimroth's E(sub T)(30) as solvent parameters. There is linear relation between the energy of the fluorescence transition and solvent polarity. The degree of stabilization of the excited state charge transfer was found to be consistent with the intramolecular molecular charge transfer. Excited dipole moment was studied by utilizing the solvatochromic shift method.

  2. Transition from capacitive coupling to direct charge transfer in asymmetric terahertz plasmonic assemblies.

    PubMed

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

    2016-11-15

    We experimentally and numerically analyze the charge transfer THz plasmons using an asymmetric plasmonic assembly of metallic V-shaped blocks. The asymmetric design of the blocks allows for the excitation of classical dipolar and multipolar modes due to the capacitive coupling. Introducing a conductive microdisk between the blocks, we facilitated the excitation of the charge transfer plasmons and studied their characteristics along with the capacitive coupling by varying the size of the disk.

  3. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

    DOE PAGES

    Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud; ...

    2016-10-18

    We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS 2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

  4. Ultrafast Charge Transfer and Hybrid Exciton Formation in 2D/0D Heterostructures

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

    Boulesbaa, Abdelaziz; Wang, Kai; Mahjouri-Samani, Masoud

    We report that photoinduced interfacial charge transfer is at the heart of many applications, including photovoltaics, photocatalysis, and photodetection. With the emergence of a new class of semiconductors such as monolayer two-dimensional transition metal dichalcogenides (2D-TMDs), charge transfer at the 2D/2D heterojunctions attracted several efforts due to the remarkable optical and electrical properties of 2D-TMDs. Unfortunately, in 2D/2D heterojunctions, for a given combination of two materials, the relative energy band alignment and the charge transfer efficiency are locked. Due to their large variety and broad size tunability, semiconductor quantum dots (0D-QDs) interfaced with 2D-TMDs may become an attractive heterostructure formore » optoelectronic applications. Here, we incorporate femtosecond pump-probe spectroscopy to reveal the sub-45 fs charge transfer at a 2D/0D heterostructure composed of tungsten disulfide monolayers (2D-WS 2) and a single layer of cadmium selenide (CdSe)/zinc sulfide (ZnS) core/shell 0D-QDs. Furthermore, ultrafast dynamics and steady-state measurements suggested that following electron transfer from the 2D to the 0D, hybrid excitons (HXs), wherein the electron resides in the 0D and hole resides in the 2D-TMD monolayer, are formed with a binding energy on the order of ~140 meV, which is several times lower than that of tightly bound excitons in 2D-TMDs.« less

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  6. Repair of DNA double-strand breaks and cell killing by charged particles

    NASA Astrophysics Data System (ADS)

    Eguchi-Kasai, K.; Murakami, M.; Itsukaichi, H.; Fukutsu, K.; Yatagai, F.; Kanai, T.; Ohara, H.; Sato, K.

    It has been suggested that it is not simple double-strand breaks (dsb) but the non-reparable breaks which correlate well with the high biological effectiveness of high LET radiations for cell killing. We have compared the effects of charged particles on cell death in 3 pairs of cell lines which are normal or defective in the repair of DNA dsbs. For the cell lines SL3-147, M10, and SX10 which are deficient in DNA dsb repair, RBE values were close to unity for cell killing induced by charged particles with linear energy transfer (LET) up to 200 keV/mum and were even smaller than unity for the LET region greater than 300 keV/mum. The inactivation cross section (ICS) increased with LET for all 3 pairs. The ICS of dsb repair deficient mutants was always larger than that of their parents for all the LET ranges, but with increasing LET the difference in ICS between the mutant and its parent became smaller. Since a small difference in ICS remained at LET of about 300 keV/mum, dsb repair may still take place at this high LET, even if its role is apparently small. These results suggest that the DNA repair system does not play a major role in protection against the attack of high LET radiations and that a main cause of cell death is non-reparable dsb which are produced at a higher yield compared with low LET radiations. No correlation was observed between DNA content or nuclear area and ICS.

  7. Direct Observation of Charge Transfer at a MgO(111) Surface

    NASA Astrophysics Data System (ADS)

    Subramanian, A.; Marks, L. D.; Warschkow, O.; Ellis, D. E.

    2004-01-01

    Transmission electron diffraction (TED) combined with direct methods have been used to study the √(3)×√(3)R30° reconstruction on the polar (111) surface of MgO and refine the valence charge distribution. The surface is nonstoichiometric and is terminated by a single magnesium atom. A charge-compensating electron hole is localized in the next oxygen layer and there is a nominal charge transfer from the oxygen atoms to the top magnesium atom. The partial charges that we obtain for the surface atoms are in reasonable agreement with empirical bond-valence estimations.

  8. [Double toe to hand transfer in children with symbrachydactyly].

    PubMed

    Rivas, S; López-Gutiérrez, J C; Lovic, A; Díaz, M; Andrés, A M; Ros, Z

    2006-07-01

    Symbrachydactyly is fairly frequent congenital malformation that appears during first weeks of pregnancy. The range of clinical presentations goes from hypoplastic fingers to true agenesis. Although it usually appears in a random fashion, sometimes it is associated to other systemic malformations. The aim of this study is to check the functional, cosmetic and psychological results of those patients affected of grade IV symbrachydactyly treated using a double second toe transfer. The method employed is a retrospective study of the clinical records from 6 patients (5 males and 1 female) operated in our Department during the last five years. The follow up period was from 3 months to five years. Transfer from the second toe to the first ray was performed during the first surgical period, while transfer to the fourth ray was done in a second procedure. The mean age for the first operation was 19 months, and 30 months for the second one. There were no flap failure or major surgical complications. Tenolysis and tenoplasty was done in two patients to improve flap function and position. Motion rehabilitation was installed during the postoperative period. Functional, opposing pinch, and cosmetic results were satisfactory. Parents "and patients" psychological acceptance was also good. No walk disturbance was observed. Double second toe to hand transfer is a good option for the symbrachydactyly treatment in cases of thumb agenesis. Rehabilitation is the key clue for functional recovery. Surgery improves social and family relationships.

  9. Bands dispersion and charge transfer in β-BeH2

    NASA Astrophysics Data System (ADS)

    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.

  10. Designing a Spin-one Mott Insulator: Complete Charge Transfer in Nickelate-Titanate Heterostructures

    NASA Astrophysics Data System (ADS)

    Chen, Hanghui; Marianetti, Chris; Millis, Andrew

    2013-03-01

    Ab initio calculations are performed to show that complete charge transfer may occur from the TiO2 to the NiO2 layers in (LaTiO3)1/(LaNiO3)1 superlattices. Although the two component materials are an S = 1 / 2 Mott insulator and a weakly correlated paramagnetic metal, strong correlation effects on Ni d states can render the superlattice an unusual S = 1 charge transfer insulator, with the Ti- d band empty, the Ni in the d8 state and the oxygen bands filled. The charge transfer gap is set by the Ti/Ni d level splitting. Magnetic, photoemission and x-ray scattering experiments are suggested to test the theory. The results show that heterostructuring can lead to very high levels of electron doping of oxides. This research was supported by the Army Research Office under ARO-Ph 56032 and DOE-ER-046169.

  11. Charge-transfer mechanisms for high-T/sub c/ superconductivity

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

    Jarrell, M.; Krishnamurthy, H.R.; Cox, D.L.

    1988-09-01

    We report results from a Bardeen-Cooper-Schrieffer (BCS) analysis of the Weber d-d exciton model of the high-temperature superconductors. The pairing between oxygen holes is mediated by localized intrasite charge-transfer excitations between the d/sub x//sub <2/-y/sup =/ and the d/sub 3//sub z//sub <2/-r/sup =/ Cu orbitals. For reasonable oxygen on-site Coulomb energies, we find s-wave superconductivity for low filling fraction (<0.44), and d-wave superconductivity for larger filling. The same symmetry analysis applies to a localized version of the intersite Cu-O charge-transfer model of Varma, Schmitt-Rink, and Abrahams. We explore the limitations imposed by the Weber model symmetry, and interpret optical datamore » based upon the d-d exciton picture. We briefly discuss the suppression of antiferromagnetism of the Cu moments by the Ruderman-Kittel-Kasuya-Yoshida interaction in the metallic limit.« less

  12. Charge transfer in photorechargeable composite films of TiO2 and polyaniline

    NASA Astrophysics Data System (ADS)

    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.

  13. Correlating electronic and vibrational motions in charge transfer systems

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

    Khalil, Munira

    2014-06-27

    The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

  14. Pattern classification using charge transfer devices

    NASA Technical Reports Server (NTRS)

    1980-01-01

    The feasibility of using charge transfer devices in the classification of multispectral imagery was investigated by evaluating particular devices to determine their suitability in matrix multiplication subsystem of a pattern classifier and by designing a protype of such a system. Particular attention was given to analog-analog correlator devices which consist of two tapped delay lines, chip multipliers, and a summed output. The design for the classifier and a printed circuit layout for the analog boards were completed and the boards were fabricated. A test j:g for the board was built and checkout was begun.

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

    PubMed

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

    2017-10-11

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

  16. Charge transfer interactions in oligomer coated gold nanoclusters

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

    Newmai, M. Boazbou; Kumar, Pandian Senthil, E-mail: duplasmonics@gmail.com

    Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, whichmore » could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.« less

  17. Carbon-, sulfur-, and phosphorus-based charge transfer reactions in inductively coupled plasma-atomic emission spectrometry

    NASA Astrophysics Data System (ADS)

    Grindlay, Guillermo; Gras, Luis; Mora, Juan; de Loos-Vollebregt, Margaretha T. C.

    2016-01-01

    In this work, the influence of carbon-, sulfur-, and phosphorus-based charge transfer reactions on the emission signal of 34 elements (Ag, Al, As, Au, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe, Ga, Hg, I, In, Ir, K, Li, Mg, Mn, Na, Ni, P, Pb, Pd, Pt, S, Sb, Se, Sr, Te, and Zn) in axially viewed inductively coupled plasma-atomic emission spectrometry has been investigated. To this end, atomic and ionic emission signals for diluted glycerol, sulfuric acid, and phosphoric acid solutions were registered and results were compared to those obtained for a 1% w w- 1 nitric acid solution. Experimental results show that the emission intensities of As, Se, and Te atomic lines are enhanced by charge transfer from carbon, sulfur, and phosphorus ions. Iodine and P atomic emission is enhanced by carbon- and sulfur-based charge transfer whereas the Hg atomic emission signal is enhanced only by carbon. Though signal enhancement due to charge transfer reactions is also expected for ionic emission lines of the above-mentioned elements, no experimental evidence has been found with the exception of Hg ionic lines operating carbon solutions. The effect of carbon, sulfur, and phosphorus charge transfer reactions on atomic emission depends on (i) wavelength characteristics. In general, signal enhancement is more pronounced for electronic transitions involving the highest upper energy levels; (ii) plasma experimental conditions. The use of robust conditions (i.e. high r.f. power and lower nebulizer gas flow rates) improves carbon, sulfur, and phosphorus ionization in the plasma and, hence, signal enhancement; and (iii) the presence of other concomitants (e.g. K or Ca). Easily ionizable elements reduce ionization in the plasma and consequently reduce signal enhancement due to charge transfer reactions.

  18. Investigation of surface charge density on solid-liquid interfaces by modulating the electrical double layer.

    PubMed

    Moon, Jong Kyun; Song, Myung Won; Pak, Hyuk Kyu

    2015-05-20

    A solid surface in contact with water or aqueous solution usually carries specific electric charges. These surface charges attract counter ions from the liquid side. Since the geometry of opposite charge distribution parallel to the solid-liquid interface is similar to that of a capacitor, it is called an electrical double layer capacitor (EDLC). Therefore, there is an electrical potential difference across an EDLC in equilibrium. When a liquid bridge is formed between two conducting plates, the system behaves as two serially connected EDLCs. In this work, we propose a new method for investigating the surface charge density on solid-liquid interfaces. By mechanically modulating the electrical double layers and simultaneously applying a dc bias voltage across the plates, an ac electric current can be generated. By measuring the voltage drop across a load resistor as a function of bias voltage, we can study the surface charge density on solid-liquid interfaces. Our experimental results agree very well with the simple equivalent electrical circuit model proposed here. Furthermore, using this method, one can determine the polarity of the adsorbed state on the solid surface depending on the material used. We expect this method to aid in the study of electrical phenomena on solid-liquid interfaces.

  19. A simple model of solvent-induced symmetry-breaking charge transfer in excited quadrupolar molecules

    NASA Astrophysics Data System (ADS)

    Ivanov, Anatoly I.; Dereka, Bogdan; Vauthey, Eric

    2017-04-01

    A simple model has been developed to describe the symmetry-breaking of the electronic distribution of AL-D-AR type molecules in the excited state, where D is an electron donor and AL and AR are identical acceptors. The origin of this process is usually associated with the interaction between the molecule and the solvent polarization that stabilizes an asymmetric and dipolar state, with a larger charge transfer on one side than on the other. An additional symmetry-breaking mechanism involving the direct Coulomb interaction of the charges on the acceptors is proposed. At the same time, the electronic coupling between the two degenerate states, which correspond to the transferred charge being localised either on AL or AR, favours a quadrupolar excited state with equal amount of charge-transfer on both sides. Because of these counteracting effects, symmetry breaking is only feasible when the electronic coupling remains below a threshold value, which depends on the solvation energy and the Coulomb repulsion energy between the charges located on AL and AR. This model allows reproducing the solvent polarity dependence of the symmetry-breaking reported recently using time-resolved infrared spectroscopy.

  20. Possible charge analogues of spin transfer torques in bulk superconductors

    NASA Astrophysics Data System (ADS)

    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.

  1. Laboratory Studies of Thermal Energy Charge Transfer of Silicon and Iron Ions in Astrophysical Plasmas

    NASA Technical Reports Server (NTRS)

    Kwong, Victor H. S.

    1997-01-01

    The laser ablation/ion storage facility at the UNLV Physics Department is dedicated to the study of atomic processes in low temperature plasmas. Our current program is directed to the study of charge transfer of multiply charged ions and neutrals that are of importance to astrophysics at energies less than 1 eV (about 10(exp 4) K). Specifically, we measure the charge transfer rate coefficient of ions such as N(2+), Si(3+), Si(3+), with helium and Fe(2+) with molecular and atomic hydrogen. All these ions are found in a variety of astrophysical plasmas. Their electron transfer reactions with neutral atoms can affect the ionization equilibrium of the plasma.

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

    PubMed

    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.

  3. Semiconducting double-dot exchange-only qubit dynamics in the presence of magnetic and charge noises

    NASA Astrophysics Data System (ADS)

    Ferraro, E.; Fanciulli, M.; De Michielis, M.

    2018-06-01

    The effects of magnetic and charge noises on the dynamical evolution of the double-dot exchange-only qubit (DEOQ) is theoretically investigated. The DEOQ consisting of three electrons arranged in an electrostatically defined double quantum dot deserves special interest in quantum computation applications. Its advantages are in terms of fabrication, control and manipulation in view of implementation of fast single and two-qubit operations through only electrical tuning. The presence of the environmental noise due to nuclear spins and charge traps, in addition to fluctuations in the applied magnetic field and charge fluctuations on the electrostatic gates adopted to confine the electrons, is taken into account including random magnetic field and random coupling terms in the Hamiltonian. The behavior of the return probability as a function of time for initial conditions of interest is presented. Moreover, through an envelope-fitting procedure on the return probabilities, coherence times are extracted when model parameters take values achievable experimentally in semiconducting devices.

  4. Effects of low charge injection densities on corrosion responses of pulsed 316LVM stainless steel electrodes.

    PubMed

    Riedy, L W; Walter, J S

    1996-06-01

    The safe charge injection density for pulsing of 316LVM electrodes has been reported to be 40 microC/cm2. However, only 20 microC/cm2 is available for nonfaradic charge transfer and double layer charge injection. Therefore, we evaluated long term pulsing at 20 microC/cm2 with capacitor coupling.

  5. Charge Carrier Dynamics in Cs2AgBiBr6 Double Perovskite

    PubMed Central

    2018-01-01

    Double perovskites, comprising two different cations, are potential nontoxic alternatives to lead halide perovskites. Here, we characterized thin films and crystals of Cs2AgBiBr6 by time-resolved microwave conductance (TRMC), which probes formation and decay of mobile charges upon pulsed irradiation. Optical excitation of films results in the formation of charges with a yield times mobility product, φΣμ > 1 cm2/Vs. On excitation of millimeter-sized crystals, the TRMC signals show, apart from a fast decay, a long-lived tail. Interestingly, this tail is dominant when exciting close to the bandgap, implying the presence of mobile charges with microsecond lifetimes. From the temperature and intensity dependence of the TRMC signals, we deduce a shallow trap state density of around 1016/cm3 in the bulk of the crystal. Despite this high concentration, trap-assisted recombination of charges in the bulk appears to be slow, which is promising for photovoltaic applications. PMID:29545908

  6. BiVO4/WO3/SnO2 Double-Heterojunction Photoanode with Enhanced Charge Separation and Visible-Transparency for Bias-Free Solar Water-Splitting with a Perovskite Solar Cell.

    PubMed

    Baek, Ji Hyun; Kim, Byeong Jo; Han, Gill Sang; Hwang, Sung Won; Kim, Dong Rip; Cho, In Sun; Jung, Hyun Suk

    2017-01-18

    Coupling dissimilar oxides in heterostructures allows the engineering of interfacial, optical, charge separation/transport and transfer properties of photoanodes for photoelectrochemical (PEC) water splitting. Here, we demonstrate a double-heterojunction concept based on a BiVO 4 /WO 3 /SnO 2 triple-layer planar heterojunction (TPH) photoanode, which shows simultaneous improvements in the charge transport (∼93% at 1.23 V vs RHE) and transmittance at longer wavelengths (>500 nm). The TPH photoanode was prepared by a facile solution method: a porous SnO 2 film was first deposited on a fluorine-doped tin oxide (FTO)/glass substrate followed by WO 3 deposition, leading to the formation of a double layer of dense WO 3 and a WO 3 /SnO 2 mixture at the bottom. Subsequently, a BiVO 4 nanoparticle film was deposited by spin coating. Importantly, the WO 3 /(WO 3 +SnO 2 ) composite bottom layer forms a disordered heterojunction, enabling intimate contact, lower interfacial resistance, and efficient charge transport/transfer. In addition, the top BiVO 4 /WO 3 heterojunction layer improves light absorption and charge separation. The resultant TPH photoanode shows greatly improved internal quantum efficiency (∼80%) and PEC water oxidation performance (∼3.1 mA/cm 2 at 1.23 V vs RHE) compared to the previously reported BiVO 4 /WO 3 photoanodes. The PEC performance was further improved by a reactive-ion etching treatment and CoO x electrocatalyst deposition. Finally, we demonstrated a bias-free and stable solar water-splitting by constructing a tandem PEC device with a perovskite solar cell (STH ∼3.5%).

  7. Ion-atom charge-transfer reactions and a hot intercloud medium. [in interstellar space

    NASA Technical Reports Server (NTRS)

    Steigman, G.

    1975-01-01

    An investigation is conducted concerning the ionization equilibrium of carbon in a hot intercloud medium (ICM), taking into account various charge-transfer reactions. Attention is given to problems related to observations of carbon along the lines of sight to several unreddened stars. It is pointed out that the observed underabundance of C III and overabundance of C I can be consistent with the presence of a hot, partially ionized ICM, provided that two of the charge-transfer reactions considered are rapid at thermal energies.

  8. Elucidating the Charge Transfer Mechanism in Radical Polymer Thin Films

    NASA Astrophysics Data System (ADS)

    Mukherjee, Sanjoy; Boudouris, Bryan

    The active role of polymers in organic electronics has attracted significant attention in recent decades. Beyond conventional conjugated polymers, recently radical polymers have received a great deal of consideration by the community. Radical polymers are redox-active macromolecules with non-conjugated backbones functionalized with persistent radical sites. Because of their nascent nature, many open questions regarding the physics of their solid-state charge transfer mechanism still exist. In order to address these questions, well-defined radical polymers were synthesized and blended in a manner such that there was tight control over the radical density within the conducting thin films. We demonstrate that the systematic manipulation of the radical-to-radical spacing in open-shell macromolecules leads to exponential changes in the macroscopic electrical conductivity, and temperature-independent charge transport behaviour. Thus, a clear picture emerges that charge transfer in radical polymers is dictated by a tunnelling mechanism between proximal sites. This behavior is consistent with a distinct mechanism similar to redox reactions in biological media, but is unique relative to transport in common conjugated polymers. These results constitute the first experimental insight into the mechanism of solid-state electrical conduction in radical polymers.

  9. Effect of the surface charge discretization on electric double layers: a Monte Carlo simulation study.

    PubMed

    Madurga, Sergio; Martín-Molina, Alberto; Vilaseca, Eudald; Mas, Francesc; Quesada-Pérez, Manuel

    2007-06-21

    The structure of the electric double layer in contact with discrete and continuously charged planar surfaces is studied within the framework of the primitive model through Monte Carlo simulations. Three different discretization models are considered together with the case of uniform distribution. The effect of discreteness is analyzed in terms of charge density profiles. For point surface groups, a complete equivalence with the situation of uniformly distributed charge is found if profiles are exclusively analyzed as a function of the distance to the charged surface. However, some differences are observed moving parallel to the surface. Significant discrepancies with approaches that do not account for discreteness are reported if charge sites of finite size placed on the surface are considered.

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

    NASA Astrophysics Data System (ADS)

    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

  11. Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering.

    PubMed

    Lukman, Steven; Chen, Kai; Hodgkiss, Justin M; Turban, David H P; Hine, Nicholas D M; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C; Musser, Andrew J

    2016-12-07

    Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.

  12. Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering

    PubMed Central

    Lukman, Steven; Chen, Kai; Hodgkiss, Justin M.; Turban, David H. P.; Hine, Nicholas D. M.; Dong, Shaoqiang; Wu, Jishan; Greenham, Neil C.; Musser, Andrew J.

    2016-01-01

    Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics. PMID:27924819

  13. Coarse-Grained Theory of Biological Charge Transfer with Spatially and Temporally Correlated Noise.

    PubMed

    Liu, Chaoren; Beratan, David N; Zhang, Peng

    2016-04-21

    System-environment interactions are essential in determining charge-transfer (CT) rates and mechanisms. We developed a computationally accessible method, suitable to simulate CT in flexible molecules (i.e., DNA) with hundreds of sites, where the system-environment interactions are explicitly treated with numerical noise modeling of time-dependent site energies and couplings. The properties of the noise are tunable, providing us a flexible tool to investigate the detailed effects of correlated thermal fluctuations on CT mechanisms. The noise is parametrizable by molecular simulation and quantum calculation results of specific molecular systems, giving us better molecular resolution in simulating the system-environment interactions than sampling fluctuations from generic spectral density functions. The spatially correlated thermal fluctuations among different sites are naturally built-in in our method but are not readily incorporated using approximate spectral densities. Our method has quantitative accuracy in systems with small redox potential differences (charge delocalization and charge-transfer rates; however, in a system of units with different site energies, spatial correlations slow the fluctuations to bring units into degeneracy, in turn, slowing the charge-transfer rates. The spatial and temporal correlations of condensed phase medium fluctuations provide another source to control and tune the kinetics and dynamics of charge-transfer systems.

  14. Infrared laser driven double proton transfer. An optimal control theory study

    NASA Astrophysics Data System (ADS)

    Abdel-Latif, Mahmoud K.; Kühn, Oliver

    2010-02-01

    Laser control of ultrafast double proton transfer is investigated for a two-dimensional model system describing stepwise and concerted transfer pathways. The pulse design has been done by employing optimal control theory in combination with the multiconfiguration time-dependent Hartree wave packet propagation. The obtained laser fields correspond to multiple pump-dump pulse sequences. Special emphasis is paid to the relative importance of stepwise and concerted transfer pathways for the driven wave packet and its dependence on the parameters of the model Hamiltonian as well as on the propagation time. While stepwise transfer is dominating in all cases considered, for high barrier systems concerted transfer proceeding via tunneling can make a contribution.

  15. Heat Transfer of Nanofluid in a Double Pipe Heat Exchanger.

    PubMed

    Aghayari, Reza; Maddah, Heydar; Zarei, Malihe; Dehghani, Mehdi; Kaskari Mahalle, Sahar Ghanbari

    2014-01-01

    This paper investigates the enhancement of heat transfer coefficient and Nusselt number of a nanofluid containing nanoparticles (γ-AL2O3) with a particle size of 20 nm and volume fraction of 0.1%-0.3% (V/V). Effects of temperature and concentration of nanoparticles on Nusselt number changes and heat transfer coefficient in a double pipe heat exchanger with counter turbulent flow are investigated. Comparison of experimental results with valid theoretical data based on semiempirical equations shows an acceptable agreement. Experimental results show a considerable increase in heat transfer coefficient and Nusselt number up to 19%-24%, respectively. Also, it has been observed that the heat transfer coefficient increases with the operating temperature and concentration of nanoparticles.

  16. Charge transfer and charge localization in extended radical cations: Investigation of model molecules for peptides

    NASA Astrophysics Data System (ADS)

    Weinkauf, Rainer; Lehrer, Florian

    1998-12-01

    Molecules consisting of a flexible tail and an aromatic chromophore are used as model systems to understand the situation of a single chromophore in a small peptide. Their S0-S1 resonant multiphoton ionization (REMPI) spectra show, that in neutral molecules the tail-chromophore interaction is weak and electronic excitation is localized at the chromophore. For molecules, where the ionization energy of the tail is considerable higher than that of the chromophore, by high resolution REMPI photoelectron spectroscopy we find the charge to be localized on the aromatic chromophore. This scheme also in suitable peptides allows local ionization at the aromatic chromophore. An estimate for various charge positions in peptide chains, however, shows, that for most of the amino acids electron hole positions in the nitrogen and oxygen "lone pair" orbitals of the peptide bond are nearly degenerate. REMPI photoelectron spectra of phenylethylamine, which as a model system contains such two degenerate charge positions, show small energetic shift of the ionization energy but strong geometry changes upon electron removal. This result is interpreted as direct ionization into a mixed charge delocalized state. Consequences for the charge transfer mechanism in peptides are discussed.

  17. Conjugated block copolymers as model materials to examine charge transfer in donor-acceptor systems

    NASA Astrophysics Data System (ADS)

    Gomez, Enrique; Aplan, Melissa; Lee, Youngmin

    Weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. The lack of control of interfacial structure has also prevented studies of how driving forces promote charge photogeneration, leading to conflicting hypotheses in the organic photovoltaic literature. Our approach has focused on utilizing block copolymer architectures -where critical interfaces are controlled and stabilized by covalent bonds- to provide the hierarchical structure needed for high-performance organic electronics from self-assembled soft materials. For example, we have demonstrated control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers to achieve 3% power conversion efficiencies in non-fullerene photovoltaics. Furthermore, incorporating the donor-acceptor interface within the molecular structure facilitates studies of charge transfer processes. Conjugated block copolymers enable studies of the driving force needed for exciton dissociation to charge transfer states, which must be large to maximize charge photogeneration but must be minimized to prevent losses in photovoltage in solar cell devices. Our work has systematically varied the chemical structure, energetics, and dielectric constant to perturb charge transfer. As a consequence, we predict a minimum dielectric constant needed to minimize the driving force and therefore simultaneously maximize photocurrent and photovoltage in organic photovoltaic devices.

  18. Investigation of Charge Transfer Kinetics at Carbon/Hydroquinone Interfaces for Redox-Active-Electrolyte Supercapacitors.

    PubMed

    Park, Jinwoo; Kumar, Vipin; Wang, Xu; Lee, Pooi See; Kim, Woong

    2017-10-04

    The redox-active electrolyte supercapacitor (RAES) is a relatively new type of energy storage device. Simple addition of selected redox species in the electrolyte can greatly enhance the energy density of supercapacitors relative to traditional electric double layer capacitors (EDLCs) owing to redox reactions. Studies on the kinetics at the interface of the electrode and redox mediator are important when developing RAESs. In this work, we employ highly accurate scanning electrochemical microscopy (SECM) to extract the kinetic constants at carbon/hydroquinone interfaces. The charge transfer rate constants are 1.2 × 10 -2 and 1.3 × 10 -2 cm s -1 for the carbon nanotube/hydroquinone and reduced graphene oxide/hydroquinone interfaces, respectively. These values are higher than those obtained by the conventional cyclic voltammetry method, approximately by an order of magnitude. The evaluation of heterogeneous rate constants with SECM would be the cornerstone for understanding and developing high performance RAESs.

  19. Overcharging and charge reversal in the electrical double layer around the point of zero charge.

    PubMed

    Guerrero-García, G Iván; González-Tovar, Enrique; Chávez-Páez, Martín; Lozada-Cassou, Marcelo

    2010-02-07

    The ionic adsorption around a weakly charged spherical colloid, immersed in size-asymmetric 1:1 and 2:2 salts, is studied. We use the primitive model (PM) of an electrolyte to perform Monte Carlo simulations as well as theoretical calculations by means of the hypernetted chain/mean spherical approximation (HNC/MSA) and the unequal-radius modified Gouy-Chapman (URMGC) integral equations. Structural quantities such as the radial distribution functions, the integrated charge, and the mean electrostatic potential are reported. Our Monte Carlo "experiments" evidence that near the point of zero charge, the smallest ionic species is preferentially adsorbed onto the macroparticle, independently of the sign of the charge carried by this tiniest electrolytic component, giving rise to the appearance of the phenomena of charge reversal (CR) and overcharging (OC). Accordingly, colloidal CR, due to an excessive attachment of counterions, is observed when the macroion is slightly charged and the coions are larger than the counterions. In the opposite situation, i.e., if the counterions are larger than the coions, the central macroion acquires additional like-charge (coions) and hence becomes "overcharged," a feature theoretically predicted in the past [F. Jiménez-Angeles and M. Lozada-Cassou, J. Phys. Chem. B 108, 7286 (2004)]. In other words, here we present the first simulation data on OC in the PM electrical double layer, showing that close to the point of zero charge, this novel effect surges as a consequence of the ionic size asymmetry. We also find that the HNC/MSA theory captures well the CR and OC phenomena exhibited by the computer experiments, especially as the macroion's charge increases. On the contrary, even if URMGC also displays CR and OC, its predictions do not compare favorably with the Monte Carlo data, evidencing that the inclusion of hard-core correlations in Monte Carlo and HNC/MSA enhances and extends those effects. We explain our findings in terms of the

  20. Advanced Doubling Adding Method for Radiative Transfer in Planetary Atmospheres

    NASA Astrophysics Data System (ADS)

    Liu, Quanhua; Weng, Fuzhong

    2006-12-01

    The doubling adding method (DA) is one of the most accurate tools for detailed multiple-scattering calculations. The principle of the method goes back to the nineteenth century in a problem dealing with reflection and transmission by glass plates. Since then the doubling adding method has been widely used as a reference tool for other radiative transfer models. The method has never been used in operational applications owing to tremendous demand on computational resources from the model. This study derives an analytical expression replacing the most complicated thermal source terms in the doubling adding method. The new development is called the advanced doubling adding (ADA) method. Thanks also to the efficiency of matrix and vector manipulations in FORTRAN 90/95, the advanced doubling adding method is about 60 times faster than the doubling adding method. The radiance (i.e., forward) computation code of ADA is easily translated into tangent linear and adjoint codes for radiance gradient calculations. The simplicity in forward and Jacobian computation codes is very useful for operational applications and for the consistency between the forward and adjoint calculations in satellite data assimilation.

  1. Electronic and Vibrational Coherence in Charge-Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Scherer, Norbert

    1996-03-01

    The ultrafast dynamics associated with optically-induced intervalence charge-transfer reactions in solution and protein environments are reported. These studies include the Fe^(II)-Fe^(III) MMCT complex Prussian blue and the mixed valence dimer (CN)_5Ru^(II)CNRuRu^(III)(NH_3)_5. The protein systems include blue copper proteins and the bacterial photosynthetic reaction center. The experimental approaches include photon echo, wavelength-resolved pump-probe and anisotropy measurements performed with 12-16fs duration optical pulses. Complicated time-domain waveforms reflect the several different p[rocesses and time scales for relaxation of coherences (both electronic and vibrational) and populations within these systems. The photon echo and anisotropy results probe electronic coherence and dephasing prior to back electron transfer. Wavelength-resolved pump-probe results reveal vibrational modes coupled to the CT-coordinate as well as formation of new product states or vibrational cooling in the ground state following back electron transfer.

  2. Impact of double counting and transfer bias on estimated rates and outcomes of acute myocardial infarction.

    PubMed

    Westfall, J M; McGloin, J

    2001-05-01

    Ischemic heart disease is the leading cause of death in the United States. Recent studies report inconsistent findings on the changes in the incidence of hospitalizations for ischemic heart disease. These reports have relied primarily on hospital discharge data. Preliminary data suggest that a significant percentage of patients suffering acute myocardial infarction (MI) in rural communities are transferred to urban centers for care. Patients transferred to a second hospital may be counted twice for one episode of ischemic heart disease. To describe the impact of double counting and transfer bias on the estimation of incidence rates and outcomes of ischemic heart disease, specifically acute MI, in the United States. Analysis of state hospital discharge data from Kansas, Colorado (State Inpatient Database [SID]), Nebraska, Arizona, New Jersey, Michigan, Pennsylvania, and Illinois (SID) for the years 1995 to 1997. A matching algorithm was developed for hospital discharges to determine patients counted twice for one episode of ischemic heart disease. Validation of our matching algorithm. Patients reported to have suffered ischemic heart disease (ICD9 codes 410-414, 786.5). Number of patients counted twice for one episode of acute MI. It is estimated that double count rates range from 10% to 15% for all states and increased over the 3 years. Moderate sized rural counties had the highest estimated double count rates at 15% to 20% with a few counties having estimated double count rates a high as 35% to 50%. Older patients and females were less likely to be double counted (P <0.05). Double counting patients has resulted in a significant overestimation in the incidence rate for hospitalization for acute MI. Correction of this double counting reveals a significantly lower incidence rate and a higher in-hospital mortality rate for acute MI. Transferred patients differ significantly from nontransferred patients, introducing significant bias into MI outcome studies. Double

  3. Charge transfer and adsorption-desorption kinetics in carbon nanotube and graphene gas sensing

    NASA Astrophysics Data System (ADS)

    Liang, Sang-Zi; Chen, Gugang; Harutyunyan, Avetik; Cole, Milton; Sofo, Jorge

    2014-03-01

    Detection of molecules in the gas phase by carbon nanotube and graphene has great application potentials due to the high sensitivity and surface-to-volume ratio. In chemiresistor, the conductance of the materials has been proposed to change as a result of charge transfer from the adsorbed molecules. Due to self-interaction errors, calculations using LDA or GGA density functionals have an innate disadvantage in dealing with charge transfer situations. A model which takes into consideration the dielectric interaction between the graphene surface and the molecule is employed to estimate the distance where charge transfer becomes favorable. Adsorption-desorption kinetics is studied with a modified Langmuir model, including sites from which the molecules do not desorb within the experimental time. Assuming a constant mobility, the model reproduces existing experimental conductance data. Its parameters provide information about the microscopic process during the detection and varying them allows optimization of aspects of sensor performance, including sensitivity, detection limit and response time. This work is supported by Honda Research Institute USA, Inc.

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

    NASA Astrophysics Data System (ADS)

    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.

  5. Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF–TCNQ as an Example

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

    Park, Changwon; Atalla, Viktor; Smith, Sean

    Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor–acceptor molecules, tetrathiafulvalene–tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, onemore » can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. In conclusion, our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.« less

  6. Understanding the Charge Transfer at the Interface of Electron Donors and Acceptors: TTF–TCNQ as an Example

    DOE PAGES

    Park, Changwon; Atalla, Viktor; Smith, Sean; ...

    2017-06-16

    Charge transfer between an electron donor and an electron acceptor is widely accepted as being independent of their relative configurations if the interaction between them is weak; however, the limit of this concept for an interacting system has not yet been well established. Our study of prototypical electron donor–acceptor molecules, tetrathiafulvalene–tetracyanoquinodimethane, using density functional theory based on an advanced functional, clearly demonstrates that for interacting molecules, their configurational arrangement is as important as their individual electronic properties in the asymptotic limit to determine the charge transfer direction. For the first time, we demonstrate that by changing their relative orientation, onemore » can reverse the charge transfer direction of the pair, causing the molecules to exchange roles as donor and acceptor. In conclusion, our theory has important implications for understanding the interfacial charge-transfer mechanism of hybrid systems and related phenomena.« less

  7. The Case Against Charge Transfer Interactions in Dissolved Organic Matter Photophysics.

    PubMed

    McKay, Garrett; Korak, Julie A; Erickson, Paul R; Latch, Douglas E; McNeill, Kristopher; Rosario-Ortiz, Fernando L

    2018-01-16

    The optical properties of dissolved organic matter influence chemical and biological processes in all aquatic ecosystems. Dissolved organic matter optical properties have been attributed to a charge-transfer model in which donor-acceptor complexes play a primary role. This model was evaluated by measuring the absorbance and fluorescence response of organic matter isolates to changes in solvent temperature, viscosity, and polarity, which affect the position and intensity of spectra for known donor-acceptor complexes of organic molecules. Absorbance and fluorescence spectral shape were largely unaffected by these changes, indicating that the distribution of absorbing and emitting species was unchanged. Overall, these results call into question the wide applicability of the charge-transfer model for explaining organic matter optical properties and suggest that future research should explore other models for dissolved organic matter photophysics.

  8. Open-Circuit Voltage Losses in Selenium-Substituted Organic Photovoltaic Devices from Increased Density of Charge-Transfer States

    DOE PAGES

    Sulas, Dana B.; Yao, Kai; Intemann, Jeremy J.; ...

    2015-09-12

    Using an analysis based on Marcus theory, we characterize losses in open-circuit voltage (V OC) due to changes in charge-transfer state energy, electronic coupling, and spatial density of charge-transfer states in a series of polymer/fullerene solar cells. Here, we use a series of indacenodithiophene polymers and their selenium-substituted analogs as electron donor materials and fullerenes as the acceptors. By combining device measurements and spectroscopic studies (including subgap photocurrent, electroluminescence, and, importantly, time-resolved photoluminescence of the charge-transfer state) we are able to isolate the values for electronic coupling and the density of charge-transfer states (NCT), rather than the more commonly measuredmore » product of these values. We find values for NCT that are surprisingly large (~4.5 × 10 21–6.2 × 10 22 cm -3), and we find that a significant increase in N CT upon selenium substitution in donor polymers correlates with lower VOC for bulk heterojunction photovoltaic devices. The increase in N CT upon selenium substitution is also consistent with nanoscale morphological characterization. Using transmission electron microscopy, selected area electron diffraction, and grazing incidence wide-angle X-ray scattering, we find evidence of more intermixed polymer and fullerene domains in the selenophene blends, which have higher densities of polymer/fullerene interfacial charge-transfer states. Our results provide an important step toward understanding the spatial nature of charge-transfer states and their effect on the open-circuit voltage of polymer/fullerene solar cells« less

  9. Molecular dynamics and charge transport in organic semiconductors: a classical approach to modeling electron transfer

    DOE PAGES

    Pelzer, Kenley M.; Vázquez-Mayagoitia, Álvaro; Ratcliff, Laura E.; ...

    2017-01-01

    Organic photovoltaics (OPVs) are a promising carbon-neutral energy conversion technology, with recent improvements pushing power conversion efficiencies over 10%. A major factor limiting OPV performance is inefficiency of charge transport in organic semiconducting materials (OSCs). Due to strong coupling with lattice degrees of freedom, the charges form polarons, localized quasi-particles comprised of charges dressed with phonons. These polarons can be conceptualized as pseudo-atoms with a greater effective mass than a bare charge. Here we propose that due to this increased mass, polarons can be modeled with Langevin molecular dynamics (LMD), a classical approach with a computational cost much lower thanmore » most quantum mechanical methods. Here we present LMD simulations of charge transfer between a pair of fullerene molecules, which commonly serve as electron acceptors in OSCs. We find transfer rates consistent with experimental measurements of charge mobility, suggesting that this method may provide quantitative predictions of efficiency when used to simulate materials on the device scale. Our approach also offers information that is not captured in the overall transfer rate or mobility: in the simulation data, we observe exactly when and why intermolecular transfer events occur. In addition, we demonstrate that these simulations can shed light on the properties of polarons in OSCs. In conclusion, much remains to be learned about these quasi-particles, and there are no widely accepted methods for calculating properties such as effective mass and friction. Lastly, our model offers a promising approach to exploring mass and friction as well as providing insight into the details of polaron transport in OSCs.« less

  10. Economic evaluations of single- versus double-embryo transfer in IVF.

    PubMed

    Fiddelers, A A A; Severens, J L; Dirksen, C D; Dumoulin, J C M; Land, J A; Evers, J L H

    2007-01-01

    Multiple pregnancies lead to complications and induce high costs. The most successful way to decrease multiple pregnancies in IVF is to transfer only one embryo, which might reduce the efficacy of treatment. The objective of this review is to determine which embryo-transfer policy is most cost-effective: elective single-embryo transfer (eSET) or double-embryo transfer (DET). Several databases were searched for (cost* or econ*) and (single embryo* or double embryo* or one embryo* or two embryo* or elect* embryo or multip* embryo*). On the basis of five exclusion criteria, titles and abstracts were screened by two individual reviewers. The remaining papers were read for further selection, and data were extracted from the selected studies. A total of 496 titles were identified through the searches and resulted in the selection of one observational study and three randomized studies. Study characteristics, total costs and probability of live births were extracted. Besides this, cost-effectiveness and incremental cost-effectiveness were derived. It can be concluded that DET is the most expensive strategy. DET is also most effective if performed in one fresh cycle. eSET is only preferred from a cost-effectiveness point of view when performed in good prognosis patients and when frozen/thawed cycles are included. If frozen/thawed cycles are excluded, the choice between eSET and DET depends on how much society is willing to pay for one extra successful pregnancy.

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

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

    Cohen, S.G.

    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 ..cap alpha..-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 withmore » 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.« less

  12. Charging in the ac Conductance of a Double Barrier Resonant Tunneling Structure

    NASA Technical Reports Server (NTRS)

    Anantram, M. P.; Saini, Subhash (Technical Monitor)

    1998-01-01

    There have been many studies of the linear response ac conductance of a double barrier resonant tunneling structure (DBRTS), both at zero and finite dc biases. While these studies are important, they fail to self consistently include the effect of the time dependent charge density in the well. In this paper, we calculate the ac conductance at both zero and finite do biases by including the effect of the time dependent charge density in the well in a self consistent manner. The charge density in the well contributes to both the flow of displacement currents in the contacts and the time dependent potential in the well. We find that including these effects can make a significant difference to the ac conductance and the total ac current is not equal to the simple average of the non-selfconsistently calculated conduction currents in the two contacts. This is illustrated by comparing the results obtained with and without the effect of the time dependent charge density included correctly. Some possible experimental scenarios to observe these effects are suggested.

  13. Field Effect Modulation of Heterogeneous Charge Transfer Kinetics at Back-Gated Two-Dimensional MoS2 Electrodes.

    PubMed

    Wang, Yan; Kim, Chang-Hyun; Yoo, Youngdong; Johns, James E; Frisbie, C Daniel

    2017-12-13

    The ability to improve and to modulate the heterogeneous charge transfer kinetics of two-dimensional (2D) semiconductors, such as MoS 2 , is a major challenge for electrochemical and photoelectrochemical applications of these materials. Here we report a continuous and reversible physical method for modulating the heterogeneous charge transfer kinetics at a monolayer MoS 2 working electrode supported on a SiO 2 /p-Si substrate. The heavily doped p-Si substrate serves as a back gate electrode; application of a gate voltage (V BG ) to p-Si tunes the electron occupation in the MoS 2 conduction band and shifts the conduction band edge position relative to redox species dissolved in electrolyte in contact with the front side of the MoS 2 . The gate modulation of both charge density and energy band alignment impacts charge transfer kinetics as measured by cyclic voltammetry (CV). Specifically, cyclic voltammograms combined with numerical simulations suggest that the standard heterogeneous charge transfer rate constant (k 0 ) for MoS 2 in contact with the ferrocene/ferrocenium (Fc 0/+ ) redox couple can be modulated by over 2 orders of magnitude from 4 × 10 -6 to 1 × 10 -3 cm/s, by varying V BG . In general, the field effect offers the potential to tune the electrochemical properties of 2D semiconductors, opening up new possibilities for fundamental studies of the relationship between charge transfer kinetics and independently controlled electronic band alignment and band occupation.

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

    PubMed

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

    2014-05-28

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

  15. Interfaces between strongly correlated oxides: controlling charge transfer and induced magnetism by hybridization

    NASA Astrophysics Data System (ADS)

    Bibes, Manuel

    At interfaces between conventional materials, band bending and alignment are controlled by differences in electrochemical potential. Applying this concept to oxides in which interfaces can be polar and cations may adopt a mixed valence has led to the discovery of novel two-dimensional states between simple band insulators such as LaAlO3 and SrTiO3. However, many oxides have a more complex electronic structure, with charge, orbital and/or spin orders arising from correlations between transition metal and oxygen ions. Strong correlations thus offer a rich playground to engineer functional interfaces but their compatibility with the classical band alignment picture remains an open question. In this talk we will show that beyond differences in electron affinities and polar effects, a key parameter determining charge transfer at correlated oxide interfaces is the energy required to alter the covalence of the metal-oxygen bond. Using the perovskite nickelate (RNiO3) family as a template, we have probed charge reconstruction at interfaces with gadolinium titanate GdTiO3 using soft X-ray absorption spectroscopy and hard X-ray photoemission spectroscopy. We show that the charge transfer is thwarted by hybridization effects tuned by the rare-earth (R) size. Charge transfer results in an induced ferromagnetic-like state in the nickelate (observed by XMCD), exemplifying the potential of correlated interfaces to design novel phases. Further, our work clarifies strategies to engineer two-dimensional systems through the control of both doping and covalence. Work supported by ERC CoG MINT #615759.

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    Sukhomlinov, Sergey V.; Müser, Martin H.

    2015-12-01

    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, PC ≡ 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.

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

    PubMed

    Baumeier, Björn; Andrienko, Denis; Rohlfing, Michael

    2012-08-14

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

  19. Charge Transfer Inefficiency in Pinned Photodiode CMOS image sensors: Simple Montecarlo modeling and experimental measurement based on a pulsed storage-gate method

    NASA Astrophysics Data System (ADS)

    Pelamatti, Alice; Goiffon, Vincent; Chabane, Aziouz; Magnan, Pierre; Virmontois, Cédric; Saint-Pé, Olivier; de Boisanger, Michel Breart

    2016-11-01

    The charge transfer time represents the bottleneck in terms of temporal resolution in Pinned Photodiode (PPD) CMOS image sensors. This work focuses on the modeling and estimation of this key parameter. A simple numerical model of charge transfer in PPDs is presented. The model is based on a Montecarlo simulation and takes into account both charge diffusion in the PPD and the effect of potential obstacles along the charge transfer path. This work also presents a new experimental approach for the estimation of the charge transfer time, called pulsed Storage Gate (SG) method. This method, which allows reproduction of a ;worst-case; transfer condition, is based on dedicated SG pixel structures and is particularly suitable to compare transfer efficiency performances for different pixel geometries.

  20. Spectral resolution of states relevant to photoinduced charge transfer in modified pentacene/ZnO field-effect transistors

    NASA Astrophysics Data System (ADS)

    Spalenka, Josef W.; Mannebach, Ehren M.; Bindl, Dominick J.; Arnold, Michael S.; Evans, Paul G.

    2011-11-01

    Pentacene field-effect transistors incorporating ZnO quantum dots can be used as a sensitive probe of the optical properties of a buried donor-acceptor interface. Photoinduced charge transfer between pentacene and ZnO in these devices varies with incident photon energy and reveals which energies will contribute most to charge transfer in other structures. A subsequent slow return to the dark state following the end of illumination arises from near-interface traps. Charge transfer has a sharp onset at 1.7 eV and peaks at 1.82 and 2.1 eV due to transitions associated with excitons, features absent in pentacene FETs without ZnO.

  1. Electronegativity, charge transfer, crystal field strength, and the point charge model revisited.

    PubMed

    Tanner, Peter A; Ning, Lixin

    2013-02-21

    Although the optical spectra of LnCl(6)(3-) systems are complex, only two crystal field parameters, B(40) and B(60), are required to model the J-multiplet crystal field splittings in octahedral symmetry. It is found that these parameters exhibit R(-5) and R(-7) dependence, respectively, upon the ionic radius Ln(3+)(VI), but not upon the Ln-Cl distance. More generally, the crystal field strengths of LnX(6) systems (X = Br, Cl, F, O) exhibit linear relationships with ligand electronegativity, charge transfer energy, and fractional ionic character of the Ln-X bond.

  2. Delayed Triplet-State Formation through Hybrid Charge Transfer Exciton at Copper Phthalocyanine/GaAs Heterojunction.

    PubMed

    Lim, Heeseon; Kwon, Hyuksang; Kim, Sang Kyu; Kim, Jeong Won

    2017-10-05

    Light absorption in organic molecules on an inorganic substrate and subsequent electron transfer to the substrate create so-called hybrid charge transfer exciton (HCTE). The relaxation process of the HCTE states largely determines charge separation efficiency or optoelectronic device performance. Here, the study on energy and time-dispersive behavior of photoelectrons at the hybrid interface of copper phthalocyanine (CuPc)/p-GaAs(001) upon light excitation of GaAs reveals a clear pathway for HCTE relaxation and delayed triplet-state formation. According to the ground-state energy level alignment at the interface, CuPc/p-GaAs(001) shows initially fast hole injection from GaAs to CuPc. Thus, the electrons in GaAs and holes in CuPc form an unusual HCTE state manifold. Subsequent electron transfer from GaAs to CuPc generates the formation of the triplet state in CuPc with a few picoseconds delay. Such two-step charge transfer causes delayed triplet-state formation without singlet excitation and subsequent intersystem crossing within the CuPc molecules.

  3. Communication: Correct charge transfer in CT complexes from the Becke'05 density functional

    NASA Astrophysics Data System (ADS)

    Becke, Axel D.; Dale, Stephen G.; Johnson, Erin R.

    2018-06-01

    It has been known for over twenty years that density functionals of the generalized-gradient approximation (GGA) type and exact-exchange-GGA hybrids with low exact-exchange mixing fraction yield enormous errors in the properties of charge-transfer (CT) complexes. Manifestations of this error have also plagued computations of CT excitation energies. GGAs transfer far too much charge in CT complexes. This error has therefore come to be called "delocalization" error. It remains, to this day, a vexing unsolved problem in density-functional theory (DFT). Here we report that a 100% exact-exchange-based density functional known as Becke'05 or "B05" [A. D. Becke, J. Chem. Phys. 119, 2972 (2003); 122, 064101 (2005)] predicts excellent charge transfers in classic CT complexes involving the electron donors NH3, C2H4, HCN, and C2H2 and electron acceptors F2 and Cl2. Our approach is variational, as in our recent "B05min" dipole moments paper [Dale et al., J. Chem. Phys. 147, 154103 (2017)]. Therefore B05 is not only an accurate DFT for thermochemistry but is promising as a solution to the delocalization problem as well.

  4. Charge Transfer-Mediated Singlet Fission

    NASA Astrophysics Data System (ADS)

    Monahan, N.; Zhu, X.-Y.

    2015-04-01

    Singlet fission, the splitting of a singlet exciton into two triplet excitons in molecular materials, is interesting not only as a model many-electron problem, but also as a process with potential applications in solar energy conversion. Here we discuss limitations of the conventional four-electron and molecular dimer model in describing singlet fission in crystalline organic semiconductors, such as pentacene and tetracene. We emphasize the need to consider electronic delocalization, which is responsible for the decisive role played by the Mott-Wannier exciton, also called the charge transfer (CT) exciton, in mediating singlet fission. At the strong electronic coupling limit, the initial excitation creates a quantum superposition of singlet, CT, and triplet-pair states, and we present experimental evidence for this interpretation. We also discuss the most recent attempts at translating this mechanistic understanding into design principles for CT state-mediated intramolecular singlet fission in oligomers and polymers.

  5. Azimuthally and radially excited charge transfer plasmon and Fano lineshapes in conductive sublayer-mediated nanoassemblies.

    PubMed

    Ahmadivand, Arash; Gerislioglu, Burak; Pala, Nezih

    2017-11-01

    Here, the plasmon responses of both symmetric and antisymmetric oligomers on a conductive substrate under linear, azimuthal, and radial polarization excitations are analyzed numerically. By observing charge transfer plasmons under cylindrical vector beam (CVB) illumination for what we believe is the first time, we show that our studies open new horizons to induce significant charge transfer plasmons and antisymmetric Fano resonance lineshapes in metallic substrate-mediated plasmonic nanoclusters under both azimuthal and radial excitation as CVBs.

  6. Ab initio treatment of ion-induced charge transfer dynamics of isolated 2-deoxy-D-ribose.

    PubMed

    Bacchus-Montabonel, Marie-Christine

    2014-08-21

    Modeling-induced radiation damage in biological systems, in particular, in DNA building blocks, is of major concern in cancer therapy studies. Ion-induced charge-transfer dynamics may indeed be involved in proton and hadrontherapy treatments. We have thus performed a theoretical approach of the charge-transfer dynamics in collision of C(4+) ions and protons with isolated 2-deoxy-D-ribose in a wide collision energy range by means of ab initio quantum chemistry molecular methods. The comparison of both projectile ions has been performed with regard to previous theoretical and experimental results. The charge transfer appears markedly less efficient with the 2-deoxy-D-ribose target than that with pyrimidine nucleobases, which would induce an enhancement of the fragmentation process in agreement with experimental measurements. The mechanism has been analyzed with regard to inner orbital excitations, and qualitative tendencies have been pointed out for studies on DNA buiding block damage.

  7. The Nature of the Intramolecular Charge Transfer State in Peridinin

    PubMed Central

    Wagner, Nicole L.; Greco, Jordan A.; Enriquez, Miriam M.; Frank, Harry A.; Birge, Robert R.

    2013-01-01

    Experimental and theoretical evidence is presented that supports the theory that the intramolecular charge transfer (ICT) state of peridinin is an evolved state formed via excited-state bond-order reversal and solvent reorganization in polar media. The ICT state evolves in <100 fs and is characterized by a large dipole moment (∼35 D). The charge transfer character involves a shift of electron density within the polyene chain, and it does not involve participation of molecular orbitals localized in either of the β-rings. Charge is moved from the allenic side of the polyene into the furanic ring region and is accompanied by bond-order reversal in the central portion of the polyene chain. The electronic properties of the ICT state are generated via mixing of the “11Bu+” ionic state and the lowest-lying “21Ag–” covalent state. The resulting ICT state is primarily 1Bu+-like in character and exhibits not only a large oscillator strength but an unusually large doubly excited character. In most solvents, two populations exist in equilibrium, one with a lowest-lying ICT ionic state and a second with a lowest-lying “21Ag–” covalent state. The two populations are separated by a small barrier associated with solvent relaxation and cavity formation. PMID:23528091

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

    NASA Astrophysics Data System (ADS)

    Chábera, Pavel; Liu, Yizhu; Prakash, Om; Thyrhaug, Erling; Nahhas, Amal El; Honarfar, Alireza; Essén, Sofia; Fredin, Lisa A.; Harlang, Tobias C. B.; Kjær, Kasper S.; Handrup, Karsten; Ericson, Fredric; Tatsuno, Hideyuki; Morgan, Kelsey; Schnadt, Joachim; Häggström, Lennart; Ericsson, Tore; Sobkowiak, Adam; Lidin, Sven; Huang, Ping; Styring, Stenbjörn; Uhlig, Jens; Bendix, Jesper; Lomoth, Reiner; Sundström, Villy; Persson, Petter; Wärnmark, Kenneth

    2017-03-01

    Transition-metal complexes are used as photosensitizers, in light-emitting diodes, for biosensing and in photocatalysis. A key feature in these applications is excitation from the ground state to a charge-transfer state; the long charge-transfer-state lifetimes typical for complexes of ruthenium and other precious metals are often essential to ensure high performance. There is much interest in replacing these scarce elements with Earth-abundant metals, with iron and copper being particularly attractive owing to their low cost and non-toxicity. But despite the exploration of innovative molecular designs, it remains a formidable scientific challenge to access Earth-abundant transition-metal complexes with long-lived charge-transfer excited states. No known iron complexes are considered photoluminescent at room temperature, and their rapid excited-state deactivation precludes their use as photosensitizers. Here we present the iron complex [Fe(btz)3]3+ (where btz is 3,3‧-dimethyl-1,1‧-bis(p-tolyl)-4,4‧-bis(1,2,3-triazol-5-ylidene)), and show that the superior σ-donor and π-acceptor electron properties of the ligand stabilize the excited state sufficiently to realize a long charge-transfer lifetime of 100 picoseconds (ps) and room-temperature photoluminescence. This species is a low-spin Fe(III) d5 complex, and emission occurs from a long-lived doublet ligand-to-metal charge-transfer (2LMCT) state that is rarely seen for transition-metal complexes. The absence of intersystem crossing, which often gives rise to large excited-state energy losses in transition-metal complexes, enables the observation of spin-allowed emission directly to the ground state and could be exploited as an increased driving force in photochemical reactions on surfaces. These findings suggest that appropriate design strategies can deliver new iron-based materials for use as light emitters and photosensitizers.

  9. Theoretical Insights Into the Excited State Double Proton Transfer Mechanism of Deep Red Pigment Alkannin.

    PubMed

    Zhao, Jinfeng; Dong, Hao; Zheng, Yujun

    2018-02-08

    As the most important component of deep red pigments, alkannin is investigated theoretically in detail based on time-dependent density functional theory (TDDFT) method. Exploring the dual intramolecular hydrogen bonds (O1-H2···O3 and O4-H5···O6) of alkannin, we confirm the O1-H2···O3 may play a more important role in the first excited state than the O4-H5···O6 one. Infrared (IR) vibrational analyses and subsequent charge redistribution also support this viewpoint. Via constructing the S 1 -state potential energy surface (PES) and searching transition state (TS) structures, we illuminate the excited state double proton transfer (ESDPT) mechanism of alkannin is the stepwise process that can be first launched by the O1-H2···O3 hydrogen bond wire in gas state, acetonitrile (CH 3 CN) and cyclohexane (CYH) solvents. We present a novel mechanism that polar aprotic solvents can contribute to the first-step proton transfer (PT) process in the S 1 state, and nonpolar solvents play important roles in lowering the potential energy barrier of the second-step PT reaction.

  10. TiO2/water Nanofluid Heat Transfer in Heat Exchanger Equipped with Double Twisted-Tape Inserts

    NASA Astrophysics Data System (ADS)

    Eiamsa-ard, S.; Ketrain, R.; Chuwattanakul, V.

    2018-05-01

    Nowadays, heat transfer enhancement plays an important role in improving efficiency of heat transfer and thermal systems for numerous areas such as heat recovery processes, chemical reactors, air-conditioning/refrigeration system, food engineering, solar air/water heater, cooling of high power electronics etc. The present work presents the experimental results of the heat transfer enhancement of TiO2/water nanofluid in a heat exchanger tube fitted with double twisted tapes. The study covered twist ratios of twisted tapes (y/w) of 1.5, 2.0, and 2.5) while the concentration of the nanofluid was kept constant at 0.05% by volume. Observations show that heat transfer, friction loss and thermal performance increase as twist ratio (y/w) decreases. The use of the nanofluid in the tube equipped with the double twisted-tapes with the smallest twist ratio (y/w = 1.5) results in the increases of heat transfer rates and friction factor up to 224.8% and 8.98 times, respectively as compared to those of water. In addition, the experimental results performed that double twisted tapes induced dual swirling-flows which played an important role in improving fluid mixing and heat transfer enhancement. It is also observed that the TiO2/water nanofluid was responsible for low pressure loss behaviors.

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

    PubMed Central

    Boll, Rebecca; Erk, Benjamin; Coffee, Ryan; Trippel, Sebastian; Kierspel, Thomas; Bomme, Cédric; Bozek, John D.; Burkett, Mitchell; Carron, Sebastian; Ferguson, Ken R.; Foucar, Lutz; Küpper, Jochen; Marchenko, Tatiana; Miron, Catalin; Patanen, Minna; Osipov, Timur; Schorb, Sebastian; Simon, Marc; Swiggers, Michelle; Techert, Simone; Ueda, Kiyoshi; Bostedt, Christoph; Rolles, Daniel; Rudenko, Artem

    2016-01-01

    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. PMID:27051675

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

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

    Yukihira, Nao; Sugai, Yuko; Fujiwara, Masazumi

    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 intomore » 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.« less

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

    PubMed

    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.

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

    PubMed Central

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

    2017-01-01

    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-Mx (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-Mx 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. PMID:28767053

  15. Crater Formation on Electrodes during Charge Transfer with Aqueous Droplets or Solid Particles

    NASA Astrophysics Data System (ADS)

    Elton, Eric S.; Rosenberg, Ethan R.; Ristenpart, William D.

    2017-11-01

    We report that metallic electrodes are physically pitted during charge transfer events with water droplets or other conductive objects moving in strong electric fields (>1 kV/cm). Post situ microscopic inspection of the electrode shows that an individual charge transfer event yields a crater approximately 1 to 3 microns wide, often with features similar to splash coronae. We interpret the crater formation in terms of localized melting of the electrode via resistive heating concurrent with dielectric breakdown through the surrounding insulating fluid. A scaling analysis indicates that the crater diameter scales as the inverse cube root of the melting point temperature Tm of the metal, in accord with measurements on several metals (660°C <=Tm <= 3414°C). The process of crater formation provides a possible explanation for the longstanding difficulty in quantitatively corroborating Maxwell's prediction for the amount of charge acquired by spheres contacting a planar electrode.

  16. Effect of proton transfer on the electronic coupling in DNA

    NASA Astrophysics Data System (ADS)

    Rak, Janusz; Makowska, Joanna; Voityuk, Alexander A.

    2006-06-01

    The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, Vda, in DNA are studied on the bases of quantum chemical calculations. Four dimers [AT,AT], [GC,GC], [GC,AT] and [GC,TA)] are considered. Three techniques - the generalized Mulliken-Hush scheme, the fragment charge method and the diabatic states method - are employed to estimate Vda for hole transfer between base pairs. We show that both single- and double proton transfer (PT) reactions may substantially affect the electronic coupling in DNA. The electronic coupling in [AT,AT] is predicted to be most sensitive to PT. Single PT within the first base pair in the dimer leads to increase in the hole transfer efficiency by a factor of 4, while proton transfer within the second pair should substantially, by 2.7 times, decrease the rate of charge transfer. Thus, directional asymmetry of the PT effects on the electronic coupling is predicted. The changes in the Vda matrix elements correlate with the topological properties of orbitals of donor and acceptor and can be qualitatively rationalized in terms of resonance structures of donor and acceptor. Atomic pair contributions to the Vda matrix elements are also analyzed.

  17. Charge transfer and injection barrier at the metal-organic interfaces

    NASA Astrophysics Data System (ADS)

    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.

  18. Photooxidation of Diimine Dithiolate Platinium(II) Complexes Induced by Charge Transfer to Diimine Excitation.

    PubMed

    Zhang, Yin; Ley, Kevin D.; Schanze, Kirk S.

    1996-11-20

    A photochemical and photophysical investigation was carried out on (tbubpy)Pt(II)(dpdt) and (tbubpy)Pt(II)(edt) (1 and 2, respectively, where tbubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dpdt = meso-1,2-diphenyl-1,2-ethanedithiolate and edt = 1,2-ethanedithiolate). Luminescence and transient absorption studies reveal that these complexes feature a lowest excited state with Pt(S)(2) --> tbubpy charge transfer to diimine character. Both complexes are photostable in deoxygenated solution; however, photolysis into the visible charge transfer band in air-saturated solution induces moderately efficient photooxidation. Photooxidation of 1 produces the dehydrogenation product (tbubpy)Pt(II)(1,2-diphenyl-1,2-ethenedithiolate) (4). By contrast, photooxidation of 2 produces S-oxygenated complexes in which one or both thiolate ligands are converted to sulfinate (-SO(2)R) ligands. Mechanistic photochemical studies and transient absorption spectroscopy reveal that photooxidation occurs by (1) energy transfer from the charge transfer to diimine excited state of 1 to (3)O(2) to produce (1)O(2) and (2) reaction between (1)O(2) and the ground state 1. Kinetic data indicates that excited state 1 produces (1)O(2) efficiently and that reaction between ground state 1 and (1)O(2) occurs with k approximately 3 x 10(8) M(-)(1) s(-)(1).

  19. First principles molecular dynamics of molten NaI: Structure, self-diffusion, polarization effects, and charge transfer

    NASA Astrophysics Data System (ADS)

    Galamba, N.; Costa Cabral, B. J.

    2007-09-01

    The structure and self-diffusion of NaI and NaCl at temperatures close to their melting points are studied by first principles Hellmann-Feynman molecular dynamics (HFMD). The results are compared with classical MD using rigid-ion (RI) and shell-model (ShM) interionic potentials. HFMD for NaCl was reported before at a higher temperature [N. Galamba and B. J. Costa Cabral, J. Chem. Phys. 126, 124502 (2007)]. The main differences between the structures predicted by HFMD and RI MD for NaI concern the cation-cation and the anion-cation pair correlation functions. A ShM which allows only for the polarization of I- reproduces the main features of the HFMD structure of NaI. The inclusion of polarization effects for both ionic species leads to a more structured ionic liquid, although a good agreement with HFMD is also observed. HFMD Green-Kubo self-diffusion coefficients are larger than those obtained from RI and ShM simulations. A qualitative study of charge transfer in molten NaI and NaCl was also carried out with the Hirshfeld charge partitioning method. Charge transfer in molten NaI is comparable to that in NaCl, and results for NaCl at two temperatures support the view that the magnitude of charge transfer is weakly state dependent for ionic systems. Finally, Hirshfeld charge distributions indicate that differences between RI and HFMD results are mainly related to polarization effects, while the influence of charge transfer fluctuations is minimal for these systems.

  20. Probing and Exploiting the Interplay between Nuclear and Electronic Motion in Charge Transfer Processes.

    PubMed

    Delor, Milan; Sazanovich, Igor V; Towrie, Michael; Weinstein, Julia A

    2015-04-21

    The Born-Oppenheimer approximation refers to the assumption that the nuclear and electronic wave functions describing a molecular system evolve and can be determined independently. It is now well-known that this approximation often breaks down and that nuclear-electronic (vibronic) coupling contributes greatly to the ultrafast photophysics and photochemistry observed in many systems ranging from simple molecules to biological organisms. In order to probe vibronic coupling in a time-dependent manner, one must use spectroscopic tools capable of correlating the motions of electrons and nuclei on an ultrafast time scale. Recent developments in nonlinear multidimensional electronic and vibrational spectroscopies allow monitoring both electronic and structural factors with unprecedented time and spatial resolution. In this Account, we present recent studies from our group that make use of different variants of frequency-domain transient two-dimensional infrared (T-2DIR) spectroscopy, a pulse sequence combining electronic and vibrational excitations in the form of a UV-visible pump, a narrowband (12 cm(-1)) IR pump, and a broadband (400 cm(-1)) IR probe. In the first example, T-2DIR is used to directly compare vibrational dynamics in the ground and relaxed electronic excited states of Re(Cl)(CO)3(4,4'-diethylester-2,2'-bipyridine) and Ru(4,4'-diethylester-2,2'-bipyridine)2(NCS)2, prototypical charge transfer complexes used in photocatalytic CO2 reduction and electron injection in dye-sensitized solar cells. The experiments show that intramolecular vibrational redistribution (IVR) and vibrational energy transfer (VET) are up to an order of magnitude faster in the triplet charge transfer excited state than in the ground state. These results show the influence of electronic arrangement on vibrational coupling patterns, with direct implications for vibronic coupling mechanisms in charge transfer excited states. In the second example, we show unambiguously that electronic and

  1. Ultrafast optical excitations in supramolecular metallacycles with charge transfer properties.

    PubMed

    Flynn, Daniel C; Ramakrishna, Guda; Yang, Hai-Bo; Northrop, Brian H; Stang, Peter J; Goodson, Theodore

    2010-02-03

    New organometallic materials such as two-dimensional metallacycles and three-dimensional metallacages are important for the development of novel optical, electronic, and energy related applications. In this article, the ultrafast dynamics of two different platinum-containing metallacycles have been investigated by femtosecond fluorescence upconversion and transient absorption. These measurements were carried out in an effort to probe the charge transfer dynamics and the rate of intersystem crossing in metallacycles of different geometries and dimensions. The processes of ultrafast intersystem crossing and charge transfer vary between the two different classes of metallacyclic systems studied. For rectangular anthracene-containing metallacycles, the electronic coupling between adjacent ligands was relatively weak, whereas for the triangular phenanthrene-containing structures, there was a clear interaction between the conjugated ligand and the metal complex center. The transient lifetimes increased with increasing conjugation in that case. The results show that differences in the dimensionality and structure of metallacycles result in different optical properties, which may be utilized in the design of nonlinear optical materials and potential new, longer-lived excited state materials for further electronic applications.

  2. Single helically folded aromatic oligoamides that mimic the charge surface of double-stranded B-DNA

    NASA Astrophysics Data System (ADS)

    Ziach, Krzysztof; Chollet, Céline; Parissi, Vincent; Prabhakaran, Panchami; Marchivie, Mathieu; Corvaglia, Valentina; Bose, Partha Pratim; Laxmi-Reddy, Katta; Godde, Frédéric; Schmitter, Jean-Marie; Chaignepain, Stéphane; Pourquier, Philippe; Huc, Ivan

    2018-05-01

    Numerous essential biomolecular processes require the recognition of DNA surface features by proteins. Molecules mimicking these features could potentially act as decoys and interfere with pharmacologically or therapeutically relevant protein-DNA interactions. Although naturally occurring DNA-mimicking proteins have been described, synthetic tunable molecules that mimic the charge surface of double-stranded DNA are not known. Here, we report the design, synthesis and structural characterization of aromatic oligoamides that fold into single helical conformations and display a double helical array of negatively charged residues in positions that match the phosphate moieties in B-DNA. These molecules were able to inhibit several enzymes possessing non-sequence-selective DNA-binding properties, including topoisomerase 1 and HIV-1 integrase, presumably through specific foldamer-protein interactions, whereas sequence-selective enzymes were not inhibited. Such modular and synthetically accessible DNA mimics provide a versatile platform to design novel inhibitors of protein-DNA interactions.

  3. Photoinduced electron transfer in a molecular dyad by nanosecond pump-pump-probe spectroscopy.

    PubMed

    Ha-Thi, M-H; Pham, V-T; Pino, T; Maslova, V; Quaranta, A; Lefumeux, C; Leibl, W; Aukauloo, A

    2018-06-01

    The design of robust and inexpensive molecular photocatalysts for the conversion of abundant stable molecules like H2O and CO2 into an energetic carrier is one of the major fundamental questions for scientists nowadays. The outstanding challenge is to couple single photoinduced charge separation events with the sequential accumulation of redox equivalents at the catalytic unit for performing multielectronic catalytic reactions. Herein, double excitation by nanosecond pump-pump-probe experiments was used to interrogate the photoinduced charge transfer and charge accumulation on a molecular dyad composed of a porphyrin chromophore and a ruthenium-based catalyst in the presence of a reversible electron acceptor. An accumulative charge transfer state is unattainable because of rapid reverse electron transfer to the photosensitizer upon the second excitation and the low driving force of the forward photodriven electron transfer reaction. Such a method allows the fundamental understanding of the relaxation mechanism after two sequential photon absorptions, deciphering the undesired electron transfer reactions that limit the charge accumulation efficiency. This study is a step toward the improvement of synthetic strategies of molecular photocatalysts for light-induced charge accumulation and more generally, for solar energy conversion.

  4. A multi-state fragment charge difference approach for diabatic states in electron transfer: Extension and automation

    NASA Astrophysics Data System (ADS)

    Yang, Chou-Hsun; Hsu, Chao-Ping

    2013-10-01

    The electron transfer (ET) rate prediction requires the electronic coupling values. The Generalized Mulliken-Hush (GMH) and Fragment Charge Difference (FCD) schemes have been useful approaches to calculate ET coupling from an excited state calculation. In their typical form, both methods use two eigenstates in forming the target charge-localized diabatic states. For problems involve three or four states, a direct generalization is possible, but it is necessary to pick and assign the locally excited or charge-transfer states involved. In this work, we generalize the 3-state scheme for a multi-state FCD without the need of manual pick or assignment for the states. In this scheme, the diabatic states are obtained separately in the charge-transfer or neutral excited subspaces, defined by their eigenvalues in the fragment charge-difference matrix. In each subspace, the Hamiltonians are diagonalized, and there exist off-diagonal Hamiltonian matrix elements between different subspaces, particularly the charge-transfer and neutral excited diabatic states. The ET coupling values are obtained as the corresponding off-diagonal Hamiltonian matrix elements. A similar multi-state GMH scheme can also be developed. We test the new multi-state schemes for the performance in systems that have been studied using more than two states with FCD or GMH. We found that the multi-state approach yields much better charge-localized states in these systems. We further test for the dependence on the number of state included in the calculation of ET couplings. The final coupling values are converged when the number of state included is increased. In one system where experimental value is available, the multi-state FCD coupling value agrees better with the previous experimental result. We found that the multi-state GMH and FCD are useful when the original two-state approach fails.

  5. Crater Formation on Electrodes during Charge Transfer with Aqueous Droplets or Solid Particles

    NASA Astrophysics Data System (ADS)

    Elton, E. S.; Rosenberg, E. R.; Ristenpart, W. D.

    2017-09-01

    We report that metallic electrodes are physically pitted during charge transfer events with water droplets or other conductive objects moving in strong electric fields (>1 kV /cm ). Post situ microscopic inspection of the electrode shows that an individual charge transfer event yields a crater approximately 1-3 μ m wide, often with features similar to a splash corona. We interpret the crater formation in terms of localized melting of the electrode via resistive heating concurrent with dielectric breakdown through the surrounding insulating fluid. A scaling analysis indicates that the crater diameter scales as the inverse cube root of the melting point temperature Tm of the metal, in accord with measurements on several metals (660 °C ≤Tm≤3414 °C ). The process of crater formation provides a possible explanation for the longstanding difficulty in quantitatively corroborating Maxwell's prediction for the amount of charge acquired by spheres contacting a planar electrode.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Shukla, Madhulata; Srivastava, Nitin; Saha, Satyen

    2012-08-01

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

  9. Charge Transfer Directed Radical Substitution Enables para-Selective C–H Functionalization

    PubMed Central

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

    2016-01-01

    Efficient C–H functionalization requires selectivity for specific C–H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho- and meta- selectivity, but a general strategy for para-selective C–H functionalization has remained elusive. Herein, we introduce a previously unappreciated concept which enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit areneto-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate that the selectivity is predictable by a simple theoretical tool and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of charge transfer directed radical substitution could serve as the basis for the development of new, highly selective C–H functionalization reactions. PMID:27442288

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

    DOE PAGES

    Ma, X.; Fang, F.; Li, Q.; ...

    2015-10-28

    In this study, 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 recoverymore » 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.« less

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts

    NASA Astrophysics Data System (ADS)

    Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

    2013-01-01

    New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals.

  13. Charge-transfer-directed radical substitution enables para-selective C-H functionalization

    NASA Astrophysics Data System (ADS)

    Boursalian, Gregory B.; Ham, Won Seok; Mazzotti, Anthony R.; Ritter, Tobias

    2016-08-01

    Efficient C-H functionalization requires selectivity for specific C-H bonds. Progress has been made for directed aromatic substitution reactions to achieve ortho and meta selectivity, but a general strategy for para-selective C-H functionalization has remained elusive. Herein we introduce a previously unappreciated concept that enables nearly complete para selectivity. We propose that radicals with high electron affinity elicit arene-to-radical charge transfer in the transition state of radical addition, which is the factor primarily responsible for high positional selectivity. We demonstrate with a simple theoretical tool that the selectivity is predictable and show the utility of the concept through a direct synthesis of aryl piperazines. Our results contradict the notion, widely held by organic chemists, that radical aromatic substitution reactions are inherently unselective. The concept of radical substitution directed by charge transfer could serve as the basis for the development of new, highly selective C-H functionalization reactions.

  14. QLog Solar-Cell Mode Photodiode Logarithmic CMOS Pixel Using Charge Compression and Readout.

    PubMed

    Ni, Yang

    2018-02-14

    In this paper, we present a new logarithmic pixel design currently under development at New Imaging Technologies SA (NIT). This new logarithmic pixel design uses charge domain logarithmic signal compression and charge-transfer-based signal readout. This structure gives a linear response in low light conditions and logarithmic response in high light conditions. The charge transfer readout efficiently suppresses the reset (KTC) noise by using true correlated double sampling (CDS) in low light conditions. In high light conditions, thanks to charge domain logarithmic compression, it has been demonstrated that 3000 electrons should be enough to cover a 120 dB dynamic range with a mobile phone camera-like signal-to-noise ratio (SNR) over the whole dynamic range. This low electron count permits the use of ultra-small floating diffusion capacitance (sub-fF) without charge overflow. The resulting large conversion gain permits a single photon detection capability with a wide dynamic range without a complex sensor/system design. A first prototype sensor with 320 × 240 pixels has been implemented to validate this charge domain logarithmic pixel concept and modeling. The first experimental results validate the logarithmic charge compression theory and the low readout noise due to the charge-transfer-based readout.

  15. Photoinduced charge-transfer materials for nonlinear optical applications

    DOEpatents

    McBranch, Duncan W.

    2006-10-24

    A method using polyelectrolyte self-assembly for preparing multi-layered organic molecular materials having individual layers which exhibit ultrafast electron and/or energy transfer in a controlled direction occurring over the entire structure. Using a high molecular weight, water-soluble, anionic form of poly-phenylene vinylene, self-assembled films can be formed which show high photoluminescence quantum efficiency (QE). The highest emission QE is achieved using poly(propylene-imine) (PPI) dendrimers as cationic binders. Self-quenching of the luminescence is observed as the solid polymer film thickness is increased and can be reversed by inserting additional spacer layers of transparent polyelectrolytes between each active conjugated layer, such that the QE grows with thickness. A red shift of the luminescence is also observed as additional PPV layers are added. This effect persists as self-quenching is eliminated. Charge transfer superlattices can be formed by additionally incorporating C.sub.60 acceptor layers.

  16. Investigations on the charge transfer mechanism at donor/acceptor interfaces in the quest for descriptors of organic solar cell performance.

    PubMed

    Muraoka, Azusa; Fujii, Mikiya; Mishima, Kenji; Matsunaga, Hiroki; Benten, Hiroaki; Ohkita, Hideo; Ito, Shinzaburo; Yamashita, Koichi

    2018-05-07

    Herein, we theoretically and experimentally investigated the mechanisms of charge separation processes of organic thin-film solar cells. PTB7, PTB1, and PTBF2 have been chosen as donors and PC 71 BM has been chosen as an acceptor considering that effective charge generation depends on the difference between the material combinations. Experimental results of transient absorption spectroscopy show that the hot process is a key step for determining external quantum efficiency (EQE) in these systems. From the quantum chemistry calculations, it has been found that EQE tends to increase as the transferred charge, charge transfer distance, and variation of dipole moments between the ground and excited states of the donor/acceptor complexes increase; this indicates that these physical quantities are a good descriptor to assess the donor-acceptor charge transfer quality contributing to the solar cell performance. We propose that designing donor/acceptor interfaces with large values of charge transfer distance and variation of dipole moments of the donor/acceptor complexes is a prerequisite for developing high-efficiency polymer/PCBM solar cells.

  17. Polarization and charge transfer in the hydration of chloride ions

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

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

    2010-01-07

    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.more » 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.« less

  18. Heat-transfer analysis of double-pipe heat exchangers for indirect-cycle SCW NPP

    NASA Astrophysics Data System (ADS)

    Thind, Harwinder

    SuperCritical-Water-cooled Reactors (SCWRs) are being developed as one of the Generation-IV nuclear-reactor concepts. SuperCritical Water (SCW) Nuclear Power Plants (NPPs) are expected to have much higher operating parameters compared to current NPPs, i.e., pressure of about 25 MPa and outlet temperature up to 625 °C. This study presents the heat transfer analysis of an intermediate Heat exchanger (HX) design for indirect-cycle concepts of Pressure-Tube (PT) and Pressure-Vessel (PV) SCWRs. Thermodynamic configurations with an intermediate HX gives a possibility to have a single-reheat option for PT and PV SCWRs without introducing steam-reheat channels into a reactor. Similar to the current CANDU and Pressurized Water Reactor (PWR) NPPs, steam generators separate the primary loop from the secondary loop. In this way, the primary loop can be completely enclosed in a reactor containment building. This study analyzes the heat transfer from a SCW primary (reactor) loop to a SCW and Super-Heated Steam (SHS) secondary (turbine) loop using a double-pipe intermediate HX. The numerical model is developed with MATLAB and NIST REFPROP software. Water from the primary loop flows through the inner pipe, and water from the secondary loop flows through the annulus in the counter direction of the double-pipe HX. The analysis on the double-pipe HX shows temperature and profiles of thermophysical properties along the heated length of the HX. It was found that the pseudocritical region has a significant effect on the temperature profiles and heat-transfer area of the HX. An analysis shows the effect of variation in pressure, temperature, mass flow rate, and pipe size on the pseudocritical region and the heat-transfer area of the HX. The results from the numerical model can be used to optimize the heat-transfer area of the HX. The higher pressure difference on the hot side and higher temperature difference between the hot and cold sides reduces the pseudocritical-region length, thus

  19. Charge-Transfer Analysis of 2p3d Resonant Inelastic X-ray Scattering of Cobalt Sulfide and Halides

    PubMed Central

    2017-01-01

    We show that with 2p3d resonant inelastic X-ray scattering (RIXS) we can accurately determine the charge-transfer parameters of CoF2, CoCl2, CoBr2, and CoS. The 160 meV resolution RIXS results are compared with charge-transfer multiplet calculations. The improved resolution and the direct observation of the crystal field and charge-transfer excitations allow the determination of more accurate parameters than could be derived from X-ray absorption and X-ray photoemission, both limited in resolution by their lifetime broadening. We derive the crystal field and charge-transfer parameters of the Co2+ ions, which provides the nature of the ground state of the Co2+ ions with respect to symmetry and hybridization. In addition, the increased spectral resolution allows the more accurate determination of the atomic Slater integrals. The results show that the crystal field energy decreases with increasing ligand covalency. The L2 edge RIXS spectra show that the intensity of the (Coster–Kronig induced) nonresonant X-ray emission is a measure of ligand covalency. PMID:29170686

  20. Charge transfer polarisation wave in high Tc oxides and superconductive pairing

    NASA Technical Reports Server (NTRS)

    Chakraverty, B. K.

    1991-01-01

    A general formalism of quantized charge transfer polarization waves was developed. The nature of possible superconductive pairing between oxygen holes is discussed. Unlike optical phonons, these polarization fields will give rise to dielectric bipolarons or bipolaron bubbles. In the weak coupling limit, a new class of superconductivity is to be expected.

  1. Transfer of a wave packet in double-well potential

    NASA Astrophysics Data System (ADS)

    Yang, Hai-Feng; Hu, Yao-Hua; Tan, Yong-Gang

    2018-04-01

    Energy potentials with double-well structures are typical in atoms and molecules systems. A manipulation scheme using Half Cycles Pulses (HCPs) is proposed to transfer a Gaussian wave packet between the two wells. On the basis of quantum mechanical simulations, the time evolution and the energy distribution of the wave packet are evaluated. The effect of time parameters, amplitude, and number of HCPs on spatial and energy distribution of the final state and transfer efficiency are investigated. After a carefully tailored HCPs sequence is applied to the initial wave packet localized in one well, the final state is a wave packet localized in the other well and populated at the lower energy levels with narrower distribution. The present scheme could be used to control molecular reactions and to prepare atoms with large dipole moments.

  2. Macroscopic acoustoelectric charge transport in graphene

    NASA Astrophysics Data System (ADS)

    Bandhu, L.; Lawton, L. M.; Nash, G. R.

    2013-09-01

    We demonstrate macroscopic acoustoelectric transport in graphene, transferred onto piezoelectric lithium niobate substrates, between electrodes up to 500 μm apart. Using double finger interdigital transducers we have characterised the acoustoelectric current as a function of both surface acoustic wave intensity and frequency. The results are consistent with a relatively simple classical relaxation model, in which the acoustoelectric current is proportional to both the surface acoustic wave intensity and the attenuation of the wave caused by the charge transport.

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

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

    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

    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 indicatemore » 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.« less

  4. Preparation and spectroscopic studies on charge-transfer complexes of 2,2'-bipyridine with picric and chloranilic acids

    NASA Astrophysics Data System (ADS)

    Teleb, Said M.; Gaballa, Akmal S.

    2005-11-01

    Charge-transfer (CT) complexes formed on the reaction of 2,2'-bipyridine with some acceptors such as picric acid (HPA) and chloranilic acid (H 2CA) have been studied in CHCl 3 and MeOH at room temperature. Based on elemental analysis and IR spectra of the solid CT complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge-transfer complexes [(bpyH)(PA)] and [(bpyH 2)(CA)], respectively. The infrared and 1H NMR spectroscopic data indicate a charge-transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding. The formation constants ( KC) for the complexes were shown to be dependent on the structure of the electron acceptors used.

  5. Preparation and spectroscopic studies on charge-transfer complexes of 2,2'-bipyridine with picric and chloranilic acids.

    PubMed

    Teleb, Said M; Gaballa, Akmal S

    2005-11-01

    Charge-transfer (CT) complexes formed on the reaction of 2,2'-bipyridine with some acceptors such as picric acid (HPA) and chloranilic acid (H(2)CA) have been studied in CHCl(3) and MeOH at room temperature. Based on elemental analysis and IR spectra of the solid CT complexes along with the photometric titration curves for the reactions, the data obtained indicate the formation of 1:1 charge-transfer complexes [(bpyH)(PA)] and [(bpyH(2))(CA)], respectively. The infrared and (1)H NMR spectroscopic data indicate a charge-transfer interaction associated with a proton migration from the acceptor to the donor followed by intramolecular hydrogen bonding. The formation constants (K(C)) for the complexes were shown to be dependent on the structure of the electron acceptors used.

  6. Spectroscopy of charge transfer states in Mg1 - x Ni x O

    NASA Astrophysics Data System (ADS)

    Churmanov, V. N.; Sokolov, V. I.; Pustovarov, V. A.; Gruzdev, N. B.; Mironova-Ulmane, N.

    2016-10-01

    Photoluminescence and photoluminescence excitation spectra of solid solution Mg1- x Ni x O ( x = 0.008) have been analyzed. The contributions of charge transfer electronic states and nonradiative Auger relaxation to the formation of the photoluminescence spectrum are discussed.

  7. Momentum transfer in relativistic heavy ion charge-exchange reactions

    NASA Technical Reports Server (NTRS)

    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.

  8. The R package 'RLumModel': Simulating charge transfer in quartz

    NASA Astrophysics Data System (ADS)

    Friedrich, Johannes; Kreutzer, Sebastian; Schmidt, Christoph

    2017-04-01

    Kinetic models of quartz luminescence have gained an important role for predicting experimental results and for understanding charge transfers in (natural) quartz as well as for other dosimetric materials, e.g., Al2O3:C. We present the R package 'RLumModel', offering an easy-to-use tool for simulating quartz luminescence signals (TL, OSL, LM-OSL and RF) based on five integrated and published parameter sets as well as the possibility to use own parameters. Simulation commands can be created (a) using the Risø Sequence Editor, (b) a built-in SAR sequence generator or (c) self-explanatory keywords for customised sequences. Results can be analysed seamlessly using the R package 'Luminescence' along with a visualisation of concentrations of electrons and holes in every trap/centre as well as in the valence and conduction band during all stages of the simulation. Modelling luminescence signals can help understanding charge transfer processes occurring in nature or during measurements in the laboratory. This will lead to a better understanding of several processes concerning geoscientific questions, because quartz is the second most abundant mineral in the Earth's continental crust.

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

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

    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'-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 densitymore » 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.« less

  10. Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

    PubMed Central

    Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

    2008-01-01

    Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

  11. Strong Deformation of the Thick Electric Double Layer around a Charged Particle during Sedimentation or Electrophoresis.

    PubMed

    Khair, Aditya S

    2018-01-23

    The deformation of the electric double layer around a charged colloidal particle during sedimentation or electrophoresis in a binary, symmetric electrolyte is studied. The surface potential of the particle is assumed to be small compared to the thermal voltage scale. Additionally, the Debye length is assumed to be large compared to the particle size. These assumptions enable a linearization of the electrokinetic equations. The particle appears as a point charge in this thick-double-layer limit; the distribution of charge in the diffuse cloud surrounding it is determined by a balance of advection due to the particle motion, Brownian diffusion of ions, and electrostatic screening of the particle by the cloud. The ability of advection to deform the charge cloud from its equilibrium state is parametrized by a Péclet number, Pe. For weak advection (Pe ≪ 1), the cloud is only slightly deformed. In contrast, the cloud can be completely stripped from the particle at Pe ≫ 1; consequently, electrokinetic effects on the particle motion vanish in this regime. Therefore, in sedimentation the drag limits to Stokes' law for an uncharged particle as Pe → ∞. Likewise, the particle velocity for electrophoresis approaches Huckel's result. The strongly deformed cloud at large Pe is predicted to generate a concomitant increase in the sedimentation field in a dilute settling suspension.

  12. A 1D radiative transfer benchmark with polarization via doubling and adding

    NASA Astrophysics Data System (ADS)

    Ganapol, B. D.

    2017-11-01

    Highly precise numerical solutions to the radiative transfer equation with polarization present a special challenge. Here, we establish a precise numerical solution to the radiative transfer equation with combined Rayleigh and isotropic scattering in a 1D-slab medium with simple polarization. The 2-Stokes vector solution for the fully discretized radiative transfer equation in space and direction derives from the method of doubling and adding enhanced through convergence acceleration. Updates to benchmark solutions found in the literature to seven places for reflectance and transmittance as well as for angular flux follow. Finally, we conclude with the numerical solution in a partially randomly absorbing heterogeneous medium.

  13. Development of a Si/ SiO 2-based double quantum dot charge qubit with dispersive microwave readout

    NASA Astrophysics Data System (ADS)

    House, M. G.; Henry, E.; Schmidt, A.; Naaman, O.; Siddiqi, I.; Pan, H.; Xiao, M.; Jiang, H. W.

    2011-03-01

    Coupling of a high-Q microwave resonator to superconducting qubits has been successfully used to prepare, manipulate, and read out the state of a single qubit, and to mediate interactions between qubits. Our work is geared toward implementing this architecture in a semiconductor qubit. We present the design and development of a lateral quantum dot in which a superconducting microwave resonator is capacitively coupled to a double dot charge qubit. The device is a silicon MOSFET structure with a global gate which is used to accumulate electrons at a Si/ Si O2 interface. A set of smaller gates are used to deplete these electrons to define a double quantum dot and adjacent conduction channels. Two of these depletion gates connect directly to the conductors of a 6 GHz co-planar stripline resonator. We present measurements of transport and conventional charge sensing used to characterize the double quantum dot, and demonstrate that it is possible to reach the few-electron regime in this system. This work is supported by the DARPA-QuEST program.

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

    NASA Astrophysics Data System (ADS)

    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

  15. Coherence, Energy and Charge Transfers in De-Excitation Pathways of Electronic Excited State of Biomolecules in Photosynthesis

    NASA Astrophysics Data System (ADS)

    Bohr, Henrik G.; Malik, F. Bary

    2013-11-01

    The observed multiple de-excitation pathways of photo-absorbed electronic excited state in the peridinin-chlorophyll complex, involving both energy and charge transfers among its constituents, are analyzed using the bio-Auger (B-A) theory. It is also shown that the usually used Förster-Dexter theory, which does not allow for charge transfer, is a special case of B-A theory. The latter could, under appropriate circumstances, lead to excimers.

  16. Sunlight assisted direct amide formation via a charge-transfer complex.

    PubMed

    Cohen, Irit; Mishra, Abhaya K; Parvari, Galit; Edrei, Rachel; Dantus, Mauricio; Eichen, Yoav; Szpilman, Alex M

    2017-09-12

    We report on the use of charge-transfer complexes between amines and carbon tetrachloride, as a novel way to activate the amine for photochemical reactions. This principle is demonstrated in a mild, transition metal free, visible light assisted, dealkylative amide formation from feedstock carboxylic acids and amines. The low absorption coefficient of the complex allows deep light penetration and thus scale up to a gram scale.

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

    NASA Astrophysics Data System (ADS)

    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

  18. Doping graphene films via chemically mediated charge transfer.

    PubMed

    Ishikawa, Ryousuke; Bando, Masashi; Morimoto, Yoshitaka; Sandhu, Adarsh

    2011-01-31

    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.

  19. Energy transfer through a multi-layer liner for shaped charges

    DOEpatents

    Skolnick, Saul; Goodman, Albert

    1985-01-01

    This invention relates to the determination of parameters for selecting materials for use as liners in shaped charges to transfer the greatest amount of energy to the explosive jet. Multi-layer liners constructed of metal in shaped charges for oil well perforators or other applications are selected in accordance with the invention to maximize the penetrating effect of the explosive jet by reference to four parameters: (1) Adjusting the explosive charge to liner mass ratio to achieve a balance between the amount of explosive used in a shaped charge and the areal density of the liner material; (2) Adjusting the ductility of each layer of a multi-layer liner to enhance the formation of a longer energy jet; (3) Buffering the intermediate layers of a multi-layer liner by varying the properties of each layer, e.g., composition, thickness, ductility, acoustic impedance and areal density, to protect the final inside layer of high density material from shattering upon impact of the explosive force and, instead, flow smoothly into a jet; and (4) Adjusting the impedance of the layers in a liner to enhance the transmission and reduce the reflection of explosive energy across the interface between layers.

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

    NASA Astrophysics Data System (ADS)

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

    2017-09-01

    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 μmax of ANIH and ANICl crystals is 1.3893 and 0.0272 cm2 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.

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

    PubMed

    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.

  2. QLog Solar-Cell Mode Photodiode Logarithmic CMOS Pixel Using Charge Compression and Readout †

    PubMed Central

    Ni, Yang

    2018-01-01

    In this paper, we present a new logarithmic pixel design currently under development at New Imaging Technologies SA (NIT). This new logarithmic pixel design uses charge domain logarithmic signal compression and charge-transfer-based signal readout. This structure gives a linear response in low light conditions and logarithmic response in high light conditions. The charge transfer readout efficiently suppresses the reset (KTC) noise by using true correlated double sampling (CDS) in low light conditions. In high light conditions, thanks to charge domain logarithmic compression, it has been demonstrated that 3000 electrons should be enough to cover a 120 dB dynamic range with a mobile phone camera-like signal-to-noise ratio (SNR) over the whole dynamic range. This low electron count permits the use of ultra-small floating diffusion capacitance (sub-fF) without charge overflow. The resulting large conversion gain permits a single photon detection capability with a wide dynamic range without a complex sensor/system design. A first prototype sensor with 320 × 240 pixels has been implemented to validate this charge domain logarithmic pixel concept and modeling. The first experimental results validate the logarithmic charge compression theory and the low readout noise due to the charge-transfer-based readout. PMID:29443903

  3. Boosting the efficiency of quantum dot sensitized solar cells through modulation of interfacial charge transfer.

    PubMed

    Kamat, Prashant V

    2012-11-20

    The demand for clean energy will require the design of nanostructure-based light-harvesting assemblies for the conversion of solar energy into chemical energy (solar fuels) and electrical energy (solar cells). Semiconductor nanocrystals serve as the building blocks for designing next generation solar cells, and metal chalcogenides (e.g., CdS, CdSe, PbS, and PbSe) are particularly useful for harnessing size-dependent optical and electronic properties in these nanostructures. This Account focuses on photoinduced electron transfer processes in quantum dot sensitized solar cells (QDSCs) and discusses strategies to overcome the limitations of various interfacial electron transfer processes. The heterojunction of two semiconductor nanocrystals with matched band energies (e.g., TiO(2) and CdSe) facilitates charge separation. The rate at which these separated charge carriers are driven toward opposing electrodes is a major factor that dictates the overall photocurrent generation efficiency. The hole transfer at the semiconductor remains a major bottleneck in QDSCs. For example, the rate constant for hole transfer is 2-3 orders of magnitude lower than the electron injection from excited CdSe into oxide (e.g., TiO(2)) semiconductor. Disparity between the electron and hole scavenging rate leads to further accumulation of holes within the CdSe QD and increases the rate of electron-hole recombination. To overcome the losses due to charge recombination processes at the interface, researchers need to accelerate electron and hole transport. The power conversion efficiency for liquid junction and solid state quantum dot solar cells, which is in the range of 5-6%, represents a significant advance toward effective utilization of nanomaterials for solar cells. The design of new semiconductor architectures could address many of the issues related to modulation of various charge transfer steps. With the resolution of those problems, the efficiencies of QDSCs could approach those of dye

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

    PubMed

    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.

  5. Interaction and charge transfer between dielectric spheres: Exact and approximate analytical solutions.

    PubMed

    Lindén, Fredrik; Cederquist, Henrik; Zettergren, Henning

    2016-11-21

    We present exact analytical solutions for charge transfer reactions between two arbitrarily charged hard dielectric spheres. These solutions, and the corresponding exact ones for sphere-sphere interaction energies, include sums that describe polarization effects to infinite orders in the inverse of the distance between the sphere centers. In addition, we show that these exact solutions may be approximated by much simpler analytical expressions that are useful for many practical applications. This is exemplified through calculations of Langevin type cross sections for forming a compound system of two colliding spheres and through calculations of electron transfer cross sections. We find that it is important to account for dielectric properties and finite sphere sizes in such calculations, which for example may be useful for describing the evolution, growth, and dynamics of nanometer sized dielectric objects such as molecular clusters or dust grains in different environments including astrophysical ones.

  6. Effect of interstitial palladium on plasmon-driven charge transfer in nanoparticle dimers.

    PubMed

    Lerch, Sarah; Reinhard, Björn M

    2018-04-23

    Capacitive plasmon coupling between noble metal nanoparticles (NPs) is characterized by an increasing red-shift of the bonding dipolar plasmon mode (BDP) in the classical electromagnetic coupling regime. This model breaks down at short separations where plasmon-driven charge transfer induces a gap current between the NPs with a magnitude and separation dependence that can be modulated if molecules are present in the gap. Here, we use gap contained DNA as a scaffold for the growth of palladium (Pd) NPs in the gap between two gold NPs and investigate the effect of increasing Pd NP concentration on the BDP mode. Consistent with enhanced plasmon-driven charge transfer, the integration of discrete Pd NPs depolarizes the capacitive BDP mode over longer interparticle separations than is possible in only DNA-linked Au NPs. High Pd NP densities in the gap increases the gap conductance and induces the transition from capacitive to conductive coupling.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

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

    NASA Astrophysics Data System (ADS)

    Sun, Baichuan; Barnard, Amanda S.

    2016-07-01

    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.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

  9. [Diffusion and diffusion-osmosis models of the charged macromolecule transfer in barriers of biosystems].

    PubMed

    Varakin, A I; Mazur, V V; Arkhipova, N V; Serianov, Iu V

    2009-01-01

    Mathematical models of the transfer of charged macromolecules have been constructed on the basis of the classical equations of electromigration diffusion of Helmholtz-Smolukhovskii, Goldman, and Goldman-Hodgkin-Katz. It was shown that ion transfer in placental (mimicking lipid-protein barriers) and muscle barriers occurs by different mechanisms. In placental barriers, the electromigration diffusion occurs along lipid-protein channels formed due to the conformational deformation of phospholipid and protein molecules with the coefficients of diffusion D = (2.6-3.6) x 10(-8) cm2/s. The transfer in muscle barriers is due to the migration across charged interfibrillar channels with the negative diffusion activation energy, which is explained by changes in the structure of muscle fibers and expenditures of thermal energy for the extrusion of Cl- from channel walls with the diffusion coefficient D = (6.0-10.0) x 10(-6) cm2/s.

  10. Two-dimensional analytical model of double-gate tunnel FETs with interface trapped charges including effects of channel mobile charge carriers

    NASA Astrophysics Data System (ADS)

    Xu, Huifang; Dai, Yuehua

    2017-02-01

    A two-dimensional analytical model of double-gate (DG) tunneling field-effect transistors (TFETs) with interface trapped charges is proposed in this paper. The influence of the channel mobile charges on the potential profile is also taken into account in order to improve the accuracy of the models. On the basis of potential profile, the electric field is derived and the expression for the drain current is obtained by integrating the BTBT generation rate. The model can be used to study the impact of interface trapped charges on the surface potential, the shortest tunneling length, the drain current and the threshold voltage for varying interface trapped charge densities, length of damaged region as well as the structural parameters of the DG TFET and can also be utilized to design the charge trapped memory devices based on TFET. The biggest advantage of this model is that it is more accurate, and in its expression there are no fitting parameters with small calculating amount. Very good agreements for both the potential, drain current and threshold voltage are observed between the model calculations and the simulated results. Project supported by the National Natural Science Foundation of China (No. 61376106), the University Natural Science Research Key Project of Anhui Province (No. KJ2016A169), and the Introduced Talents Project of Anhui Science and Technology University.

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

    PubMed Central

    Ramana, CV; Becker, U; Shutthanandan, V; Julien, CM

    2008-01-01

    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 significant increase in

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

    PubMed

    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

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

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

    Pershin, Anton; Szalay, Péter G.

    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, itmore » 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.« less

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

    PubMed

    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.

  15. Oxygen vacancies promoted interfacial charge carrier transfer of CdS/ZnO heterostructure for photocatalytic hydrogen generation.

    PubMed

    Xie, Ying Peng; Yang, Yongqiang; Wang, Guosheng; Liu, Gang

    2017-10-01

    The solid-state Z-scheme trinary/binary heterostructures show the advantage of utilizing the high-energy photogenerated charge carriers in photocatalysis. However, the key factors controlling such Z-scheme in the binary heterostructures are still unclear. In this paper, we showed that oxygen vacancies could act as an interface electron transfer mediator to promote the direct Z-scheme charge transfer process in binary semiconductor heterostructures of CdS/ZnS. Increasing the concentration of surface oxygen vacancies of ZnO crystal can greatly enhance photocatalytic hydrogen generation of CdS/ZnO heterostructure. This was attributed to the strengthened direct Z-scheme charge transfer process in CdS/ZnO, as evidenced by steady-state/time-resolved photoluminescence spectroscopy and selective photodeposition of metal particles on the heterostructure. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. Metal-to-metal charge transfer transitions - Interpretation of visible-region spectra of the moon and lunar materials

    NASA Technical Reports Server (NTRS)

    Loeffler, B. M.; Burns, R. G.; Tossell, J. A.

    1975-01-01

    Prominent bands in the spectral profiles of Fe-Ti phases in lunar samples have been attributed to charge-transfer transitions between Fe and Ti cations, and a model is presented for calculating charge transfer energies from energy levels computed by the SCF-X(alpha) scattered wave molecular orbital method for isolated MO6 octahedral coordination clusters containing Fe(2+), Fe(3+), Ti(3+), and Ti(4+) cations. The calculated charge transfer energy for the Fe(2+) to Ti(4+) transition correlates well with a measured spectral feature around 0.6 micron in ilmenite, and, since ilmenite is a major constituent of mare basalts and dark-mantling material, the observed darkness and blueness of the regolith in lunar black spots is attributed primarily to this transition. The Ti(3+) to Ti(4+) transition is thought to contribute to some phases.

  17. Global and Local Partitioning of the Charge Transferred in the Parr-Pearson Model.

    PubMed

    Orozco-Valencia, Angel Ulises; Gázquez, José L; Vela, Alberto

    2017-05-25

    Through a simple proposal, the charge transfer obtained from the cornerstone theory of Parr and Pearson is partitioned, for each reactant, in two channels: an electrophilic, through which the species accepts electrons, and the other, a nucleophilic, where the species donates electrons. It is shown that this global model allows us to determine unambiguously the charge-transfer mechanism prevailing in a given reaction. The partitioning is extended to include local effects through the Fukui functions of the reactants. This local model is applied to several emblematic reactions in organic and inorganic chemistry, and we show that besides improving the correlations obtained with the global model it provides valuable information concerning the atoms in the reactants playing the most important roles in the reaction and thus improving our understanding of the reaction under study.

  18. Modeling the double charge exchange response function for a tetraneutron system

    NASA Astrophysics Data System (ADS)

    Lazauskas, R.; Carbonell, J.; Hiyama, E.

    2017-07-01

    This work is an attempt to model the 4 n response function of a recent RIKEN experimental study of the double charge exchange  4 He( 8 He, 8 Be) 4n reaction in order to put in evidence an eventual enhancement mechanism of the zero-energy cross section, including a near-threshold resonance. This resonance can indeed be reproduced only by adding to the standard nuclear Hamiltonian an unphysically large T =3/2 attractive 3 n -force that destroys the neighboring nuclear chart. No other mechanisms, like cusps or related structures, were found.

  19. Synthesis, structural, spectroscopic and optical studies of charge transfer complex salts.

    PubMed

    Manikandan, Maruthappan; Mahalingam, Thaiyan; Hayakawa, Yasuhiro; Ravi, Ganesan

    2013-01-15

    New charge transfer molecular complex adducts of picric acid (C6H3N3O7) with triethylamine (C6H15N) and dimethylformamide (HCON(CH3)2) were synthesized successfully for the first time. Chemical composition and stoichiometry of the synthesized complex salts were verified by CHN elemental analysis. Solubility of the complex salts have been determined by gravimetric method and single crystals of two new salts were grown by low temperature solution growth technique. Crystal system, crystalline nature and cell parameters of the grown crystals were determined by single crystal X-ray diffraction (SXRD) and powder X-ray diffraction (PXRD) analyses. The formations of the charge-transfer complex, functional groups and the modes of vibrations have been confirmed by Fourier transform infrared (FTIR) spectroscopy. In order to know the linear and nonlinear optical suitability for device fabrication, UV-Vis (UV) spectral analysis and relative second harmonic generation (SHG) efficiency test were performed for the grown crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Charge-transfer complexes of sulfamethoxazole drug with different classes of acceptors

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Korashy, Sabry A.; El-Deen, Ibrahim M.; El-Sayed, Shaima M.

    2010-09-01

    The charge-transfer complexes of the donor sulfamethoxazole (SZ) with iodine (I 2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), p-chloranil (CHL) and picric acid (PA) have been studied spectrophotometrically in chloroform or methanol at room temperature using absorption spectrophotometer. The results indicate that formation of CT-complexes in case of four acceptors. The stoichiometry of the complexes was found to be 1:1 ratio by molar ratio method between donor and acceptor with maximum absorption bands (CT band). The data are discussed in terms of formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G°), oscillator strength (ƒ), transition dipole moment ( μ), resonance energy ( RN) and ionization potential ( ID). The results indicate that the formation constant ( KCT) for the complexes were shown to be dependent upon the nature of electron acceptor, donor and polarity of solvents which were used. IR, 1H NMR, mass spectra, UV-Vis techniques, elemental analyses (CHN) and TG-DTG investigation were used to characterize the four sulfamethoxazole charge-transfer complexes.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Nanoscale charge transfer and diffusion at the MoS2/SiO2 interface by atomic force microscopy: contact injection versus triboelectrification.

    PubMed

    Xu, Rui; Ye, Shili; Xu, Kunqi; Lei, Le; Hussain, Sabir; Zheng, Zhiyue; Pang, Fei; Xing, Shuya; Liu, Xinmeng; Ji, Wei; Cheng, Zhihai

    2018-08-31

    Understanding the process of charge generation, transfer, and diffusion between two-dimensional (2D) materials and their supporting substrates is very important for potential applications of 2D materials. Compared with the systematic studies of triboelectric charging in a bulk sample, a fundamental understanding of the triboelectrification of the 2D material/insulator system is rather limited. Here, the charge transfer and diffusion of both the SiO 2 surface and MoS 2 /SiO 2 interface through contact electrification and frictional electrification are investigated systematically in situ by scanning Kelvin probe microscopy and dual-harmonic electrostatic force microscopy. Different from the simple static charge transfer between SiO 2 and the PtSi alloy atomic force microscope (AFM) tip, the charge transfer between the tip and the MoS 2 /SiO 2 system is complicated. Triboelectric charges, generated by contact or frictional electrification with the AFM tip, are trapped at the MoS 2 /SiO 2 interface and act as floating gates. The local charge discharge processes can be obtained by monitoring the surface potential. The charge decay time (τ) of the MoS 2 /SiO 2 interface is one (or two) orders of magnitude larger than the decay time τ of the SiO 2 surface. This work facilitates an understanding of the triboelectric and de-electrification of the interface between 2D materials and substrates. In addition to the charge transfer and diffusion, we demonstrate the nanopatterns of surface and interfacial charges, which have great potential for the application of self-assembly of charged nanostructures.

  3. Antineutrino Charged-Current Reactions on Hydrocarbon with Low Momentum Transfer

    NASA Astrophysics Data System (ADS)

    Gran, R.; Betancourt, M.; Elkins, M.; Rodrigues, P. A.; Akbar, F.; Aliaga, L.; Andrade, D. A.; Bashyal, A.; Bellantoni, L.; Bercellie, A.; Bodek, A.; Bravar, A.; Budd, H.; Vera, G. F. R. Caceres; Cai, T.; Carneiro, M. F.; Coplowe, D.; da Motta, H.; Dytman, S. A.; Díaz, G. A.; Felix, J.; Fields, L.; Fine, R.; Gallagher, H.; Ghosh, A.; Haider, H.; Han, J. Y.; Harris, D. A.; Henry, S.; Jena, D.; Kleykamp, J.; Kordosky, M.; Le, T.; Leistico, J. R.; Lovlein, A.; Lu, X.-G.; Maher, E.; Manly, S.; Mann, W. A.; Marshall, C. M.; McFarland, K. S.; McGowan, A. M.; Messerly, B.; Miller, J.; Mislivec, A.; Morfín, J. G.; Mousseau, J.; Naples, D.; Nelson, J. K.; Nguyen, C.; Norrick, A.; Nuruzzaman, Olivier, A.; Paolone, V.; Patrick, C. E.; Perdue, G. N.; Ramírez, M. A.; Ransome, R. D.; Ray, H.; Ren, L.; Rimal, D.; Ruterbories, D.; Schellman, H.; Salinas, C. J. Solano; Su, H.; Sultana, M.; Falero, S. Sánchez; Valencia, E.; Wolcott, J.; Wospakrik, M.; Yaeggy, B.; Minerva Collaboration

    2018-06-01

    We report on multinucleon effects in low momentum transfer (<0.8 GeV /c ) antineutrino interactions on plastic (CH) scintillator. These data are from the 2010-2011 antineutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well described when a screening effect at a low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasielastic, Δ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this antineutrino sample. We present the results as a double-differential cross section to accelerate the investigation of alternate models for antineutrino scattering off nuclei.

  4. Antineutrino Charged-Current Reactions on Hydrocarbon with Low Momentum Transfer.

    PubMed

    Gran, R; Betancourt, M; Elkins, M; Rodrigues, P A; Akbar, F; Aliaga, L; Andrade, D A; Bashyal, A; Bellantoni, L; Bercellie, A; Bodek, A; Bravar, A; Budd, H; Vera, G F R Caceres; Cai, T; Carneiro, M F; Coplowe, D; da Motta, H; Dytman, S A; Díaz, G A; Felix, J; Fields, L; Fine, R; Gallagher, H; Ghosh, A; Haider, H; Han, J Y; Harris, D A; Henry, S; Jena, D; Kleykamp, J; Kordosky, M; Le, T; Leistico, J R; Lovlein, A; Lu, X-G; Maher, E; Manly, S; Mann, W A; Marshall, C M; McFarland, K S; McGowan, A M; Messerly, B; Miller, J; Mislivec, A; Morfín, J G; Mousseau, J; Naples, D; Nelson, J K; Nguyen, C; Norrick, A; Nuruzzaman; Olivier, A; Paolone, V; Patrick, C E; Perdue, G N; Ramírez, M A; Ransome, R D; Ray, H; Ren, L; Rimal, D; Ruterbories, D; Schellman, H; Salinas, C J Solano; Su, H; Sultana, M; Falero, S Sánchez; Valencia, E; Wolcott, J; Wospakrik, M; Yaeggy, B

    2018-06-01

    We report on multinucleon effects in low momentum transfer (<0.8  GeV/c) antineutrino interactions on plastic (CH) scintillator. These data are from the 2010-2011 antineutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well described when a screening effect at a low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasielastic, Δ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this antineutrino sample. We present the results as a double-differential cross section to accelerate the investigation of alternate models for antineutrino scattering off nuclei.

  5. A multiscale model for charge inversion in electric double layers

    NASA Astrophysics Data System (ADS)

    Mashayak, S. Y.; Aluru, N. R.

    2018-06-01

    Charge inversion is a widely observed phenomenon. It is a result of the rich statistical mechanics of the molecular interactions between ions, solvent, and charged surfaces near electric double layers (EDLs). Electrostatic correlations between ions and hydration interactions between ions and water molecules play a dominant role in determining the distribution of ions in EDLs. Due to highly polar nature of water, near a surface, an inhomogeneous and anisotropic arrangement of water molecules gives rise to pronounced variations in the electrostatic and hydration energies of ions. Classical continuum theories fail to accurately describe electrostatic correlations and molecular effects of water in EDLs. In this work, we present an empirical potential based quasi-continuum theory (EQT) to accurately predict the molecular-level properties of aqueous electrolytes. In EQT, we employ rigorous statistical mechanics tools to incorporate interatomic interactions, long-range electrostatics, correlations, and orientation polarization effects at a continuum-level. Explicit consideration of atomic interactions of water molecules is both theoretically and numerically challenging. We develop a systematic coarse-graining approach to coarse-grain interactions of water molecules and electrolyte ions from a high-resolution atomistic scale to the continuum scale. To demonstrate the ability of EQT to incorporate the water orientation polarization, ion hydration, and electrostatic correlations effects, we simulate confined KCl aqueous electrolyte and show that EQT can accurately predict the distribution of ions in a thin EDL and also predict the complex phenomenon of charge inversion.

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

    DOE PAGES

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

    2015-09-15

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

  7. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA) 2] and [(o-TOL)(CA) 2] have been prepared. The 13C NMR, 1H NMR, 1H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH 2 groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.

  8. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids.

    PubMed

    Refat, Moamen S; Saad, Hosam A; Adam, Abdel Majid A

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA)(2)] and [(o-TOL)(CA)(2)] have been prepared. The (13)C NMR, (1)H NMR, (1)H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH(2) groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic. Copyright © 2011 Elsevier B.V. All rights reserved.

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

    PubMed

    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.

  10. Charge Transfer and Support Effects in Heterogeneous Catalysis

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

    Hervier, Antoine

    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/TiO 2 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 throughmore » Pt and overcome the Schottky barrier at the interface with TiO 2. 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/TiO 2 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 D 2 compared to H 2, contrary to what is expected given the higher mass of D 2. Reversible changes in the rectification factor of the diode are observed when switching between D 2 and H 2. 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 H 2 oxidation. Absorption of the light in the Si, combined with the band bending at the interface, gives rise to a steady-state flow of hot holes to the

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

    PubMed

    Zhou, Changjie; Yang, Weihuang; Zhu, Huili

    2015-06-07

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

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

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. 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

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

    Cramer, Christopher J.

    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.

  15. Charge Transfer Modulated Self-Assembly in Poly(aryl ether) Dendron Derivatives with Improved Stability and Transport Characteristics.

    PubMed

    Satapathy, Sitakanta; Prasad, Edamana

    2016-10-05

    Alteration of native gelation properties of anthracene and pyrene cored first generation poly(aryl ether) dendrons, G1-An and G1-Py, by introducing a common acceptor, 2,4,7-trinitro-9H-fluoren-9-one (TNF), results in forming charge transfer gels in long chain alcoholic solvents. This strategy leads to significant perturbation of optical and electronic properties within the gel matrix. Consequently, a noticeable increase of their electrical conductivities is observed, making these poly(aryl ether) dendron based gels potential candidates for organic electronics. While the dc-conductivity (σ) value for the native gel from G1-An is 2.8 × 10 -4 S m -1 , the value increased 3 times (σ = 8.7 × 10 -4 S m -1 ) for its corresponding charge transfer gel. Further, the dc-conductivity for the native gel self-assembled from G1-Py dramatically enhanced by approximately an order of magnitude from 4.9 × 10 -4 to 1.3 × 10 -3 S m -1 , under the influence of an acceptor. Apart from H-bonding and π···π interactions, charge transfer results in the formation of a robust 3D network of fibers, with improved aspect ratio, providing high thermo-mechanical stability to the gels compared to the native ones. The charge transfer gels self-assembled from G1-An/TNF (1:1) and G1-Py/TNF exhibit a 7.3- and 2.5-fold increase in their yield stress, respectively, compared to their native assemblies. A similar trend follows in the case of their thermal stabilities. This is attributed to the typical bilayer self-assembly of the former which is not present in the case of G1-Py/TNF charge transfer gel. Density functional calculations provide deeper insights accounting for the role of charge transfer interactions in the mode of self-assembly. The 1D potential energy surface for the G1-An/TNF dimer and G1-Py/TNF dimer is found to be 11.8 and 1.9 kcal mol -1 more stable than their corresponding native gel dimers, G1-An/G1-An and G1-Py/G1-Py, respectively.

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Cost-effectiveness of single versus double embryo transfer in IVF in relation to female age.

    PubMed

    van Loendersloot, Laura L; Moolenaar, Lobke M; van Wely, Madelon; Repping, Sjoerd; Bossuyt, Patrick M; Hompes, Peter G A; van der Veen, Fulco; Mol, Ben Willem J

    2017-07-01

    To evaluate the cost-effectiveness of single embryo transfer followed by an additional frozen-thawed single embryo transfer, if more embryos are available, as compared to double embryo transfer in relation to female age. We used a decision tree model to evaluate the costs from a healthcare provider perspective and the pregnancy rates of two embryo transfer policies: one fresh single embryo transfer followed by an additional frozen-thawed single embryo transfer, if more embryos are available (strategy I), and double embryo transfer (strategy II). The analysis was performed on an intention-to-treat basis. Sensitivity analyses were carried out to evaluate the robustness of our model and to identify which model parameters had the strongest impact on the results. SET followed by an additional frozen-thawed single embryo transfer if available was dominant, less costly and more effective, over DET in women under 32 years. In women aged 32 or older DET was more effective than SET followed by an additional frozen-thawed single embryo transfer if available but also more costly. SET followed by an additional frozen-thawed single embryo transfer should be the preferred strategy in women under 32 undergoing IVF. The choice for SET followed by an additional frozen-thawed single embryo transfer or DET in women aged 32 or older depends on individual patient preferences and on how much society is willing to pay for an extra child. There is a strong need for a randomized clinical trial comparing the cost and effects of SET followed by an additional frozen-thawed single embryo transfer and DET in the latter category of women. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

    Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas

    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 overlapmore » 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.« less

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

    PubMed

    Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas; Neugebauer, Johannes

    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 Ångstroms. Numerical examples are provided for molecular clusters comprised of up to 56 non-covalently bound molecules.

  20. Excited State Structural Dynamics of Carotenoids and ChargeTransfer Systems

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

    Van Tassle, Aaron Justin

    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 statemore » 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.« less

  1. Charge Profile Analysis Reveals That Activation of Pro-apoptotic Regulators Bax and Bak Relies on Charge Transfer Mediated Allosteric Regulation

    PubMed Central

    Ionescu, Crina-Maria; Svobodová Vařeková, Radka; Prehn, Jochen H. M.; Huber, Heinrich J.; Koča, Jaroslav

    2012-01-01

    The pro-apoptotic proteins Bax and Bak are essential for executing programmed cell death (apoptosis), yet the mechanism of their activation is not properly understood at the structural level. For the first time in cell death research, we calculated intra-protein charge transfer in order to study the structural alterations and their functional consequences during Bax activation. Using an electronegativity equalization model, we investigated the changes in the Bax charge profile upon activation by a functional peptide of its natural activator protein, Bim. We found that charge reorganizations upon activator binding mediate the exposure of the functional sites of Bax, rendering Bax active. The affinity of the Bax C-domain for its binding groove is decreased due to the Arg94-mediated abrogation of the Ser184-Asp98 interaction. We further identified a network of charge reorganizations that confirms previous speculations of allosteric sensing, whereby the activation information is conveyed from the activation site, through the hydrophobic core of Bax, to the well-distanced functional sites of Bax. The network was mediated by a hub of three residues on helix 5 of the hydrophobic core of Bax. Sequence and structural alignment revealed that this hub was conserved in the Bak amino acid sequence, and in the 3D structure of folded Bak. Our results suggest that allostery mediated by charge transfer is responsible for the activation of both Bax and Bak, and that this might be a prototypical mechanism for a fast activation of proteins during signal transduction. Our method can be applied to any protein or protein complex in order to map the progress of allosteric changes through the proteins' structure. PMID:22719244

  2. Exciplex: An Intermolecular Charge-Transfer Approach for TADF.

    PubMed

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  4. Charge Transfer and Collection in Dilute Organic Donor-Acceptor Heterojunction Blends.

    PubMed

    Ding, Kan; Liu, Xiao; Forrest, Stephen R

    2018-05-09

    Experimental and theoretical approaches are used to understand the role of nanomorphology on exciton dissociation and charge collection at dilute donor-acceptor (D-A) organic heterojunctions (HJs). Specifically, two charge transfer (CT) states in D-A mixed HJs comprising nanocrystalline domains of tetraphenyldibenzoperiflanthene (DBP) as the donor and C 70 as the acceptor are unambiguously related to the nanomorphology of the mixed layer. Alternating DBP:C 70 multilayer stacks are used to identify and control the optical properties of the CT states, as well as to simulate the dilute mixed heterojunctions. A kinetic Monte Carlo model along with photoluminescence spectroscopy and scanning transmission electron microscopy are used to quantitatively evaluate the layer morphology under various growth conditions. As a result, we are able to understand the counterintuitive observation of high charge extraction efficiency and device performance of DBP:C 70 mixed layer photovoltaics at surprisingly low (∼10%) donor concentrations.

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

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

    2000-01-01

    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.

  7. Spectral and photophysical properties of intramolecular charge transfer fluorescence probe: 4'-Dimethylamino-2,5-dihydroxychalcone

    NASA Astrophysics Data System (ADS)

    Xu, Zhicheng; Bai, Guan; Dong, Chuan

    2005-12-01

    The spectral and photophysical properties of a new intramolecular charge transfer (ICT) probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC) were studied in different solvents by using steady-state absorption and emission spectroscopy. Whereas the absorption spectrum undergoes minor change with increasing polarity of the solvents, the fluorescence spectrum experiences a distinct bathochromic shift in the band position and the fluorescence quantum yield increases reaching a maximum before decrease with increasing the solvent polarity. The magnitude of change in the dipole moment was calculated based on the Lippert-Mataga equation. These results give the evidence about the intramolecular charge transfer character in the emitting singlet state of this compound.

  8. Spectral and photophysical properties of intramolecular charge transfer fluorescence probe: 4'-dimethylamino-2,5-dihydroxychalcone.

    PubMed

    Xu, Zhicheng; Bai, Guan; Dong, Chuan

    2005-12-01

    The spectral and photophysical properties of a new intramolecular charge transfer (ICT) probe, namely 4'-dimethylamino-2,5-dihydroxychalcone (DMADHC) were studied in different solvents by using steady-state absorption and emission spectroscopy. Whereas the absorption spectrum undergoes minor change with increasing polarity of the solvents, the fluorescence spectrum experiences a distinct bathochromic shift in the band position and the fluorescence quantum yield increases reaching a maximum before decrease with increasing the solvent polarity. The magnitude of change in the dipole moment was calculated based on the Lippert-Mataga equation. These results give the evidence about the intramolecular charge transfer character in the emitting singlet state of this compound.

  9. Double heterojunction nanowire photocatalysts for hydrogen generation

    NASA Astrophysics Data System (ADS)

    Tongying, P.; Vietmeyer, F.; Aleksiuk, D.; Ferraudi, G. J.; Krylova, G.; Kuno, M.

    2014-03-01

    Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ~434.29 +/- 27.40 μmol h-1 g-1 under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core

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

    PubMed

    Mandal, I; Paul, S; Venkatramani, R

    2018-04-17

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

  11. Modulation of spin transfer torque amplitude in double barrier magnetic tunnel junctions

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

    Clément, P.-Y.; Baraduc, C., E-mail: claire.baraduc@cea.fr; Chshiev, M.

    2015-09-07

    Magnetization switching induced by spin transfer torque is used to write magnetic memories (Magnetic Random Access Memory, MRAM) but can be detrimental to the reading process. It would be quite convenient therefore to modulate the efficiency of spin transfer torque. A solution is adding an extra degree of freedom by using double barrier magnetic tunnel junctions with two spin-polarizers, with controllable relative magnetic alignment. We demonstrate, for these structures, that the amplitude of in-plane spin transfer torque on the middle free layer can be efficiently tuned via the magnetic configuration of the electrodes. Using the proposed design could thus pavemore » the way towards more reliable read/write schemes for MRAM. Moreover, our results suggest an intriguing effect associated with the out-of-plane (field-like) spin transfer torque, which has to be further investigated.« less

  12. Photoinduced Charge Transfer from Titania to Surface Doping Site

    PubMed Central

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

    2013-01-01

    We evaluate a theoretical model in which Ru is substituting for Ti at the (100) surface of anatase TiO2. Charge transfer from the photo-excited TiO2 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 TiO2 nanorod and catalytic site. A slab of TiO2 represents a fragment of TiO2 nanorod in the anatase phase. Titanium to ruthenium replacement is performed in a way to match the symmetry of TiO2 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 TiO2 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. PMID:23795229

  13. Photoinduced Charge Transfer from Titania to Surface Doping Site.

    PubMed

    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.

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

    PubMed

    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.

  15. Ultrafast charge transfer between MoTe2 and MoS2 monolayers

    NASA Astrophysics Data System (ADS)

    Pan, Shudi; Ceballos, Frank; Bellus, Matthew Z.; Zereshki, Peymon; Zhao, Hui

    2017-03-01

    High quality and stable electrical contact between metal and two-dimensional materials, such as transition metal dichalcogenides, is a necessary requirement that has yet to be achieved in order to successfully exploit the advantages that these materials offer to electronics and optoelectronics. MoTe2, owing to its phase changing property, can potentially offer a solution. A recent study demonstrated that metallic phase of MoTe2 connects its semiconducting phase with very low resistance. To utilize this property to connect other two-dimensional materials, it is important to achieve efficient charge transfer between MoTe2 and other semiconducting materials. Using MoS2 as an example, we report ultrafast and efficient charge transfer between MoTe2 and MoS2 monolayers. In the transient absorption measurements, an ultrashort pump pulse is used to selectively excite electrons in MoTe2. The appearance of the excited electrons in the conduction band of MoS2 is monitored by using a probe pulse that is tuned to the resonance of MoS2. We found that electrons transfer to MoS2 on a time scale of at most 0.3 ps. The transferred electrons give rise to a large transient absorption signal at both A-exciton and B-exciton resonances due to the screening effect. We also observed ultrafast transfer of holes from MoS2 to MoTe2. Our results suggest the feasibility of using MoTe2 as a bridge material to connect MoS2 and other transition metal dichalcogenides, and demonstrate a new transition metal dichalcogenide heterostructure involving MoTe2, which extends the spectral range of such structures to infrared.

  16. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies

    NASA Technical Reports Server (NTRS)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.

    2002-01-01

    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  17. Antineutrino Charged-Current Reactions on Hydrocarbon with Low Momentum Transfer

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

    Gran, R.; Betancourt, M.; Elkins, M.

    We report on multi-nucleon effects in low momentum transfer (more » $< 0.8$ GeV/c) anti-neutrino interactions on scintillator. These data are from the 2010-11 anti-neutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well-described when a screening effect at low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasi-elastic, $$\\Delta$$ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this anti-neutrino sample. We present the results as a double-differential cross section to accelerate investigation of alternate models for anti-neutrino scattering off nuclei.« less

  18. Antineutrino Charged-Current Reactions on Hydrocarbon with Low Momentum Transfer

    DOE PAGES

    Gran, R.; Betancourt, M.; Elkins, M.; ...

    2018-06-01

    We report on multi-nucleon effects in low momentum transfer (more » $< 0.8$ GeV/c) anti-neutrino interactions on scintillator. These data are from the 2010-11 anti-neutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well-described when a screening effect at low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasi-elastic, $$\\Delta$$ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this anti-neutrino sample. We present the results as a double-differential cross section to accelerate investigation of alternate models for anti-neutrino scattering off nuclei.« less

  19. Influence of Processing Additives on Charge-Transfer Time Scales and Sound Velocity in Organic Bulk Heterojunction Films.

    PubMed

    Kaake, Loren G; Welch, Gregory C; Moses, Daniel; Bazan, Guillermo C; Heeger, Alan J

    2012-05-17

    The role of processing additives in organic bulk heterojunction thin films was investigated by means of transient absorption spectroscopy. The rate of ultrafast charge transfer was found to increase when a small amount of diiodooctane was used during film formation. In addition, coherent acoustic phonons were observed, and their velocity was determined. A strong correlation between the sound velocity and the charge-transfer time scale was observed, both of which could be explained by a subtle increase in thin film density.

  20. Non-perturbative Quantification of Ionic Charge Transfer through Nm-Scale Protein Pores Using Graphene Microelectrodes

    NASA Astrophysics Data System (ADS)

    Ping, Jinglei; Johnson, A. T. Charlie; A. T. Charlie Johnson Team

    Conventional electrical methods for detecting charge transfer through protein pores perturb the electrostatic condition of the solution and chemical reactivity of the pore, and are not suitable to be used for complex biofluids. We developed a non-perturbative methodology ( fW input power) for quantifying trans-pore electrical current and detecting the pore status (i.e., open vs. closes) via graphene microelectrodes. Ferritin was used as a model protein featuring a large interior compartment, well-separated from the exterior solution with discrete pores as charge commuting channels. The charge flowing through the ferritin pores transfers into the graphene microelectrode and is recorded by an electrometer. In this example, our methodology enables the quantification of an inorganic nanoparticle-protein nanopore interaction in complex biofluids. The authors acknowledge the support from the Defense Advanced Research Projects Agency (DARPA) and the U.S. Army Research Office under Grant Number W911NF1010093.

  1. Boundary layer charge dynamics in ionic liquid-ionic polymer transducers

    NASA Astrophysics Data System (ADS)

    Davidson, Jacob D.; Goulbourne, N. C.

    2011-01-01

    Ionic polymer transducers (IPTs), also known as ionic polymer-metal composites, are soft sensors and actuators which operate through a coupling of microscale chemical, electrical, and mechanical interactions. The use of an ionic liquid as solvent for an IPT has been shown to dramatically increase transducer lifetime in free-air use, while also allowing for higher applied voltages without electrolysis. In this work, we apply Nernst-Planck/Poisson theory to model charge transport in an ionic liquid IPT by considering a certain fraction of the ionic liquid ions as mobile charge carriers, a phenomenon which is unique to ionic liquid IPTs compared to their water-based counterparts. Numerical simulations are performed using the finite element method to examine how the introduction of another pair of mobile ions affects boundary layer charge dynamics, concentration, and charge density distributions in the electric double layer, and the overall charge transferred and current response of the IPT. Due to interactions with the Nafion ionomer, not all of the ionic liquid ions will function as mobile charge carriers; only a certain fraction will exist as "free" ions. The presence of mobile ionic liquid ions in the transducer will increase the overall charge transferred when a voltage is applied, and cause the current in the transducer to decay more slowly. The additional mobile ions also cause the ionic concentration profiles to exhibit a nonlinear dynamic response, characterized by nonmonotonic ionic concentration profiles in space and time. Although the presence of mobile ionic liquid ions increases the overall amount of charge transferred, this additional charge transfer occurs in a somewhat symmetric manner. Therefore, the additional charge transferred due to the ionic liquid ions does not greatly increase the net bending moment of the transducer; in fact, it is possible that ionic liquid ion movement actually decreases the observed bending response. This suggests that an

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

    PubMed

    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.

  3. Solvophilic and solvophobic surfaces and non-Coulombic surface interactions in charge regulating electric double layers

    NASA Astrophysics Data System (ADS)

    Vangara, R.; van Swol, F.; Petsev, D. N.

    2018-01-01

    The properties of electric double layers are governed by the interface between the substrate and the adjacent electrolyte solution. This interface is involved in chemical, Coulombic, and non-Coulombic (e.g., van der Waals or Lennard-Jones) interactions with all components of the fluid phase. We present a detailed study of these interactions using a classical density functional approach. A particular focus is placed on the non-Coulombic interactions and their effect on the surface chemistry and charge regulation. The solution structure near the charged interface is also analyzed and used to offer a thorough interpretation of established concepts such as the Stern and diffuse ionic layers.

  4. Optimization of pentacene double floating gate memories based on charge injection regulated by SAM functionalization

    NASA Astrophysics Data System (ADS)

    Li, S.; Guérin, D.; Lenfant, S.; Lmimouni, K.

    2018-02-01

    Pentacene based double nano-floating gate memories (NFGM) by using gold nanoparticles (Au NPs) and reduced graphene oxide (rGO) sheets as charge trapping layers are prepared and demonstrated. Particularly, the NFGM chemically treated by 2,3,4,5,6-pentafluorobenzenethiol (PFBT) self-assembled monolayers (SAM) exhibits excellent memory performances, including high mobility of 0.23 cm2V-1s-1, the large memory window of 51 V, and the stable retention property more than 108 s. Comparing the performances of NFGM without treating with PFBT SAM, the improving performances of the memory devices by SAM modification are explained by the increase of charge injection, which could be further investigated by XPS and UPS. In particular, the results highlight the utility of SAM modulations and controlling of charge transport in the development of organic transistor memories.

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

    PubMed

    Min, Sung-Wook; Yoon, Minho; Yang, Sung Jin; Ko, Kyeong Rok; Im, Seongil

    2018-01-31

    The two-dimensional transition-metal dichalcogenide semiconductor MoS 2 has received extensive attention for decades because of its outstanding electrical and mechanical properties for next-generation devices. One weakness of MoS 2 , however, is that it shows only n-type conduction, revealing its limitations for homogeneous PN diodes and complementary inverters. Here, we introduce a charge-transfer method to modify the conduction property of MoS 2 from n- to p-type. We initially deposited an n-type InGaZnO (IGZO) film on top of the MoS 2 flake so that electron charges might be transferred from MoS 2 to IGZO during air ambient annealing. As a result, electron charges were depleted in MoS 2 . Such charge depletion lowered the MoS 2 Fermi level, which makes hole conduction favorable in MoS 2 when optimum source/drain electrodes with a high work function are selected. Our IGZO-supported MoS 2 flake field effect transistors (FETs) clearly display channel-type conversion from n- to p-channel in this way. Under short- and long-annealing conditions, n- and p-channel MoS 2 FETs are achieved, respectively, and a low-voltage complementary inverter is demonstrated using both channels in a single MoS 2 flake.

  6. Time-dependent density functional theory for the charging kinetics of electric double layer containing room-temperature ionic liquids

    DOE PAGES

    Lian, Cheng; Univ. of California, Riverside, CA; Zhao, Shuangliang; ...

    2016-11-29

    Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this paper, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the durationmore » of charging. Finally and furthermore, we investigate the effects of van der Waals attraction between electrode/ionic-liquid interactions on the charging processes.« less

  7. Diffuse charge and Faradaic reactions in porous electrodes

    NASA Astrophysics Data System (ADS)

    Biesheuvel, P. M.; Fu, Yeqing; Bazant, Martin Z.

    2011-06-01

    Porous electrodes instead of flat electrodes are widely used in electrochemical systems to boost storage capacities for ions and electrons, to improve the transport of mass and charge, and to enhance reaction rates. Existing porous electrode theories make a number of simplifying assumptions: (i) The charge-transfer rate is assumed to depend only on the local electrostatic potential difference between the electrode matrix and the pore solution, without considering the structure of the double layer (DL) formed in between; (ii) the charge-transfer rate is generally equated with the salt-transfer rate not only at the nanoscale of the matrix-pore interface, but also at the macroscopic scale of transport through the electrode pores. In this paper, we extend porous electrode theory by including the generalized Frumkin-Butler-Volmer model of Faradaic reaction kinetics, which postulates charge transfer across the molecular Stern layer located in between the electron-conducting matrix phase and the plane of closest approach for the ions in the diffuse part of the DL. This is an elegant and purely local description of the charge-transfer rate, which self-consistently determines the surface charge and does not require consideration of reference electrodes or comparison with a global equilibrium. For the description of the DLs, we consider the two natural limits: (i) the classical Gouy-Chapman-Stern model for thin DLs compared to the macroscopic pore dimensions, e.g., for high-porosity metallic foams (macropores >50 nm) and (ii) a modified Donnan model for strongly overlapping DLs, e.g., for porous activated carbon particles (micropores <2 nm). Our theory is valid for electrolytes where both ions are mobile, and it accounts for voltage and concentration differences not only on the macroscopic scale of the full electrode, but also on the local scale of the DL. The model is simple enough to allow us to derive analytical approximations for the steady-state and early transients. We

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

    NASA Astrophysics Data System (ADS)

    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

  9. Photoelectrodes based on 2D opals assembled from Cu-delafossite double-shelled microspheres for an enhanced photoelectrochemical response.

    PubMed

    Oh, Yunjung; Yang, Wooseok; Tan, Jeiwan; Lee, Hyungsoo; Park, Jaemin; Moon, Jooho

    2018-02-22

    Although a unique light-harvesting property was recently demonstrated in a photocathode based on 2-dimensional (2D) opals of CuFeO 2 -shelled SiO 2 microspheres, the performance of a monolayer of ultra-thin CuFeO 2 -shelled microspheres is limited by ineffective charge separation. Herein, we propose an innovative design rule, in which an inner CuFeO 2 /outer CuAlO 2 double-shelled heterojunction is formed on each partially etched microsphere to obtain a hexagonally assembled 2D opal photoelectrode. Our Cu-delafossite double-shelled photocathode shows a dramatically improved charge separation capability, with a 9-fold increase in the photocurrent compared to that of the single-shelled counterpart. Electrochemical impedance spectroscopy clearly confirms the reduced charge transport/transfer resistance associated with the Cu-delafossite double-shelled photocathode, while surface photovoltage spectra reveal enhanced polarization of the photogenerated carrier, indicating improved charge separation capability with the aid of the heterojunction. Our finding sheds light on the importance of heterojunction interfaces in achieving optimal charge separation in opal architectures as well as the inner-shell/electrolyte interface to expedite charge separation/transport.

  10. First measurement of the muon neutrino charged current quasielastic double differential cross section

    NASA Astrophysics Data System (ADS)

    Aguilar-Arevalo, A. A.; Anderson, C. E.; Bazarko, A. O.; Brice, S. J.; Brown, B. C.; Bugel, L.; Cao, J.; Coney, L.; Conrad, J. M.; Cox, D. C.; Curioni, A.; Djurcic, Z.; Finley, D. A.; Fleming, B. T.; Ford, R.; Garcia, F. G.; Garvey, G. T.; Grange, J.; Green, C.; Green, J. A.; Hart, T. L.; Hawker, E.; Imlay, R.; Johnson, R. A.; Karagiorgi, G.; Kasper, P.; Katori, T.; Kobilarcik, T.; Kourbanis, I.; Koutsoliotas, S.; Laird, E. M.; Linden, S. K.; Link, J. M.; Liu, Y.; Liu, Y.; Louis, W. C.; Mahn, K. B. M.; Marsh, W.; Mauger, C.; McGary, V. T.; McGregor, G.; Metcalf, W.; Meyers, P. D.; Mills, F.; Mills, G. B.; Monroe, J.; Moore, C. D.; Mousseau, J.; Nelson, R. H.; Nienaber, P.; Nowak, J. A.; Osmanov, B.; Ouedraogo, S.; Patterson, R. B.; Pavlovic, Z.; Perevalov, D.; Polly, C. C.; Prebys, E.; Raaf, J. L.; Ray, H.; Roe, B. P.; Russell, A. D.; Sandberg, V.; Schirato, R.; Schmitz, D.; Shaevitz, M. H.; Shoemaker, F. C.; Smith, D.; Soderberg, M.; Sorel, M.; Spentzouris, P.; Spitz, J.; Stancu, I.; Stefanski, R. J.; Sung, M.; Tanaka, H. A.; Tayloe, R.; Tzanov, M.; van de Water, R. G.; Wascko, M. O.; White, D. H.; Wilking, M. J.; Yang, H. J.; Zeller, G. P.; Zimmerman, E. D.; MiniBooNE Collaboration

    2010-05-01

    A high-statistics sample of charged-current muon neutrino scattering events collected with the MiniBooNE experiment is analyzed to extract the first measurement of the double differential cross section ((d2σ)/(dTμdcos⁡θμ)) for charged-current quasielastic (CCQE) scattering on carbon. This result features minimal model dependence and provides the most complete information on this process to date. With the assumption of CCQE scattering, the absolute cross section as a function of neutrino energy (σ[Eν]) and the single differential cross section ((dσ)/(dQ2)) are extracted to facilitate comparison with previous measurements. These quantities may be used to characterize an effective axial-vector form factor of the nucleon and to improve the modeling of low-energy neutrino interactions on nuclear targets. The results are relevant for experiments searching for neutrino oscillations.

  11. Spectroscopy of Photovoltaic Materials: Charge-Transfer Complexes and Titanium Dioxide

    NASA Astrophysics Data System (ADS)

    Dillon, Robert John

    The successful function of photovoltaic (PV) and photocatalytic (PC) systems centers primarily on the creation and photophysics of charge separated electron-hole pairs. The pathway leading to separate carriers varies by material; organic materials typically require multiple events to charge separate, whereas inorganic semiconductors can directly produce free carriers. In this study, time-resolved spectroscopy is used to provide insight into two such systems: 1) organic charge-transfer (CT) complexes, where electrons and holes are tightly bound to each other, and 2) Au-TiO2 core-shell nanostructures, where free carriers are directly generated. 1) CT complexes are structurally well defined systems consisting of donor molecules, characterized by having low ionization potentials, and acceptor molecules, characterized by having high electron affinities. Charge-transfer is the excitation of an electron from the HOMO of a donor material directly into the LUMO of the acceptor material, leading to an electron and hole separated across the donor:acceptor interface. The energy of the CT transition is often less than that of the bandgaps of donor and acceptor materials individually, sparking much interest if PV systems can utilize the CT band to generate free carriers from low energy photons. In this work we examine the complexes formed between acceptors tetracyanobenzene (TCNB) and tetracyanoquinodimethane (TCNQ) with several aromatic donors. We find excitation of the charge-transfer band of these systems leads to strongly bound electron-hole pairs that exclusively undergo recombination to the ground state. In the case of the TCNB complexes, our initial studies were flummoxed by the samples' generally low threshold for photo and mechanical damage. As our results conflicted with previous literature, a significant portion of this study was spent quantifying the photodegradation process. 2) Unlike the previous system, free carriers are directly photogenerated in TiO2, and the

  12. Detecting RNA/DNA hybridization using double-labeled donor probes with enhanced fluorescence resonance energy transfer signals.

    PubMed

    Okamura, Yukio; Watanabe, Yuichiro

    2006-01-01

    Fluorescence resonance energy transfer (FRET) occurs when two fluorophores are in close proximity, and the emission energy of a donor fluorophore is transferred to excite an acceptor fluorophore. Using such fluorescently labeled oligonucleotides as FRET probes, makes possible specific detection of RNA molecules even if similar sequences are present in the environment. A higher ratio of signal to background fluorescence is required for more sensitive probe detection. We found that double-labeled donor probes labeled with BODIPY dye resulted in a remarkable increase in fluorescence intensity compared to single-labeled donor probes used in conventional FRET. Application of this double-labeled donor system can improve a variety of FRET techniques.

  13. Charge Versus Energy Transfer in Atomically Thin Graphene-Transition Metal Dichalcogenide van der Waals Heterostructures

    NASA Astrophysics Data System (ADS)

    Froehlicher, Guillaume; Lorchat, Etienne; Berciaud, Stéphane

    2018-01-01

    Made from stacks of two-dimensional materials, van der Waals heterostructures exhibit unique light-matter interactions and are promising for novel optoelectronic devices. The performance of such devices is governed by near-field coupling through, e.g., interlayer charge and/or energy transfer. New concepts and experimental methodologies are needed to properly describe two-dimensional heterointerfaces. Here, we report an original study of interlayer charge and energy transfer in atomically thin metal-semiconductor [i.e., graphene-transition metal dichalcogenide (TMD, here molybdenum diselenide, MoSe2 )] heterostructures using a combination of microphotoluminescence and Raman scattering spectroscopies. The photoluminescence intensity in graphene /MoSe2 is quenched by more than 2 orders of magnitude and rises linearly with the incident photon flux, demonstrating a drastically shortened (about 1 ps) room-temperature MoSe2 exciton lifetime. Key complementary insights are provided from a comprehensive analysis of the graphene and MoSe2 Raman modes, which reveals net photoinduced electron transfer from MoSe2 to graphene and hole accumulation in MoSe2 . Remarkably, the steady-state Fermi energy of graphene saturates at 290 ±15 meV above the Dirac point. This reproducible behavior is observed both in ambient air and in vacuum and is discussed in terms of intrinsic factors (i.e., band offsets) and environmental effects. In this saturation regime, balanced photoinduced flows of electrons and holes may transfer to graphene, a mechanism that effectively leads to energy transfer. Using a broad range of incident photon fluxes and diverse environmental conditions, we find that the presence of net photoinduced charge transfer has no measurable impact on the near-unity photoluminescence quenching efficiency in graphene /MoSe2 . This absence of correlation strongly suggests that energy transfer to graphene (either in the form of electron exchange or dipole-dipole interaction) is the

  14. A Double Decarboxylation in Superfolder Green Fluorescent Protein Leads to High Contrast Photoactivation.

    PubMed

    Slocum, Joshua D; Webb, Lauren J

    2017-07-06

    A photoactivatable variant of superfolder green fluorescent protein (GFP) was created by replacing the threonine at position 203 with aspartic acid. Photoactivation by exposure of this mutant to UV light resulted in conversion of the fluorophore from the neutral to the negatively charged form, accompanied by a ∼95-fold increase in fluorescence under 488 nm excitation. Mass spectrometry before and after exposure to UV light revealed a change in mass of 88 Da, attributed to the double decarboxylation of Glu 222 and Asp 203. Kinetics studies and nonlinear power-dependence of the initial rate of photoconversion indicated that the double decarboxylation occurred via a multiphoton absorption process at 254 nm. In addition to providing a photoactivatable GFP with robust folding properties, a detailed mechanistic understanding of this double decarboxylation in GFP will lead to a better understanding of charge transfer in fluorescent proteins.

  15. Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Hollstein, Maximilian; Santra, Robin; Pfannkuche, Daniela

    2017-05-01

    We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999), 10.1016/S0009-2614(99)00508-4], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

  16. Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes

    NASA Astrophysics Data System (ADS)

    Longuinhos, R.; Lúcio, A. D.; Chacham, H.; Alexandre, S. S.

    2016-05-01

    Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag4. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag4 or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag4 to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag4 hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

  17. Structure and Dynamics of Solvent Landscapes in Charge-Transfer Reactions

    NASA Astrophysics Data System (ADS)

    Leite, Vitor B. Pereira

    The dynamics of solvent polarization plays a major role in the control of charge transfer reactions. The success of Marcus theory describing the solvent influence via a single collective quadratic polarization coordinate has been remarkable. Onuchic and Wolynes have recently proposed (J. Chem Phys 98 (3) 2218, 1993) a simple model demonstrating how a many-dimensional-complex model composed by several dipole moments (representing solvent molecules or polar groups in proteins) can be reduced under the appropriate limits into the Marcus Model. This work presents a dynamical study of the same model, which is characterized by two parameters, an average dipole-dipole interaction as a term associated with the potential energy landscape roughness. It is shown why the effective potential, obtained using a thermodynamic approach, is appropriate for the dynamics of the system. At high temperatures, the system exhibits effective diffusive one-dimensional dynamics, where the Born-Marcus limit is recovered. At low temperatures, a glassy phase appears with a slow non-self-averaging dynamics. At intermediate temperatures, the concept of equivalent diffusion paths and polarization dependence effects are discussed. This approach is extended to treat more realistic solvent models. Real solvents are discussed in terms of simple parameters described above, and an analysis of how different regimes affect the rate of charge transfer is presented. Finally, these ideas are correlated to analogous problems in other areas.

  18. Charge-transfer optical absorption mechanism of DNA:Ag-nanocluster complexes.

    PubMed

    Longuinhos, R; Lúcio, A D; Chacham, H; Alexandre, S S

    2016-05-01

    Optical properties of DNA:Ag-nanoclusters complexes have been successfully applied experimentally in Chemistry, Physics, and Biology. Nevertheless, the mechanisms behind their optical activity remain unresolved. In this work, we present a time-dependent density functional study of optical absorption in DNA:Ag_{4}. In all 23 different complexes investigated, we obtain new absorption peaks in the visible region that are not found in either the isolated Ag_{4} or isolated DNA base pairs. Absorption from red to green are predominantly of charge-transfer character, from the Ag_{4} to the DNA fragment, while absorption in the blue-violet range are mostly associated to electronic transitions of a mixed character, involving either DNA-Ag_{4} hybrid orbitals or intracluster orbitals. We also investigate the role of exchange-correlation functionals in the calculated optical spectra. Significant differences are observed between the calculations using the PBE functional (without exact exchange) and the CAM-B3LYP functional (which partly includes exact exchange). Specifically, we observe a tendency of charge-transfer excitations to involve purines bases, and the PBE spectra error is more pronounced in the complexes where the Ag cluster is bound to the purines. Finally, our results also highlight the importance of adding both the complementary base pair and the sugar-phosphate backbone in order to properly characterize the absorption spectrum of DNA:Ag complexes.

  19. Synthesis and electrochemical studies of charge-transfer complexes of thiazolidine-2,4-dione with σ and π acceptors

    NASA Astrophysics Data System (ADS)

    Singh, Prashant; Kumar, Pradeep; Katyal, Anju; Kalra, Rashmi; Dass, Sujata K.; Prakash, Satya; Chandra, Ramesh

    2010-03-01

    In the present work, we report the synthesis and characterization of novel charge-transfer complexes of thiazolidine-2,4-dione (TZD) with sigma acceptor (iodine) and pi acceptors (chloranil, dichlorodicyanoquinone, picric acid and duraquinone). We also evaluated their thermal and electrochemical properties and we conclude that these complexes are frequency dependent. Charge-transfer complex between thiazolidine-2,4-dione and iodine give best conductivity. In conclusion, complex with sigma acceptors are more conducting than with pi acceptors.

  20. Molecular layers of ZnPc and FePc on Au(111) surface: Charge transfer and chemical interaction

    NASA Astrophysics Data System (ADS)

    Ahmadi, Sareh; Shariati, M. Nina; Yu, Shun; Göthelid, Mats

    2012-08-01

    We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.

  1. Tunneling dynamics of double proton transfer in formic acid and benzoic acid dimers

    NASA Astrophysics Data System (ADS)

    Smedarchina, Zorka; Fernández-Ramos, Antonio; Siebrand, Willem

    2005-04-01

    Direct dynamics calculations based on instanton techniques are reported of tunneling splittings due to double proton transfer in formic and benzoic acid dimers. The results are used to assign the observed splittings to levels for which the authors of the high-resolution spectra could not provide a definitive assignment. In both cases the splitting is shown to be due mainly to the zero-point level rather than to the vibrationally or electronically excited level whose spectrum was investigated. This leads to zero-point splittings of 375MHz for (DCOOH)2 and 1107MHz for the benzoic acid dimer. Thus, contrary to earlier calculations, it is found that the splitting is considerably larger in the benzoic than in the formic acid dimer. The calculations are extended to solid benzoic acid where the asymmetry of the proton-transfer potential induced by the crystal can be overcome by suitable doping. This has allowed direct measurement of the interactions responsible for double proton transfer, which were found to be much larger than those in the isolated dimer. To account for this observation both static and dynamic effects of the crystal forces on the intradimer hydrogen bonds are included in the calculations. The same methodology, extended to higher temperatures, is used to calculate rate constants for HH, HD, and DD transfers in neat benzoic acid crystals. The results are in good agreement with reported experimental rate constants measured by NMR relaxometry and, if allowance is made for small structural changes induced by doping, with the transfer matrix elements observed in doped crystals. Hence the method used allows a unified description of tunneling splittings in the gas phase and in doped crystals as well as of transfer rates in neat crystals.

  2. R1 in the Shaker S4 occupies the gating charge transfer center in the resting state

    PubMed Central

    Lin, Meng-chin A.; Hsieh, Jui-Yi; Mock, Allan F.

    2011-01-01

    During voltage-dependent activation in Shaker channels, four arginine residues in the S4 segment (R1–R4) cross the transmembrane electric field. It has been proposed that R1–R4 movement is facilitated by a “gating charge transfer center” comprising a phenylalanine (F290) in S2 plus two acidic residues, one each in S2 and S3. According to this proposal, R1 occupies the charge transfer center in the resting state, defined as the conformation in which S4 is maximally retracted toward the cytoplasm. However, other evidence suggests that R1 is located extracellular to the charge transfer center, near I287 in S2, in the resting state. To investigate the resting position of R1, we mutated I287 to histidine (I287H), paired it with histidine mutations of key voltage sensor residues, and determined the effect of extracellular Zn2+ on channel activity. In I287H+R1H, Zn2+ generated a slow component of activation with a maximum amplitude (Aslow,max) of ∼56%, indicating that only a fraction of voltage sensors can bind Zn2+ at a holding potential of −80 mV. Aslow,max decreased after applying either depolarizing or hyperpolarizing prepulses from −80 mV. The decline of Aslow,max after negative prepulses indicates that R1 moves inward to abolish ion binding, going beyond the point where reorientation of the I287H and R1H side chains would reestablish a binding site. These data support the proposal that R1 occupies the charge transfer center upon hyperpolarization. Consistent with this, pairing I287H with A359H in the S3–S4 loop generated a Zn2+-binding site. At saturating concentrations, Aslow,max reached 100%, indicating that Zn2+ traps the I287H+A359H voltage sensor in an absorbing conformation. Transferring I287H+A359H into a mutant background that stabilizes the resting state significantly enhanced Zn2+ binding at −80 mV. Our results strongly support the conclusion that R1 occupies the gating charge transfer center in the resting conformation. PMID:21788609

  3. Non-Linearity in Wide Dynamic Range CMOS Image Sensors Utilizing a Partial Charge Transfer Technique.

    PubMed

    Shafie, Suhaidi; Kawahito, Shoji; Halin, Izhal Abdul; Hasan, Wan Zuha Wan

    2009-01-01

    The partial charge transfer technique can expand the dynamic range of a CMOS image sensor by synthesizing two types of signal, namely the long and short accumulation time signals. However the short accumulation time signal obtained from partial transfer operation suffers of non-linearity with respect to the incident light. In this paper, an analysis of the non-linearity in partial charge transfer technique has been carried, and the relationship between dynamic range and the non-linearity is studied. The results show that the non-linearity is caused by two factors, namely the current diffusion, which has an exponential relation with the potential barrier, and the initial condition of photodiodes in which it shows that the error in the high illumination region increases as the ratio of the long to the short accumulation time raises. Moreover, the increment of the saturation level of photodiodes also increases the error in the high illumination region.

  4. Charge-transfer dynamics in one-dimensional C 60 chains

    NASA Astrophysics Data System (ADS)

    Pérez-Dieste, V.; Tamai, A.; Greber, T.; Chiuzbaˇian, S. G.; Patthey, L.

    2008-06-01

    Charge transfer in highly-ordered C 60 chains grown on a Cu(5 5 3) vicinal surface is studied by means of resonant photoemission. Tuning the light polarization, autoionization of the highest occupied molecular orbital (HOMO) was expected to detect anisotropy in this one-dimensional system. For one monolayer C 60 we found no signature of autoionization. This indicates that for an electron which is excited from the C 1s level of C 60 to the lowest unoccupied molecular orbital (LUMO), hybridization leads to delocalization on the femtosecond time-scale and no influence of the light polarization is observed.

  5. Scale-model charge-transfer technique for measuring enhancement factors

    NASA Technical Reports Server (NTRS)

    Kositsky, J.; Nanevicz, J. E.

    1991-01-01

    Determination of aircraft electric field enhancement factors is crucial when using airborne field mill (ABFM) systems to accurately measure electric fields aloft. SRI used the scale model charge transfer technique to determine enhancement factors of several canonical shapes and a scale model Learjet 36A. The measured values for the canonical shapes agreed with known analytic solutions within about 6 percent. The laboratory determined enhancement factors for the aircraft were compared with those derived from in-flight data gathered by a Learjet 36A outfitted with eight field mills. The values agreed to within experimental error (approx. 15 percent).

  6. Energy and charge transfer dynamics between Alq3 and CdSeS nanocrystals.

    PubMed

    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.

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

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

    Pan, Shanlin

    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 thatmore » 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

  8. Dependence of charge transfer phenomena during solid-air two-phase flow on particle disperser

    NASA Astrophysics Data System (ADS)

    Tanoue, Ken-ichiro; Suedomi, Yuuki; Honda, Hirotaka; Furutani, Satoshi; Nishimura, Tatsuo; Masuda, Hiroaki

    2012-12-01

    An experimental investigation of the tribo-electrification of particles has been conducted during solid-air two-phase turbulent flow. The current induced in a metal plate by the impact of polymethylmethacrylate (PMMA) particles in a high-speed air flow was measured for two different plate materials. The results indicated that the contact potential difference between the particles and a stainless steel plate was positive, while for a nickel plate it was negative. These results agreed with theoretical contact charge transfer even if not only the particle size but also the kind of metal plate was changed. The specific charge of the PMMA particles during solid-air two-phase flow using an ejector, a stainless steel branch pipe, and a stainless steel straight pipe was measured using a Faraday cage. Although the charge was negative in the ejector, the particles had a positive specific charge at the outlet of the branch pipe, and this positive charge increased in the straight pipe. The charge decay along the flow direction could be reproduced by the charging and relaxation theory. However, the proportional coefficients in the theory changed with the particle size and air velocity. Therefore, an unexpected charge transfer occurred between the ejector and the branch pipe, which could not be explained solely by the contact potential difference. In the ejector, an electrical current in air might have been produced by self-discharge of particles with excess charge between the nickel diffuser in the ejector and the stainless steel nozzle or the stainless steel pipe due to a reversal in the contact potential difference between the PMMA and the stainless steel. The sign of the current depended on the particle size, possibly because the position where the particles impacted depended on their size. When dual coaxial glass pipes were used as a particle disperser, the specific charge of the PMMA particles became more positive along the particle flow direction due to the contact

  9. Transfer functions of double- and multiple-cavity Fabry-Perot filters driven by Lorentzian sources.

    PubMed

    Marti, J; Capmany, J

    1996-12-20

    We derive expressions for the transfer functions of double- and multiple-cavity Fabry-Perot filters driven by laser sources with Lorentzian spectrum. These are of interest because of their applications in sensing and channel filtering in optical frequency-division multiplexing networks.

  10. Transfer functions of double- and multiple-cavity Fabry Perot filters driven by Lorentzian sources

    NASA Astrophysics Data System (ADS)

    Marti, Javier; Capmany, Jose

    1996-12-01

    We derive expressions for the transfer functions of double- and multiple-cavity Fabry Perot filters driven by laser sources with Lorentzian spectrum. These are of interest because of their applications in sensing and channel filtering in optical frequency-division multiplexing networks.

  11. Transition-density-fragment interaction combined with transfer integral approach for excitation-energy transfer via charge-transfer states

    NASA Astrophysics Data System (ADS)

    Fujimoto, Kazuhiro J.

    2012-07-01

    A transition-density-fragment interaction (TDFI) combined with a transfer integral (TI) method is proposed. The TDFI method was previously developed for describing electronic Coulomb interaction, which was applied to excitation-energy transfer (EET) [K. J. Fujimoto and S. Hayashi, J. Am. Chem. Soc. 131, 14152 (2009)] and exciton-coupled circular dichroism spectra [K. J. Fujimoto, J. Chem. Phys. 133, 124101 (2010)]. In the present study, the TDFI method is extended to the exchange interaction, and hence it is combined with the TI method for applying to the EET via charge-transfer (CT) states. In this scheme, the overlap correction is also taken into account. To check the TDFI-TI accuracy, several test calculations are performed to an ethylene dimer. As a result, the TDFI-TI method gives a much improved description of the electronic coupling, compared with the previous TDFI method. Based on the successful description of the electronic coupling, the decomposition analysis is also performed with the TDFI-TI method. The present analysis clearly shows a large contribution from the Coulomb interaction in most of the cases, and a significant influence of the CT states at the small separation. In addition, the exchange interaction is found to be small in this system. The present approach is useful for analyzing and understanding the mechanism of EET.

  12. Double proton transfer in the complex of acetic acid with methanol: Theory versus experiment

    NASA Astrophysics Data System (ADS)

    Fernández-Ramos, Antonio; Smedarchina, Zorka; Rodríguez-Otero, Jesús

    2001-01-01

    To test the approximate instanton approach to intermolecular proton-transfer dynamics, we report multidimensional ab initio bimolecular rate constants of HH, HD, and DD exchange in the complex of acetic acid with methanol in tetrahydrofuran-d8, and compare them with the NMR (nuclear magnetic resonance) experiments of Gerritzen and Limbach. The bimolecular rate constants are evaluated as products of the exchange rates and the equilibrium rate constants of complex formation in solution. The two molecules form hydrogen-bond bridges and the exchange occurs via concerted transfer of two protons. The dynamics of this transfer is evaluated in the complete space of 36 vibrational degrees of freedom. The geometries of the two isolated molecules, the complex, and the transition states corresponding to double proton transfer are fully optimized at QCISD (quadratic configuration interaction including single and double substitutions) level of theory, and the normal-mode frequencies are calculated at MP2 (Møller-Plesset perturbation theory of second order) level with the 6-31G (d,p) basis set. The presence of the solvent is taken into account via single-point calculations over the gas phase geometries with the PCM (polarized continuum model). The proton exchange rate constants, calculated with the instanton method, show the effect of the structure and strength of the hydrogen bonds, reflected in the coupling between the tunneling motion and the other vibrations of the complex. Comparison with experiment, which shows substantial kinetic isotopic effects (KIE), indicates that tunneling prevails over classic exchange for the whole temperature range of observation. The unusual behavior of the experimental KIE upon single and double deuterium substitution is well reproduced and is related to the synchronicity of two-atom tunneling.

  13. Primary-Side Power Flow Control of Wireless Power Transfer for Electric Vehicle Charging

    DOE PAGES

    Miller, John M.; Onar, Omer C.; Chinthavali, Madhu

    2014-12-22

    Various noncontacting methods of plug-in electric vehicle charging are either under development or now deployed as aftermarket options in the light-duty automotive market. Wireless power transfer (WPT) is now the accepted term for wireless charging and is used synonymously for inductive power transfer and magnetic resonance coupling. WPT technology is in its infancy; standardization is lacking, especially on interoperability, center frequency selection, magnetic fringe field suppression, and the methods employed for power flow regulation. This paper proposes a new analysis concept for power flow in WPT in which the primary provides frequency selection and the tuned secondary, with its resemblancemore » to a power transmission network having a reactive power voltage control, is analyzed as a transmission network. Analysis is supported with experimental data taken from Oak Ridge National Laboratory s WPT apparatus. Lastly, this paper also provides an experimental evidence for frequency selection, fringe field assessment, and the need for low-latency communications in the feedback path.« less

  14. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions

    NASA Astrophysics Data System (ADS)

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G.; Qiao, Rui

    2014-07-01

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

  15. Dynamics of electrical double layer formation in room-temperature ionic liquids under constant-current charging conditions.

    PubMed

    Jiang, Xikai; Huang, Jingsong; Zhao, Hui; Sumpter, Bobby G; Qiao, Rui

    2014-07-16

    We report detailed simulation results on the formation dynamics of an electrical double layer (EDL) inside an electrochemical cell featuring room-temperature ionic liquids (RTILs) enclosed between two planar electrodes. Under relatively small charging currents, the evolution of cell potential from molecular dynamics (MD) simulations during charging can be suitably predicted by the Landau-Ginzburg-type continuum model proposed recently (Bazant et al 2011 Phys. Rev. Lett. 106 046102). Under very large charging currents, the cell potential from MD simulations shows pronounced oscillation during the initial stage of charging, a feature not captured by the continuum model. Such oscillation originates from the sequential growth of the ionic space charge layers near the electrode surface. This allows the evolution of EDLs in RTILs with time, an atomistic process difficult to visualize experimentally, to be studied by analyzing the cell potential under constant-current charging conditions. While the continuum model cannot predict the potential oscillation under such far-from-equilibrium charging conditions, it can nevertheless qualitatively capture the growth of cell potential during the later stage of charging. Improving the continuum model by introducing frequency-dependent dielectric constant and density-dependent ion diffusion coefficients may help to further extend the applicability of the model. The evolution of ion density profiles is also compared between the MD and the continuum model, showing good agreement.

  16. Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

    NASA Astrophysics Data System (ADS)

    Phillips, Patrick J.; Rui, Xue; Georgescu, Alexandru B.; Disa, Ankit S.; Longo, Paolo; Okunishi, Eiji; Walker, Fred; Ahn, Charles H.; Ismail-Beigi, Sohrab; Klie, Robert F.

    2017-05-01

    Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate R E NiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2 +/Ni3 + valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.

  17. Spin Transfer Torque in Graphene

    NASA Astrophysics Data System (ADS)

    Lin, Chia-Ching; Chen, Zhihong

    2014-03-01

    Graphene is an idea channel material for spin transport due to its long spin diffusion length. To develop graphene based spin logic, it is important to demonstrate spin transfer torque in graphene. Here, we report the experimental measurement of spin transfer torque in graphene nonlocal spin valve devices. Assisted by a small external in-plane magnetic field, the magnetization reversal of the receiving magnet is induced by pure spin diffusion currents from the injector magnet. The magnetization switching is reversible between parallel and antiparallel configurations by controlling the polarity of the applied charged currents. Current induced heating and Oersted field from the nonlocal charge flow have also been excluded in this study. Next, we further enhance the spin angular momentum absorption at the interface of the receiving magnet and graphene channel by removing the tunneling barrier in the receiving magnet. The device with a tunneling barrier only at the injector magnet shows a comparable nonlocal spin valve signal but lower electrical noise. Moreover, in the same preset condition, the critical charge current density for spin torque in the single tunneling barrier device shows a substantial reduction if compared to the double tunneling barrier device.

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

    NASA Astrophysics Data System (ADS)

    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.

  19. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

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

    Rury, Aaron S., E-mail: arury@usc.edu; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-14

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone,more » we find sub-cm{sup −1} oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.« less

  20. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    NASA Astrophysics Data System (ADS)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  1. Dendronized fullerene-porphyrin conjugates in ortho, meta, and para positions: a charge-transfer assay.

    PubMed

    Krokos, Evangelos; Schubert, Christina; Spänig, Fabian; Ruppert, Michaela; Hirsch, Andreas; Guldi, Dirk M

    2012-06-01

    The physicochemical characterization, that is, ground and excited state, of a new series of dendronized porphyrin/fullerene electron donor-acceptor conjugates in nonaqueous and aqueous environments is reported. In contrast to previous work, we detail the charge-separation and charge-recombination dynamics in zinc and copper metalloporphyrins as a function of first- and second-generation dendrons as well as a function of ortho, meta, and para substitution. Both have an appreciable impact on the microenvironments of the redox-active constituents, namely the porphyrins and the fullerenes. As a matter of fact, the resulting charge-transfer dynamics were considerably impacted by the interplay between the associated forces that reach from dendron-induced shielding to dipole-charge interactions. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Neutrino nuclear responses for double beta decays and astro neutrinos by charge exchange reactions

    NASA Astrophysics Data System (ADS)

    Ejiri, Hiroyasu

    2014-09-01

    Neutrino nuclear responses are crucial for neutrino studies in nuclei. Charge exchange reactions (CER) are shown to be used to study charged current neutrino nuclear responses associated with double beta decays(DBD)and astro neutrino interactions. CERs to be used are high energy-resolution (He3 ,t) reactions at RCNP, photonuclear reactions via IAR at NewSUBARU and muon capture reactions at MUSIC RCNP and MLF J-PARC. The Gamow Teller (GT) strengths studied by CERs reproduce the observed 2 neutrino DBD matrix elements. The GT and spin dipole (SD) matrix elements are found to be reduced much due to the nucleon spin isospin correlations and the non-nucleonic (delta isobar) nuclear medium effects. Impacts of the reductions on the DBD matrix elements and astro neutrino interactions are discussed.

  3. Theoretical insights of proton transfer and hydrogen bonded charge transfer complex of 1,2-dimethylimidazolium-3,5-dinitrobenzoate crystal

    NASA Astrophysics Data System (ADS)

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

    2018-04-01

    Proton transfer (PT) and hydrogen bonded charge transfer (HBCT) 1:1 complex of 1,2-dimethylimidazole (DMI) and 3,5-dinitrobenzoic acid (DNBA) have been theoretically analyzed and compared with reported experimental results. Both the structures in the isolated gaseous state have been optimized at DFT/B3LYP/6-311G(d,p) level of theory and further, the PT energy barrier has been calculated from potential energy surface scan. Along with structural investigations, theoretical vibrational spectra have been inspected and compared with the FTIR spectrum. Moreover, frontier molecular analysis has also been carried out.

  4. Experimental challenges for the measurement of the 116Cd(20Ne,20O)116Sn double charge exchange reaction at 15 AMeV

    NASA Astrophysics Data System (ADS)

    Carbone, D.; Cappuzzello, F.; Agodi, C.; Cavallaro, M.; Acosta, L.; Bonanno, D.; Bongiovanni, D.; Borello, T.; Boztosun, I.; Calabrese, S.; Calvo, D.; Chávez Lomelí, E. R.; Deshmukh, N.; de Faria, P. N.; Finocchiaro, P.; Fisichella, M.; Foti, A.; Gallo, G.; Hacisalihoglu, A.; Iazzi, F.; Introzzi, R.; Lanzalone, G.; Linares, R.; Longhitano, F.; Lo Presti, D.; Medina, N.; Muoio, A.; Oliveira, J. R. B.; Pakou, A.; Pandola, L.; Pinna, F.; Reito, S.; Russo, G.; Santagati, G.; Sgouros, O.; Solakcı, S. O.; Soukeras, V.; Souliotis, G.; Spatafora, A.; Torresi, D.; Tudisco, S.; Yildirim, A.; Zagatto, V. A. B.;

    2018-05-01

    The knowledge of the nuclear matrix elements (NME) entering in the expression of the half-life of the neutrinoless double beta decay is fundamental for neutrino physics. Information on the nuclear matrix elements can be obtained by measuring the absolute cross section of double charge exchange nuclear reactions. The two processes present some similarities, the initial and final-state wave functions are the same and the transition operators are similar. The experimental measurements of double charge exchange reactions induced by heavy ions present a number of challenging aspects, since such reactions are characterized by very low cross sections. Such difficulties are discussed for the measurement of the 116Cd(20Ne,20O)116Sn reaction at 15 AMeV.

  5. Gate tunable parallel double quantum dots in InAs double-nanowire devices

    NASA Astrophysics Data System (ADS)

    Baba, S.; Matsuo, S.; Kamata, H.; Deacon, R. S.; Oiwa, A.; Li, K.; Jeppesen, S.; Samuelson, L.; Xu, H. Q.; Tarucha, S.

    2017-12-01

    We report fabrication and characterization of InAs nanowire devices with two closely placed parallel nanowires. The fabrication process we develop includes selective deposition of the nanowires with micron scale alignment onto predefined finger bottom gates using a polymer transfer technique. By tuning the double nanowire with the finger bottom gates, we observed the formation of parallel double quantum dots with one quantum dot in each nanowire bound by the normal metal contact edges. We report the gate tunability of the charge states in individual dots as well as the inter-dot electrostatic coupling. In addition, we fabricate a device with separate normal metal contacts and a common superconducting contact to the two parallel wires and confirm the dot formation in each wire from comparison of the transport properties and a superconducting proximity gap feature for the respective wires. With the fabrication techniques established in this study, devices can be realized for more advanced experiments on Cooper-pair splitting, generation of Parafermions, and so on.

  6. Electron-lattice interactions strongly renormalize the charge-transfer energy in the spin-chain cuprate Li 2CuO 2

    DOE PAGES

    Johnston, Steve; Monney, Claude; Bisogni, Valentina; ...

    2016-02-17

    Strongly correlated insulators are broadly divided into two classes: Mott–Hubbard insulators, where the insulating gap is driven by the Coulomb repulsion U on the transition-metal cation, and charge-transfer insulators, where the gap is driven by the charge-transfer energy Δ between the cation and the ligand anions. The relative magnitudes of U and Δ determine which class a material belongs to, and subsequently the nature of its low-energy excitations. These energy scales are typically understood through the local chemistry of the active ions. Here we show that the situation is more complex in the low-dimensional charge-transfer insulator Li 2CuO 2, wheremore » Δ has a large non-electronic component. Combining resonant inelastic X-ray scattering with detailed modelling, we determine how the elementary lattice, charge, spin and orbital excitations are entangled in this material. This results in a large lattice-driven renormalization of Δ, which significantly reshapes the fundamental electronic properties of Li 2CuO 2.« less

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

    NASA Astrophysics Data System (ADS)

    Mizokawa, Takashi

    2013-04-01

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

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

    PubMed

    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.

  9. Container lid gasket protective strip for double door transfer system

    DOEpatents

    Allen, Jr., Burgess M

    2013-02-19

    An apparatus and a process for forming a protective barrier seal along a "ring of concern" of a transfer container used with double door systems is provided. A protective substrate is supplied between a "ring of concern" and a safety cover in which an adhesive layer of the substrate engages the "ring of concern". A compressive foam strip along an opposite side of the substrate engages a safety cover such that a compressive force is maintained between the "ring of concern" and the adhesive layer of the substrate.

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

    PubMed Central

    Kulhánek, Jiří

    2012-01-01

    Summary 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. PMID:22423270

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

    NASA Astrophysics Data System (ADS)

    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.

  12. Enhancement of IR and VCD intensities due to charge transfer.

    PubMed

    Nicu, Valentin Paul; Autschbach, Jochen; Baerends, Evert Jan

    2009-03-14

    Donor-acceptor interactions such as the one between the Cl(-) base and the N-H sigma* acceptor orbitals encountered in the complexation of Cl(-) counterions to the [Co(en)(3)](3+) transition metal complex, have been shown to cause huge enhancement (between 1 and 2 orders of magnitude) of the VCD intensities of N-H stretching modes. This effect has been fully analyzed, and could be attributed to increased charge flow from the Cl(-) donors when the N-H bonds become stretched. The transfer of charge counteracts the movement of negative electronic charge that happens along with the motion of the H nuclei, effectively reversing the electronic part of the electric dipole transition moment (EDTM) in the direction of the charge flow (z, say), and of the magnetic transition dipole moment (MDTM) in the perpendicular direction. The consequences for the IR and VCD intensity follow: IR intensity is strongly increased if the EDTM is polarized in the z direction, e.g. in A(2) modes, but not so much if it is polarized in the xy plane (E modes), the VCD is strongly enhanced if the EDTM and MTDM are polarized in the xy plane (in E modes), but less so when they are polarized in the z direction (in A(2) modes). The explanation holds generally for complexation phenomena of this sort, including the donor-acceptor part of hydrogen bonding interactions, e.g. with solvent molecules.

  13. Anti-Neutrino Charged-Current Reactions on Scintillator with Low Momentum Transfer

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

    Gran, R.; et al.

    2018-06-01

    We report on multi-nucleon effects in low momentum transfer (more » $< 0.8$ GeV/c) anti-neutrino interactions on scintillator. These data are from the 2010-11 anti-neutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well-described when a screening effect at low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasi-elastic, $$\\Delta$$ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this anti-neutrino sample. We present the results as a double-differential cross section to accelerate investigation of alternate models for anti-neutrino scattering off nuclei.« less

  14. Anti-Neutrino Charged-Current Reactions on Scintillator with Low Momentum Transfer

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

    Gran, R.; et al.

    2018-03-25

    We report on multi-nucleon effects in low momentum transfer (more » $< 0.8$ GeV/c) anti-neutrino interactions on scintillator. These data are from the 2010-11 anti-neutrino phase of the MINERvA experiment at Fermilab. The hadronic energy spectrum of this inclusive sample is well-described when a screening effect at low energy transfer and a two-nucleon knockout process are added to a relativistic Fermi gas model of quasi-elastic, $$\\Delta$$ resonance, and higher resonance processes. In this analysis, model elements introduced to describe previously published neutrino results have quantitatively similar benefits for this anti-neutrino sample. We present the results as a double-differential cross section to accelerate investigation of alternate models for anti-neutrino scattering off nuclei.« less

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

    PubMed

    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.

  16. Charge-transfer contributions to the excitonic coupling matrix element in BODIPY-based energy transfer cassettes

    NASA Astrophysics Data System (ADS)

    Spiegel, J. Dominik; Lyskov, Igor; Kleinschmidt, Martin; Marian, Christel M.

    2017-01-01

    BODIPY-based dyads serve as model systems for the investigation of excitation energy transfer (EET). Through-space EET is brought about by direct and exchange interactions between the transition densities of donor and acceptor localized states. The presence of a molecular linker gives rise to additional charge transfer (CT) contributions. Here, we present a novel approach for the calculation of the excitonic coupling matrix element (ECME) including CT contributions which is based on supermolecular one-electron transition density matrices (STD). The validity of the approach is assessed for a model system of two π -stacked ethylene molecules at varying intermolecular separation. Wave functions and electronic excitation energies of five EET cassettes comprising anthracene as exciton donor and BODIPY as exciton acceptor are obtained by the redesigned combined density functional theory and multireference configuration interaction (DFT/MRCI-R) method. CT contributions to the ECME are shown to be important in the covalently linked EET cassettes.

  17. A comparison of various surface charge transfer hole doping of graphene grown by chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Chandramohan, S.; Seo, Tae Hoon; Janardhanam, V.; Hong, Chang-Hee; Suh, Eun-Kyung

    2017-10-01

    Charge transfer doping is a renowned route to modify the electrical and electronic properties of graphene. Understanding the stability of potentially important charge-transfer materials for graphene doping is a crucial first step. Here we present a systematic comparison on the doping efficiency and stability of single layer graphene using molybdenum trioxide (MoO3), gold chloride (AuCl3), and bis(trifluoromethanesulfonyl)amide (TFSA). Chemical dopants proved to be very effective, but MoO3 offers better thermal stability and device fabrication compatibility. Single layer graphene films with sheet resistance values between 100 and 200 ohm/square were consistently produced by implementing a two-step growth followed by doping without compromising the optical transmittance.

  18. Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

    PubMed

    Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

    2014-11-14

    Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

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

    PubMed

    Li, Guangqi; Govind, Niranjan; Ratner, Mark A; Cramer, Christopher J; Gagliardi, Laura

    2015-12-17

    The mechanism of charge transfer has been observed to change from tunneling to hopping with increasing numbers of DNA base pairs in polynucleotides and with the length of molecular wires. The aim of this paper is to investigate this transition by examining the population dynamics using a tight-binding Hamiltonian with model parameters to describe a linear donor-bridge-acceptor (D-B-A) system. The model includes a primary vibration and an electron-vibration coupling at each site. A further coupling of the primary vibration with a secondary phonon bath allows the system to dissipate energy to the environment and reach a steady state. We apply the quantum master equation (QME) approach, based on second-order perturbation theory in a quantum dissipative system, to examine the dynamical processes involved in charge-transfer and follow the population transfer rate at the acceptor, ka, to shed light on the transition from tunneling to hopping. With a small tunneling parameter, V, the on-site population tends to localize and form polarons, and the hopping mechanism dominates the transfer process. With increasing V, the population tends to be delocalized and the tunneling mechanism dominates. The competition between incoherent hopping and coherent tunneling governs the mechanism of charge transfer. By varying V and the total number of sites, we also examine the onset of the transition from tunneling to hopping with increasing length.

  20. The Case Against Charge Transfer Interactions in Dissolved Organic Matter Optical Properties

    NASA Astrophysics Data System (ADS)

    McKay, G.; Korak, J.; Erickson, P. R.; Latch, D. E.; McNeill, K.; Rosario-Ortiz, F.

    2017-12-01

    The optical properties of dissolved organic matter influence chemical and biological processes in all aquatic ecosystems. Organic matter optical properties have been used by scientists and engineers for decades for remote sensing, in situ monitoring, and characterizing laboratory samples to track dissolved organic carbon concentration and character. However, there is still a lack of understanding of the origin of organic matter optical properties, which could conflict with other empirical fluorescence interpretation methods (e.g. PARAFAC). Organic matter optical properties have been attributed to a charge-transfer model in which donor-acceptor complexes play a primary role. This model was evaluated by measuring the absorbance and fluorescence response of organic matter isolates to perturbations in solvent temperature, viscosity, and polarity, which affect the position and intensity of spectra for known donor-acceptor complexes of organic molecules. Absorbance and fluorescence spectral shape were unaffected by these perturbations, indicating that the distribution of absorbing and emitting species was unchanged. These results call into question the wide applicability of the charge-transfer model for explaining organic matter optical properties and suggest that future research should explore other models for organic matter photophysics.

  1. Magnon Splitting Induced by Charge Transfer in the Three-Orbital Hubbard Model

    NASA Astrophysics Data System (ADS)

    Wang, Yao; Huang, Edwin W.; Moritz, Brian; Devereaux, Thomas P.

    2018-06-01

    Understanding spin excitations and their connection to unconventional superconductivity have remained central issues since the discovery of cuprates. Direct measurement of the dynamical spin structure factor in the parent compounds can provide key information on important interactions relevant in the doped regime, and variations in the magnon dispersion have been linked closely to differences in crystal structure between families of cuprate compounds. Here, we elucidate the relationship between spin excitations and various controlling factors thought to be significant in high-Tc materials by systematically evaluating the dynamical spin structure factor for the three-orbital Hubbard model, revealing differences in the spin dispersion along the Brillouin zone axis and the diagonal. Generally, we find that the absolute energy scale and momentum dependence of the excitations primarily are sensitive to the effective charge-transfer energy, while changes in the on-site Coulomb interactions have little effect on the details of the dispersion. In particular, our result highlights the splitting between spin excitations along the axial and diagonal directions in the Brillouin zone. This splitting decreases with increasing charge-transfer energy and correlates with changes in the apical oxygen position, and general structural variations, for different cuprate families.

  2. Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

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

    Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

    Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

  3. Substantial Intramolecular Charge Transfer Induces Long Emission Wavelengths and Mega Stokes Shifts in 6-Aminocoumarins

    DOE PAGES

    Liu, Xiaogang; Cole, Jacqueline M.; Xu, Zhaochao

    2017-06-01

    Coumarins are deployed in numerous bioimaging and biosensing applications. Among various coumarin derivatives, 6-aminocoumarins attract increasing attention for their red-shifted emissions, mega Stokes shifts, and significant solvatochromism. These spectral characteristics together with weak emission intensities have historically been ascribed to the formation of the twisted intramolecular charge transfer (TICT) state in 6-aminocoumarins. In this work, we demonstrate that it is actually substantial intramolecular charge transfer (ICT) that is responsible for these fluorescent properties. Based on this new understanding, we reanalyzed the sensing mechanism of a 6-aminocouarmin based fluorescent probe and obtained close agreement with experimental data. Lastly, our results leadmore » to a deeper understanding of the photophysics of 6-aminocoumarins and will inspire the rational development of novel fluorescent probes.« less

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  5. Intramolecular charge transfer and trans-cis isomerization of the DCM styrene dye in polar solvents. A CS INDO MRCI study

    NASA Astrophysics Data System (ADS)

    Marguet, S.; Mialocq, J. C.; Millie, P.; Berthier, G.; Momicchioli, F.

    1992-03-01

    The solvent-induced changes of trans-cis isomerization efficiency and electronic structure of the excited state of the DCM dye have been considered by means of CS INDO MRCI calculations. The potential energy curves, dipole moments and atomic charge densities as a function of two internal coordinates, namely the rotation angle about the central "double" bond and the twisting of the dimethylamino group, have been obtained for the ground state and the lowest excited states. The structural requirements for the existence of ICT (intramolecular charge transfer) excited states have been investigated by considering internal rotations about three single bonds. The reliability of the potential surfaces and of the solvation models has been discussed with reference to test-calculations on the DMABN molecule. In the first excited singlet state of DCM, the low-energy barrier for the trans-cis isomerization has been found unaffected by the solvent polarity. The only singlet excited state presenting a large ICT character has been found to be the S 2 state for a perpendicularly twisted conformation of the dimethylamino group (TICT state). The assumption of a deactivation of the trans-isomer in the locally excited state through the TICT funnel has been largely discussed with reference to the simplifications of the present theoretical approach.

  6. Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

    PubMed

    Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

    2017-08-03

    The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

  7. Numerical modeling of heat transfer during hydrogen absorption in thin double-layered annular ZrCo beds

    NASA Astrophysics Data System (ADS)

    Cui, Yehui; Zeng, Xiangguo; Kou, Huaqin; Ding, Jun; Wang, Fang

    2018-06-01

    In this work a three-dimensional (3D) hydrogen absorption model was proposed to study the heat transfer behavior in thin double-layered annular ZrCo beds. Numerical simulations were performed to investigate the effects of conversion layer thickness, thermal conductivity, cooling medium and its flow velocity on the efficiency of heat transfer. Results reveal that decreasing the layer thickness and improving the thermal conductivity enhance the ability of heat transfer. Compared with nitrogen and helium, water appears to be a better medium for cooling. In order to achieve the best efficiency of heat transfer, the flow velocity needs to be maximized.

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

    PubMed

    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.

  9. EV Charging Through Wireless Power Transfer: Analysis of Efficiency Optimization and Technology Trends

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

    Miller, John M; Rakouth, Heri; Suh, In-Soo

    This paper is aimed at reviewing the technology trends for wireless power transfer (WPT) for electric vehicles (EV). It also analyzes the factors affecting its efficiency and describes the techniques currently used for its optimization. The review of the technology trends encompasses both stationary and moving vehicle charging systems. The study of the stationary vehicle charging technology is based on current implementations and on-going developments at WiTricity and Oak Ridge National Lab (ORNL). The moving vehicle charging technology is primarily described through the results achieved by the Korean Advanced Institute of Technology (KAIST) along with on-going efforts at Stanford University.more » The factors affecting the efficiency are determined through the analysis of the equivalent circuit of magnetic resonant coupling. The air gap between both transmitting and receiving coils along with the magnetic field distribution and the relative impedance mismatch between the related circuits are the primary factors affecting the WPT efficiency. Currently the industry is looking at an air gap of 25 cm or below. To control the magnetic field distribution, Kaist has recently developed the Shaped Magnetic Field In Resonance (SMFIR) technology that uses conveniently shaped ferrite material to provide low reluctance path. The efficiency can be further increased by means of impedance matching. As a result, Delphi's implementation of the WiTricity's technology exhibits a WPT efficiency above 90% for stationary charging while KAIST has demonstrated a maximum efficiency of 83% for moving vehicle with its On Line Vehicle (OLEV) project. This study is restricted to near-field applications (short and mid-range) and does not address long-range technology such as microwave power transfer that has low efficiency as it is based on radiating electromagnetic waves. This paper exemplifies Delphi's work in powertrain electrification as part of its innovation for the real world program

  10. Associative charge transfer reactions. Temperature effects and mechanism of the gas-phase polymerization of propene initiated by a benzene radical cation.

    PubMed

    Ibrahim, Yehia; Meot-Ner Mautner, Michael; El-Shall, M Samy

    2006-07-13

    In associative charge transfer (ACT) reactions, a core ion activates ligand molecules by partial charge transfer. The activated ligand polymerizes, and the product oligomer takes up the full charge from the core ion. In the present system, benzene(+*) (Bz(+*)) reacts with two propene (Pr) molecules to form a covalently bonded ion, C(6)H(6)(+*) + 2 C(3)H(6) --> C(6)H(12)(+*) + C(6)H(6). The ACT reaction is activated by a partial charge transfer from Bz(+*) to Pr in the complex, and driven to completion by the formation of a covalent bond in the polymerized product. An alternative channel forms a stable association product (Bz.Pr)(+*), with an ACT/association product ratio of 60:40% that is independent of pressure and temperature. In contrast to the Bz(+*)/propene system, ACT polymerization is not observed in the Bz(+*)/ethylene (Et) system since charge transfer in the Bz(+*)(Et) complex is inefficient to activate the reaction. The roles of charge transfer in these complexes are verified by ab initio calculations. The overall reaction of Bz(+*) with Pr follows second-order kinetics with a rate constant of k (304 K) = 2.1 x 10(-12) cm(3) s(-1) and a negative temperature coefficient of k = aT(-5.9) (or an activation energy of -3 kcal/mol). The kinetic behavior is similar to sterically hindered reactions and suggests a [Bz(+*) (Pr)]* activated complex that proceeds to products through a low-entropy transition state. The temperature dependence shows that ACT reactions can reach a unit collision efficiency below 100 K, suggesting that ACT can initiate polymerization in cold astrochemical environments.

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

    PubMed Central

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

    2018-01-01

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

  12. Double Charge Ordering States and Spin Ordering State Observed in a RFe2O4 System

    PubMed Central

    Sun, Fei; Wang, Rui; Aku-Leh, C.; Yang, H. X.; He, Rui; Zhao, Jimin

    2014-01-01

    Charge, spin, and lattice degrees of orderings are of great interest in the layered quantum material RFe2O4 (R = Y, Er, Yb, Tm, and Lu) system. Recently many unique properties have been found using various experimental methods. However so far the nature of the two-dimensional (2D) charge ordering (CO) state is not clear and no observation of its fine structure in energy has been reported. Here we report unambiguous observation of double 2D CO states at relatively high temperature in a polycrystalline Er0.1Yb0.9Fe2O4 using Raman scattering. The energy gaps between the 3D and the double 2D states are 170 meV (41.2 THz) and 193 meV (46.6 THz), respectively. We also observed a spin ordering (SO) state at below 210 K with characteristic energy of 45 meV (10.7 THz). Our investigation experimentally identified new fine structures of quantum orders in the system, which also extends the capability of optical methods in investigating other layered quantum materials. PMID:25234133

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Absorption spectrometric study of charge transfer complex formation between 4-acetamidophenol (paracetamol) and a series of quinones including Vitamin K 3

    NASA Astrophysics Data System (ADS)

    Saha, Avijit; Mukherjee, Asok K.

    2004-07-01

    The formation of charge transfer (CT) complexes of 4-acetamidophenol (commonly called 'paracetamol') and a series of quinones (including Vitamin K 3) has been studied spectrophotometrically in ethanol medium. The vertical ionisation potential of paracetamol and the degrees of charge transfer of the complexes in their ground state has been estimated from the trends in the charge transfer bands. The oscillator and transition dipole strengths of the complexes have been determined from the CT absorption spectra at 298 K. The complexes have been found by Job's method of continuous variation to have the uncommon 2:1 (paracetamol:quinone) stoichiometry in each case. The enthalpies and entropies of formation of the complexes have been obtained by determining their formation constants at five different temperatures.

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

    PubMed

    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.

  16. Quasiparticles and charge transfer at the two surfaces of the honeycomb iridate Na2IrO3

    NASA Astrophysics Data System (ADS)

    Moreschini, L.; Lo Vecchio, I.; Breznay, N. P.; Moser, S.; Ulstrup, S.; Koch, R.; Wirjo, J.; Jozwiak, C.; Kim, K. S.; Rotenberg, E.; Bostwick, A.; Analytis, J. G.; Lanzara, A.

    2017-10-01

    Direct experimental investigations of the low-energy electronic structure of the Na2IrO3 iridate insulator are sparse and draw two conflicting pictures. One relies on flat bands and a clear gap, the other involves dispersive states approaching the Fermi level, pointing to surface metallicity. Here, by a combination of angle-resolved photoemission, photoemission electron microscopy, and x-ray absorption, we show that the correct picture is more complex and involves an anomalous band, arising from charge transfer from Na atoms to Ir-derived states. Bulk quasiparticles do exist, but in one of the two possible surface terminations the charge transfer is smaller and they remain elusive.

  17. An ab initio study of ion induced charge transfer dynamics in collision of carbon ions with thymine.

    PubMed

    Bacchus-Montabonel, Marie-Christine; Tergiman, Yvette Suzanne

    2011-05-28

    Charge transfer in collisions of carbon ions on a thymine target has been studied theoretically in a wide collision range by means of ab initio quantum chemistry molecular methods. The process appears markedly anisotropic in the whole energy domain, significantly favoured in the perpendicular orientation. A specific decrease of the charge transfer cross sections at low collision energies may be pointed out and could induce an enhancement of the complementary fragmentation processes for collision energies down to about 10 eV, as observed for the low-electron fragmentation process. Such feature may be of important interest in ion-induced biomolecular radiation damage. This journal is © the Owner Societies 2011

  18. On Practical Charge Injection at the Metal/Organic Semiconductor Interface

    PubMed Central

    Kumatani, Akichika; Li, Yun; Darmawan, Peter; Minari, Takeo; Tsukagoshi, Kazuhito

    2013-01-01

    We have revealed practical charge injection at metal and organic semiconductor interface in organic field effect transistor configurations. We have developed a facile interface structure that consisted of double-layer electrodes in order to investigate the efficiency through contact metal dependence. The metal interlayer with few nanometers thickness between electrode and organic semiconductor drastically reduces the contact resistance at the interface. The improvement has clearly obtained when the interlayer is a metal with lower standard electrode potential of contact metals than large work function of the contact metals. The electrode potential also implies that the most dominant effect on the mechanism at the contact interface is induced by charge transfer. This mechanism represents a step forward towards understanding the fundamental physics of intrinsic charge injection in all organic devices. PMID:23293741

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

    PubMed

    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.

  20. Charging system using solar panels and a highly resonant wireless power transfer model for small UAS applications

    NASA Astrophysics Data System (ADS)

    Hallman, Sydney N.; Huck, Robert C.; Sluss, James J.

    2016-05-01

    The use of a wireless charging system for small, unmanned aircraft system applications is useful for both military and commercial consumers. An efficient way to keep the aircraft's batteries charged without interrupting flight would be highly marketable. While the general concepts behind highly resonant wireless power transfer are discussed in a few publications, the details behind the system designs are not available even in academic journals, especially in relation to avionics. Combining a highly resonant charging system with a solar panel charging system can produce enough power to extend the flight time of a small, unmanned aircraft system without interruption. This paper provides an overview of a few of the wireless-charging technologies currently available and outlines a preliminary design for an aircraft-mounted battery charging system.

  1. Self-interaction effects on charge-transfer collisions

    DOE PAGES

    Quashie, Edwin E.; Saha, Bidhan C.; Andrade, Xavier; ...

    2017-04-27

    In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. In addition, we compare many different approximations of the exchange and correlation potential, using as a test system the collision of H + + CH 4 at 30 eV. We find that semilocal approximations, like the Perdew-Burke- Ernzerhof (PBE), and even hybrid functionals, such as the Becke, 3-parameter, Lee-Yang-Parr (B3LYP), produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily tomore » the proton, leading to radically different forces with respect to the non-self-interacting case. Lastly, from our results, we conclude that using a functional that is self-interaction free is essential to properly describing charge-transfer collisions between ions and molecules in TDDFT.« less

  2. Dynamic entanglement transfer in a double-cavity optomechanical system

    NASA Astrophysics Data System (ADS)

    Huan, Tiantian; Zhou, Rigui; Ian, Hou

    2015-08-01

    We give a theoretical study of a double-cavity system in which a mechanical resonator beam is coupled to two cavity modes on both sides through radiation pressures. The indirect coupling between the cavities via the resonator sets up a correlation in the optomechanical entanglements between the two cavities with the common resonator. This correlation initiates an entanglement transfer from the intracavity photon-phonon entanglements to an intercavity photon-photon entanglement. Using numerical solutions, we show two distinct regimes of the optomechanical system, in which the indirect entanglement either builds up and eventually saturates or undergoes a death-and-revival cycle, after a time lapse for initiating the cooperative motion of the left and right cavity modes.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    Auerbach, N.; Zheng, D. C.

    1992-03-01

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

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

    NASA Astrophysics Data System (ADS)

    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

  6. Charge-Transfer Complexes and Photochemistry of Ozone with Ferrocene and n-Butylferrocene: A UV-vis Matrix-Isolation Study.

    PubMed

    Pinelo, Laura F; Kugel, Roger W; Ault, Bruce S

    2015-10-15

    The reactions of ozone with ferrocene (cp2Fe) and with n-butylferrocene (n-butyl cp2Fe) were studied using matrix isolation, UV-vis spectroscopy, and theoretical calculations. The codeposition of cp2Fe with O3 and of n-butyl cp2Fe with O3 into an argon matrix led to the production of 1:1 charge-transfer complexes with absorptions at 765 and 815 nm, respectively. These absorptions contribute to the green matrix color observed upon initial deposition. The charge-transfer complexes underwent photochemical reactions upon irradiation with red light (λ ≥ 600 nm). Theoretical UV-vis spectra of the charge-transfer complexes and photochemical products were calculated using TD-DFT at the B3LYP/6-311G++(d,2p) level of theory. The calculated UV-vis spectra were in good agreement with the experimental results. MO analysis of these long-wavelength transitions showed them to be n→ π* on the ozone subunit in the complex and indicated that the formation of the charge-transfer complex between ozone and cp2Fe or n-butyl cp2Fe affects how readily the π* orbital on O3 is populated when red light (λ ≥ 600 nm) is absorbed. 1:1 complexes of cp2Fe and n-butyl cp2Fe with O2 were also observed experimentally and calculated theoretically. These results support and enhance previous infrared studies of the mechanism of photooxidation of ferrocene by ozone, a reaction that has considerable significance for the formation of iron oxide thin films for a range of applications.

  7. A polygonal double-layer coil design for high-efficiency wireless power transfer

    NASA Astrophysics Data System (ADS)

    Mao, Shitong; Wang, Hao; Mao, Zhi-Hong; Sun, Mingui

    2018-05-01

    In this work, we present a novel coil structure for the design of Wireless Power Transfer (WPT) systems via magnetic resonant coupling. The new coil consists of two layers of flat polygonal windings in square, pentagonal and hexagonal shapes. The double-layer coil can be conveniently fabricated using the print circuit broad (PCB) technology. In our design, we include an angle between the two layers which can be adjusted to change the area of inter-layer overlap. This unique structure is thoroughly investigated with respect to the quality factor Q and the power transfer efficiency (PTE) using the finite element method (FEM). An equivalent circuit is derived and used to explain the properties of the angularly shifted double-layer coil theoretically. Comparative experiments are conducted from which the performance of the new coil is evaluated quantitatively. Our results have shown that an increased shift angle improves the Q-factor, and the optimal PTE is achieved when the angle reaches the maximum. When compared to the pentagonal and hexagonal coils, the square coil achieves the highest PTE due to its lowest parasitic capacitive effects. In summary, our new coil design improves the performance of WPT systems and allows a formal design procedure for optimization in a given application.

  8. Charged-pion cross sections and double-helicity asymmetries in polarized p +p collisions at √{s }=200 GeV

    NASA Astrophysics Data System (ADS)

    Adare, A.; Aidala, C.; Ajitanand, N. N.; Akiba, Y.; Akimoto, R.; Al-Ta'Ani, H.; Alexander, J.; Andrews, K. R.; Angerami, A.; Aoki, K.; Apadula, N.; Appelt, E.; Aramaki, Y.; Armendariz, R.; Aschenauer, E. C.; Atomssa, E. T.; Awes, T. C.; Azmoun, B.; Babintsev, V.; Bai, M.; Bannier, B.; Barish, K. N.; Bassalleck, B.; Basye, A. T.; Bathe, S.; Baublis, V.; Baumann, C.; Bazilevsky, A.; Belmont, R.; Ben-Benjamin, J.; Bennett, R.; Blau, D. S.; Bok, J. S.; Boyle, K.; Brooks, M. L.; Broxmeyer, D.; Buesching, H.; Bumazhnov, V.; Bunce, G.; Butsyk, S.; Campbell, S.; Castera, P.; Chen, C.-H.; Chi, C. Y.; Chiu, M.; Choi, I. J.; Choi, J. B.; Choudhury, R. K.; Christiansen, P.; Chujo, T.; Chvala, O.; Cianciolo, V.; Citron, Z.; Cole, B. A.; Conesa Del Valle, Z.; Connors, M.; Csanád, M.; Csörgő, T.; Dairaku, S.; Datta, A.; David, G.; Dayananda, M. K.; Denisov, A.; Deshpande, A.; Desmond, E. J.; Dharmawardane, K. V.; Dietzsch, O.; Dion, A.; Donadelli, M.; Drapier, O.; Drees, A.; Drees, K. A.; Durham, J. M.; Durum, A.; D'Orazio, L.; Efremenko, Y. V.; Engelmore, T.; Enokizono, A.; En'yo, H.; Esumi, S.; Fadem, B.; Fields, D. E.; Finger, M.; Finger, M.; Fleuret, F.; Fokin, S. L.; Frantz, J. E.; Franz, A.; Frawley, A. D.; Fukao, Y.; Fusayasu, T.; Gal, C.; Garishvili, I.; Giordano, F.; Glenn, A.; Gong, X.; Gonin, M.; Goto, Y.; Granier de Cassagnac, R.; Grau, N.; Greene, S. V.; Grosse Perdekamp, M.; Gunji, T.; Guo, L.; Gustafsson, H.-Å.; Haggerty, J. S.; Hahn, K. I.; Hamagaki, H.; Hamblen, J.; Han, R.; Hanks, J.; Harper, C.; Hashimoto, K.; Haslum, E.; Hayano, R.; He, X.; Hemmick, T. K.; Hester, T.; Hill, J. C.; Hollis, R. S.; Holzmann, W.; Homma, K.; Hong, B.; Horaguchi, T.; Hori, Y.; Hornback, D.; Huang, S.; Ichihara, T.; Ichimiya, R.; Iinuma, H.; Ikeda, Y.; Imai, K.; Inaba, M.; Iordanova, A.; Isenhower, D.; Ishihara, M.; Issah, M.; Ivanischev, D.; Iwanaga, Y.; Jacak, B. V.; Jia, J.; Jiang, X.; John, D.; Johnson, B. M.; Jones, T.; Joo, K. S.; Jouan, D.; Kamin, J.; Kaneti, S.; Kang, B. H.; Kang, J. H.; Kang, J. S.; Kapustinsky, J.; Karatsu, K.; Kasai, M.; Kawall, D.; Kazantsev, A. V.; Kempel, T.; Khanzadeev, A.; Kijima, K. M.; Kim, B. I.; Kim, D. J.; Kim, E.-J.; Kim, Y.-J.; Kim, Y. K.; Kinney, E.; Kiss, Á.; Kistenev, E.; Kleinjan, D.; Kline, P.; Kochenda, L.; Komkov, B.; Konno, M.; Koster, J.; Kotov, D.; Král, A.; Kunde, G. J.; Kurita, K.; Kurosawa, M.; Kwon, Y.; Kyle, G. S.; Lacey, R.; Lai, Y. S.; Lajoie, J. G.; Lebedev, A.; Lee, D. M.; Lee, J.; Lee, K. B.; Lee, K. S.; Lee, S. H.; Lee, S. R.; Leitch, M. J.; Leite, M. A. L.; Li, X.; Lim, S. H.; Linden Levy, L. A.; Liu, H.; Liu, M. X.; Love, B.; Lynch, D.; Maguire, C. F.; Makdisi, Y. I.; Manion, A.; Manko, V. I.; Mannel, E.; Mao, Y.; Masui, H.; McCumber, M.; McGaughey, P. L.; McGlinchey, D.; McKinney, C.; Means, N.; Mendoza, M.; Meredith, B.; Miake, Y.; Mibe, T.; Mignerey, A. C.; Miki, K.; Milov, A.; Mitchell, J. T.; Miyachi, Y.; Mohanty, A. K.; Moon, H. J.; Morino, Y.; Morreale, A.; Morrison, D. P.; Motschwiller, S.; Moukhanova, T. V.; Murakami, T.; Murata, J.; Nagamiya, S.; Nagle, J. L.; Naglis, M.; Nagy, M. I.; Nakagawa, I.; Nakamiya, Y.; Nakamura, K. R.; Nakamura, T.; Nakano, K.; Newby, J.; Nguyen, M.; Nihashi, M.; Nouicer, R.; Nyanin, A. S.; Oakley, C.; O'Brien, E.; Ogilvie, C. A.; Oka, M.; Okada, K.; Oskarsson, A.; Ouchida, M.; Ozawa, K.; Pak, R.; Pantuev, V.; Papavassiliou, V.; Park, B. H.; Park, I. H.; Park, S. K.; Pate, S. F.; Patel, L.; Pei, H.; Peng, J.-C.; Pereira, H.; Peressounko, D. Yu.; Petti, R.; Pinkenburg, C.; Pisani, R. P.; Proissl, M.; Purschke, M. L.; Qu, H.; Rak, J.; Ravinovich, I.; Read, K. F.; Reygers, K.; Riabov, V.; Riabov, Y.; Richardson, E.; Roach, D.; Roche, G.; Rolnick, S. D.; Rosati, M.; Rosendahl, S. S. E.; Rubin, J. G.; Sahlmueller, B.; Saito, N.; Sakaguchi, T.; Samsonov, V.; Sano, S.; Sarsour, M.; Sato, T.; Savastio, M.; Sawada, S.; Sedgwick, K.; Seidl, R.; Seto, R.; Sharma, D.; Shein, I.; Shibata, T.-A.; Shigaki, K.; Shim, H. H.; Shimomura, M.; Shoji, K.; Shukla, P.; Sickles, A.; Silva, C. L.; Silvermyr, D.; Silvestre, C.; Sim, K. S.; Singh, B. K.; Singh, C. P.; Singh, V.; Slunečka, M.; Sodre, T.; Soltz, R. A.; Sondheim, W. E.; Sorensen, S. P.; Sourikova, I. V.; Stankus, P. W.; Stenlund, E.; Stoll, S. P.; Sugitate, T.; Sukhanov, A.; Sun, J.; Sziklai, J.; Takagui, E. M.; Takahara, A.; Taketani, A.; Tanabe, R.; Tanaka, Y.; Taneja, S.; Tanida, K.; Tannenbaum, M. J.; Tarafdar, S.; Taranenko, A.; Tennant, E.; Themann, H.; Thomas, D.; Togawa, M.; Tomášek, L.; Tomášek, M.; Torii, H.; Towell, R. S.; Tserruya, I.; Tsuchimoto, Y.; Utsunomiya, K.; Vale, C.; van Hecke, H. W.; Vazquez-Zambrano, E.; Veicht, A.; Velkovska, J.; Vértesi, R.; Virius, M.; Vossen, A.; Vrba, V.; Vznuzdaev, E.; Wang, X. R.; Watanabe, D.; Watanabe, K.; Watanabe, Y.; Watanabe, Y. S.; Wei, F.; Wei, R.; Wessels, J.; White, S. N.; Winter, D.; Woody, C. L.; Wright, R. M.; Wysocki, M.; Yamaguchi, Y. L.; Yang, R.; Yanovich, A.; Ying, J.; Yokkaichi, S.; Yoo, J. S.; You, Z.; Young, G. R.; Younus, I.; Yushmanov, I. E.; Zajc, W. A.; Zelenski, A.; Zhou, S.; Phenix Collaboration

    2015-02-01

    We present midrapidity charged-pion invariant cross sections, the ratio of the π- to π+ cross sections and the charge-separated double-spin asymmetries in polarized p +p collisions at √{s }=200 GeV . While the cross section measurements are consistent within the errors of next-to-leading-order (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations overestimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor-dependent pion fragmentation functions. The charge-separated pion asymmetries presented here sample an x range of ˜0.03 - 0.16 and provide unique information on the sign of the gluon-helicity distribution.

  9. Photochemical charge separation in zeolites: Electron transfer dynamics, nanocrystals and zeolitic membranes. Final technical report

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

    Dutta, Prabir K.

    2001-09-30

    Aluminosilicate zeolites provide an excellent host for photochemical charge separation. Because of the constraints provided by the zeolite, the back electron transfer from the reduced acceptor to the oxidized sensitizer is slowed down. This provides the opportunity to separate the charge and use it in a subsequent reaction for water oxidation and reduction. Zeolite-based ruthenium oxide catalysts have been found to be efficient for the water splitting process. This project has demonstrated the usefulness of zeolite hosts for photolytic splitting of water.

  10. Intramolecular charge transfer effects on 4-hydroxy-3-methoxybenzaldehyde

    NASA Astrophysics Data System (ADS)

    Rajendiran, N.; Balasubramanian, T.

    2008-03-01

    The absorption and fluorescence spectral characteristics of 4-hydroxy-3-methoxybenzaldehyde (HMB) have been studied in different solvents, pH and β-cyclodextrin (β-CD) and compared with 4-hydroxy-3,5-dimethoxybenzaldehyde (HDMB). The inclusion complex of HMB with β-CD is analysed by UV-vis, fluorimetry, FT-IR, 1H NMR, SEM and AM1 methods. In HMB, the normal emission (B band) is originates from a locally excited state and the longer emission (A band) is due to intramolecular charge transfer state (ICT). The OH group of HMB is present in the interior part of the β-CD cavity and aldehyde group present in the upper part of the β-CD cavity.

  11. Experimental study of low-energy charge transfer in nitrogen

    NASA Technical Reports Server (NTRS)

    Smith, A.

    1979-01-01

    Total charge transfer cross sections were obtained for the N2(+)-N2 system with relative translational ion energies between 9 and 441 eV. Data were obtained to examine the dependence of total cross section on ion energy. The effect of ion excitation on the cross sections was studied by varying the electron ionization energy in the mass spectrometer ion source over an electron energy range between 14.5 and 32.1 eV. The dependence of total cross section on the neutralization chamber gas pressure was examined by obtaining data at pressure values from 9.9 to 0.000199 torr. Cross section values obtained were compared with experimental and theoretical results of other investigations.

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

    USGS Publications Warehouse

    Sherman, David M.

    1987-01-01

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

  13. Dynamical ion transfer between coupled Coulomb crystals in a double-well potential.

    PubMed

    Klumpp, Andrea; Zampetaki, Alexandra; Schmelcher, Peter

    2017-09-01

    We investigate the nonequilibrium dynamics of coupled Coulomb crystals of different sizes trapped in a double well potential. The dynamics is induced by an instantaneous quench of the potential barrier separating the two crystals. Due to the intra- and intercrystal Coulomb interactions and the asymmetric population of the potential wells, we observe a complex reordering of ions within the two crystals as well as ion transfer processes from one well to the other. The study and analysis of the latter processes constitutes the main focus of this work. In particular, we examine the dependence of the observed ion transfers on the quench amplitude performing an analysis for different crystalline configurations ranging from one-dimensional ion chains via two-dimensional zigzag chains and ring structures to three-dimensional spherical structures. Such an analysis provides us with the means to extract the general principles governing the ion transfer dynamics and we gain some insight on the structural disorder caused by the quench of the barrier height.

  14. NiO: correlated band structure of a charge-transfer insulator.

    PubMed

    Kunes, J; Anisimov, V I; Skornyakov, S L; Lukoyanov, A V; Vollhardt, D

    2007-10-12

    The band structure of the prototypical charge-transfer insulator NiO is computed by using a combination of an ab initio band structure method and the dynamical mean-field theory with a quantum Monte-Carlo impurity solver. Employing a Hamiltonian which includes both Ni d and O p orbitals we find excellent agreement with the energy bands determined from angle-resolved photoemission spectroscopy. This brings an important progress in a long-standing problem of solid-state theory. Most notably we obtain the low-energy Zhang-Rice bands with strongly k-dependent orbital character discussed previously in the context of low-energy model theories.

  15. Charge-transfer photodissociation of adsorbed molecules via electron image states

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

    Jensen, E. T.

    The 248 and 193 nm photodissociations of submonolayer quantities of CH{sub 3}Br and CH{sub 3}I adsorbed on thin layers of n-hexane indicate that the dissociation is caused by dissociative electron attachment from subvacuum level photoelectrons created in the copper substrate. The characteristics of this photodissociation-translation energy distributions and coverage dependences show that the dissociation is mediated by an image potential state which temporarily traps the photoelectrons near the n-hexane-vacuum interface, and then the charge transfers from this image state to the affinity level of a coadsorbed halomethane which then dissociates.

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  17. Intra-molecular Charge Transfer and Electron Delocalization in Non-fullerene Organic Solar Cells

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

    Wu, Qinghe; Zhao, Donglin; Goldey, Matthew B.

    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 showsmore » 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.« less

  18. Car-Parrinello molecular dynamics study of the intramolecular vibrational mode-sensitive double proton-transfer mechanisms in porphycene.

    PubMed

    Walewski, Łukasz; Waluk, Jacek; Lesyng, Bogdan

    2010-02-18

    Car-Parrinello molecular dynamics simulations were carried out to help interpret proton-transfer processes observed experimentally in porphycene under thermodynamic equilibrium conditions (NVT ensemble) as well as during selective, nonequilibrium vibrational excitations of the molecular scaffold (NVE ensemble). In the NVT ensemble, the population of the trans form in the gas phase at 300 K is 96.5%, and of the cis-1 form is 3.5%, in agreement with experimental data. Approximately 70% of the proton-transfer events are asynchronous double proton transfers. According to the high resolution simulation data they consist of two single transfer events that rapidly take place one after the other. The average time-period between the two consecutive jumps is 220 fs. The gas phase reaction rate estimate at 300 K is 3.6 ps, which is comparable to experimentally determined rates. The NVE ensemble nonequilibrium ab initio MD simulations, which correspond to selective vibrational excitations of the molecular scaffold generated with high resolution laser spectroscopy techniques, exhibit an enhancing property of the 182 cm(-1) vibrational mode and an inhibiting property of the 114 cm(-1) one. Both of them influence the proton-transfer rate, in qualitative agreement with experimental findings. Our ab initio simulations provide new predictions regarding the influence of double-mode vibrational excitations on proton-transfer processes. They can help in setting up future programmable spectroscopic experiments for the proton-transfer translocations.

  19. Evaluation of Bulk Charging in Geostationary Transfer Orbit and Earth Escape Trajectories Using the Numit 1-D Charging Model

    NASA Technical Reports Server (NTRS)

    Minow, Joseph I.; Coffey, Victoria N.; Parker, Linda N.; Blackwell, William C., Jr.; Jun, Insoo; Garrett, Henry B.

    2007-01-01

    The NUMIT 1-dimensional bulk charging model is used as a screening to ol for evaluating time-dependent bulk internal or deep dielectric) ch arging of dielectrics exposed to penetrating electron environments. T he code is modified to accept time dependent electron flux time serie s along satellite orbits for the electron environment inputs instead of using the static electron flux environment input originally used b y the code and widely adopted in bulk charging models. Application of the screening technique ts demonstrated for three cases of spacecraf t exposure within the Earth's radiation belts including a geostationa ry transfer orbit and an Earth-Moon transit trajectory for a range of orbit inclinations. Electric fields and charge densities are compute d for dielectric materials with varying electrical properties exposed to relativistic electron environments along the orbits. Our objectiv e is to demonstrate a preliminary application of the time-dependent e nvironments input to the NUMIT code for evaluating charging risks to exposed dielectrics used on spacecraft when exposed to the Earth's ra diation belts. The results demonstrate that the NUMIT electric field values in GTO orbits with multiple encounters with the Earth's radiat ion belts are consistent with previous studies of charging in GTO orb its and that potential threat conditions for electrostatic discharge exist on lunar transit trajectories depending on the electrical proper ties of the materials exposed to the radiation environment.

  20. DFT and TD-DFT computation of charge transfer complex between o-phenylenediamine and 3,5-dinitrosalicylic acid

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

    Afroz, Ziya; Zulkarnain,; Ahmad, Afaq, E-mail: afaqahmad3@gmail.com

    2016-05-23

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  2. Free energy gap laws for the pulse-induced and stationary fluorescence quenching by reversible charge transfer in polar solutions.

    PubMed

    Khokhlova, Svetlana S; Burshtein, Anatoly I

    2011-01-21

    The Stern-Volmer constants for either pulse-induced or stationary fluorescence being quenched by a contact charge transfer are calculated and their free energy dependencies (the free energy gap laws) are specified. The reversibility of charge transfer is taken into account as well as spin conversion in radical ion pairs, followed by their recombination in either singlet or triplet neutral products. The natural decay of triplets as well as their impurity quenching by ionization are accounted for when estimating the fluorescence quantum yield and its free energy dependence.

  3. How can we make stable linear monoatomic chains? Gold-cesium binary subnanowires as an example of a charge-transfer-driven approach to alloying.

    PubMed

    Choi, Young Cheol; Lee, Han Myoung; Kim, Woo Youn; Kwon, S K; Nautiyal, Tashi; Cheng, Da-Yong; Vishwanathan, K; Kim, Kwang S

    2007-02-16

    On the basis of first-principles calculations of clusters and one dimensional infinitely long subnanowires of the binary systems, we find that alkali-noble metal alloy wires show better linearity and stability than either pure alkali metal or noble metal wires. The enhanced alternating charge buildup on atoms by charge transfer helps the atoms line up straight. The cesium doped gold wires showing significant charge transfer from cesium to gold can be stabilized as linear or circular monoatomic chains.

  4. Two-phase charge-coupled device

    NASA Technical Reports Server (NTRS)

    Kosonocky, W. F.; Carnes, J. E.

    1973-01-01

    A charge-transfer efficiency of 99.99% per stage was achieved in the fat-zero mode of operation of 64- and 128-stage two-phase charge-coupled shift registers at 1.0-MHz clock frequency. The experimental two-phase charge-coupled shift registers were constructed in the form of polysilicon gates overlapped by aluminum gates. The unidirectional signal flow was accomplished by using n-type substrates with 0.5 to 1.0 ohm-cm resistivity in conjunction with a channel oxide thickness of 1000 A for the polysilicon gates and 3000 A for the aluminum gates. The operation of the tested shift registers with fat zero is in good agreement with the free-charge transfer characteristics expected for the tested structures. The charge-transfer losses observed when operating the experimental shift registers without the fat zero are attributed to fast interface state trapping. The analytical part of the report contains a review backed up by an extensive appendix of the free-charge transfer characteristics of CCD's in terms of thermal diffusion, self-induced drift, and fringing field drift. Also, a model was developed for the charge-transfer losses resulting from charge trapping by fast interface states. The proposed model was verified by the operation of the experimental two-phase charge-coupled shift registers.

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

    NASA Technical Reports Server (NTRS)

    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.

  6. Fabrication of a highly sensitive penicillin sensor based on charge transfer techniques.

    PubMed

    Lee, Seung-Ro; Rahman, M M; Sawada, Kazuaki; Ishida, Makoto

    2009-03-15

    A highly sensitive penicillin biosensor based on a charge-transfer technique (CTTPS) has been fabricated and demonstrated in this paper. CTTPS comprised a charge accumulation technique for penicilloic acid and H(+) ions perception system. With the proposed CTTPS, it is possible to amplify the sensing signals without external amplifier by using the charge accumulation cycles. The fabricated CTTPS exhibits excellent performance for penicillin detection and exhibit a high-sensitivity (47.852 mV/mM), high signal-to-noise ratio (SNR), large span (1445 mV), wide linear range (0-25 mM), fast response time (<3s), and very good reproducibility. A very lower detection limit of about 0.01 mM was observed from the proposed sensor. Under optimum conditions, the proposed CTTPS outstripped the performance of the widely used ISFET penicillin sensor and exhibited almost eight times greater sensitivity as compared to ISFET (6.56 mV/mM). The sensor system is implemented for the measurement of the penicillin concentration in penicillin fermentation broth.

  7. Electric Double Layer Composed of an Antagonistic Salt in an Aqueous Mixture: Local Charge Separation and Surface Phase Transition

    NASA Astrophysics Data System (ADS)

    Yabunaka, Shunsuke; Onuki, Akira

    2017-09-01

    We examine an electric double layer containing an antagonistic salt in an aqueous mixture, where the cations are small and hydrophilic but the anions are large and hydrophobic. In this situation, a strong coupling arises between the charge density and the solvent composition. As a result, the anions are trapped in an oil-rich adsorption layer on a hydrophobic wall. We then vary the surface charge density σ on the wall. For σ >0 the anions remain accumulated, but for σ <0 the cations are attracted to the wall with increasing |σ |. Furthermore, the electric potential drop Ψ (σ ) is nonmonotonic when the solvent interaction parameter χ (T ) exceeds a critical value χc determined by the composition and the ion density in the bulk. This leads to a first-order phase transition between two kinds of electric double layers with different σ and common Ψ . In equilibrium such two-layer regions can coexist. The steric effect due to finite ion sizes is crucial in these phenomena.

  8. Controlling the charge transfer in phenylene-bridged borylene-amine pi-conjugated systems.

    PubMed

    Proń, Agnieszka; Zhou, Gang; Norouzi-Arasi, Hassan; Baumgarten, Martin; Müllen, Klaus

    2009-08-20

    Novel boron-nitrogen-containing pi-conjugated compounds 3,3'- and 4,4'-((2,4,6-triisopropylphenyl)borylene)bis(N,N-diarylbenzenamine) (1-2), m- and p-phenylene bridged to the boron center, respectively, have been synthesized and characterized. Optical studies by means of UV-vis absorption and emission measurements as well as DFT calculations reveal a different charge transfer behavior between the para series and the meta series at ground and excited states.

  9. The simplest equivalent circuit of a pulsed dielectric barrier discharge and the determination of the gas gap charge transfer

    NASA Astrophysics Data System (ADS)

    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.

  10. Charge transfer complex in diketopyrrolopyrrole polymers and fullerene blends: Implication for organic solar cell efficiency

    NASA Astrophysics Data System (ADS)

    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.

  11. 46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

  12. 46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

  13. 46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

  14. 46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

  15. 46 CFR 153.957 - Persons in charge of transferring liquid cargo in bulk or cleaning cargo tanks.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... SECURITY (CONTINUED) CERTAIN BULK DANGEROUS CARGOES SHIPS CARRYING BULK LIQUID, LIQUEFIED GAS, OR COMPRESSED GAS HAZARDOUS MATERIALS Operations Cargo Transfer Procedures § 153.957 Persons in charge of...

  16. Charged-pion cross sections and double-helicity asymmetries in polarized p + p collisions at √s = 200 GeV

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

    Adare, A.; Aidala, C.; Ajitanand, N. N.

    2015-02-02

    We present midrapidity charged-pion invariant cross sections, the ratio of the π⁻ to π⁺ cross sections and the charge-separated double-spin asymmetries in polarized p+p collisions at √s = 200 GeV. While the cross section measurements are consistent within the errors of next-to-leadingorder (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations over estimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor dependent pion fragmentation functions. Thus, the charge-separated pion asymmetries presented heremore » sample an x range of ~0.03–0.16 and provide unique information on the sign of the gluon-helicity distribution.« less

  17. A molecularly based theory for electron transfer reorganization energy.

    PubMed

    Zhuang, Bilin; Wang, Zhen-Gang

    2015-12-14

    Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule's permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

  18. Charge states of ions, and mechanisms of charge ordering transitions

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

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

  19. Single-step electron transfer on the nanometer scale: ultra-fast charge shift in strongly coupled zinc porphyrin-gold porphyrin dyads.

    PubMed

    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

  20. Experimental and modeling study on charge storage/transfer mechanism of graphene-based supercapacitors

    NASA Astrophysics Data System (ADS)

    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.

  1. Electric Double Layer electrostatics of spherical polyelectrolyte brushes with pH-dependent charge density

    NASA Astrophysics Data System (ADS)

    Li, Hao; Chen, Guang; Sinha, Shayandev; Das, Siddhartha; Soft Matter, Interfaces,; Energy Laboratory (Smiel) Team

    Understanding the electric double layer (EDL) electrostatics of spherical polyelectrolyte (PE) brushes, which are spherical particles grafted with PE layers, is essential for appropriate use of PE-grfated micro-nanoparticles for targeted drug delivery, oil recovery, water harvesting, emulsion stabilization, emulsion breaking, etc. Here we elucidate the EDL electrostatics of spherical PE brushes for the case where the PE exhibits pH-dependent charge density. This pH-dependence necessitates the consideration of explicit hydrogen ion concentration, which in turn dictates the distribution of monomers along the length of the grafted PE. This monomer distribution is shown to be a function of the nature of the sphere (metallic or a charged or uncharged dielectric or a liquid-filled sphere). All the calculations are performed for the case where the PE electrostatics can be decoupled from the PE elastic and excluded volume effects. Initial predictions are also provided for the case where such decoupling is not possible.

  2. Spreading of Electrolyte Drops on Charged Surfaces: Electric Double Layer Effects on Drop Dynamics

    NASA Astrophysics Data System (ADS)

    Bae, Kyeong; Sinha, Shayandev; Chen, Guang; Das, Siddhartha

    2015-11-01

    Drop spreading is one of the most fundamental topics of wetting. Here we study the spreading of electrolyte drops on charged surfaces. The electrolyte solution in contact with the charged solid triggers the formation of an electric double layer (EDL). We develop a theory to analyze how the EDL affects the drop spreading. The drop dynamics is studied by probing the EDL effects on the temporal evolution of the contact angle and the base radius (r). The EDL effects are found to hasten the spreading behaviour - this is commensurate to the EDL effects causing a ``philic'' tendency in the drops (i.e., drops attaining a contact angle smaller than its equilibrium value), as revealed by some of our recent papers. We also develop scaling laws to illustrate the manner in which the EDL effects make the r versus time (t) variation deviate from the well known r ~tn variation, thereby pinpointing the attainment of different EDL-mediated spreading regimes.

  3. Ab Initio Simulation of Charge Transfer at the Semiconductor Quantum Dot/TiO 2 Interface in Quantum Dot-Sensitized Solar Cells

    DOE PAGES

    Xin, Xukai; Li, Bo; Jung, Jaehan; ...

    2014-07-24

    Quantum dot-sensitized solar cells (QDSSCs) have emerged as a promising solar architecture for next-generation solar cells. The QDSSCs exhibit a remarkably fast electron transfer from the quantum dot (QD) donor to the TiO 2 acceptor with size quantization properties of QDs that allows for the modulation of band energies to control photoresponse and photoconversion efficiency of solar cells. In order to understand the mechanisms that underpin this rapid charge transfer, the electronic properties of CdSe and PbSe QDs with different sizes on the TiO 2 substrate are simulated using a rigorous ab initio density functional method. Our method capitalizes onmore » localized orbital basis set, which is computationally less intensive. Quite intriguingly, a remarkable set of electron bridging states between QDs and TiO 2 occurring via the strong bonding between the conduction bands of QDs and TiO 2 is revealed. Such bridging states account for the fast adiabatic charge transfer from the QD donor to the TiO 2 acceptor, and may be a general feature for strongly coupled donor/acceptor systems. All the QDs/TiO 2 systems exhibit type II band alignments, with conduction band offsets that increase with the decrease in QD size. This facilitates the charge transfer from QDs donors to TiO 2 acceptors and explains the dependence of the increased charge transfer rate with the decreased QD size.« less

  4. Final Technical Report for the Energy Frontier Research Center Understanding Charge Separation and Transfer at Interfaces in Energy Materials (EFRC:CST)

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

    Vanden Bout, David A.

    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 themore » 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.« less

  5. Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

    NASA Technical Reports Server (NTRS)

    Steinfeld, J. I.; Foy, B.; Hetzler, J.; Flannery, C.; Klaassen, J.; Mizugai, Y.; Coy, S.

    1990-01-01

    The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

  6. [Effect of Charge-Transfer Complex on Ultraviolet-Visible (UV-Vis) Absorption Property of Chromophoric Dissolved Organic Matter (CDOM) in Waters of Typical Water-Level Fluctuation Zones of the Three Gorges Reservoir Areas].

    PubMed

    Jiang, Tao; Liang, Jian; Zhang, Mu-xue; Wang, Ding-yong; Wei, Shi-qiang; Lu, Song

    2016-02-15

    As an important fraction of dissolved organic matter (DOM), chromophoric dissolved organic matter (CDOM) plays a key role in decision of the optical properties and photogeochemistry of DOM, and further affects pollutant fate and global carbon cycle. These optical properties are ascribed to two chromophoric systems including superposition of individual chromophores and charge-transfer (CT) complexation between electron donor (e.g., phenols and indoles) and acceptor (e.g., quinones and other oxidized aromatics) in DOM structures. Thus in this study, based on the "double-chromophoric system" model, DOM samples from four typical water-level fluctuation zones of Three Gorges Reservoir (TGR) areas were selected, to investigate the effect and contribution of charge-transfer complex to ultraviolet-visible (UV-Vis) absorption property of CDOM. Using NaBH, reduction method, original featureless absorption curve was classified into two independent curves caused by individual chromophoric group, which were derived from a simple superposition of independent chromophore and charge-transfer complex, respectively. Also, the changes in curve properties and specific parameters before and after NaBH4 reduction were compared. The results showed that in all DOM samples from the four sites of TGR, more than 35% of absorption was attributed from CT complex. Shibaozhai of Zhongxian and Zhenxi of Fuling showed the highest proportion ( > 50%). It suggested that the role of CT complex in CDOM property could not be neglected. After removal of CT complex, absorption curve showed blue-shift and CDOM concentration [a (355)] decreased significantly. Meanwhile, because of deforming of bonds by reduction, DOM structures became more dispersive and the molecular size was decreased, resulting in the lower spectral slope (S) observed, which evidentially supported that the supermolecular association structure of DOM was self-assembled through CT complex. Meanwhile, deceasing hydrophobic components led

  7. HST/WFC3: Evolution of the UVIS Channel's Charge Transfer Efficiency

    NASA Astrophysics Data System (ADS)

    Gosmeyer, Catherine; Baggett, Sylvia M.; Anderson, Jay; WFC3 Team

    2016-06-01

    The Wide Field Camera 3 (WFC3) on the Hubble Space Telescope (HST) contains both an IR and a UVIS channel. After more than six years on orbit, the UVIS channel performance remains stable; however, on-orbit radiation damage has caused the charge transfer efficiency (CTE) of UVIS's two CCDs to degrade. This degradation is seen as vertical charge 'bleeding' from sources during readout and its effect evolves as the CCDs age. The WFC3 team has developed software to perform corrections that push the charge back to the sources, although it cannot recover faint sources that have been bled out entirely. Observers can mitigate this effect in various ways such as by placing sources near the amplifiers, observing bright targets, and by increasing the total background to at least 12 electrons, either by using a broader filter, lengthening exposure time, or post-flashing. We present results from six years of calibration data to re-evaluate the best level of total background for mitigating CTE loss and to re-verify that the pixel-based CTE correction software is performing optimally over various background levels. In addition, we alert observers that CTE-corrected products are now available for retrieval from MAST as part of the CALWF3 v3.3 pipeline upgrade.

  8. Superconductivity, phase separation, and charge-transfer instability in the U = infinity limit of the three-band model of the CuO sub 2 planes

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

    Grilli, M.; Raimondi, R.; Castellani, C.

    1991-07-08

    The {ital U}={infinity} limit of the three-band Hubbard model with nearest-neighbor repulsion {ital V} is studied using the slave-boson approach and the large-{ital N} expansion technique to order 1/{ital N}. A charge-transfer instability is found as in weak-coupling theory. The charge-transfer instability is always associated with a diverging compressibility leading to a phase separation. Near the phase-separation, charge-transfer-instability region we find superconducting instabilities in the {ital s}- and {ital d}-wave channel. The requirement for superconductivity is that {ital V} be on the scale of the Cu-O hopping as suggested by Varma, Schmitt-Rink, and Abrahams.

  9. Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections

    DOE PAGES

    Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya; ...

    2016-08-09

    The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C 61- butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonicmore » and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.« less

  10. Understanding How Isotopes Affect Charge Transfer in P3HT/PCBM: A Quantum Trajectory-Electronic Structure Study with Nonlinear Quantum Corrections

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

    Wang, Lei; Jakowski, Jacek; Garashchuk, Sophya

    The experimentally observed effect of selective deuterium substitution on the open circuit voltage for a blend of poly(3-hexylthiophene)(P3HT) and [6,6]-phenyl-C 61- butyric acid methyl ester (PCBM) (Nat. Commun. 5:3180, 2014) is explored using a 221-atom model of a polymer-wrapped PCBM molecule. We describe the protonic and deuteronic wavefunctions for the H/D isotopologues of the hexyl side chains within a Quantum Trajectory/Electronic Structure approach where the dynamics is performed with newly developed nonlinear corrections to the quantum forces, necessary to describe the nuclear wavefunctions; the classical forces are generated with a Density Functional Tight Binding method. We used the resulting protonicmore » and deuteronic time-dependent wavefunctions to assess the effects of isotopic substitution (deuteration) on the energy gaps relevant to the charge transfer for the donor and acceptor electronic states. Furthermore, while the isotope effect on the electronic energy levels is found negligible, the quantum-induced fluctuations of the energy gap between the charge transfer and charge separated states due to nuclear wavefunctions may account for experimental trends by promoting charge transfer in P3HT/PCBM and increasing charge recombination on the donor in the deuterium substituted P3HT/PCBM.« less

  11. Charge-pump voltage converter

    DOEpatents

    Brainard, John P [Albuquerque, NM; Christenson, Todd R [Albuquerque, NM

    2009-11-03

    A charge-pump voltage converter for converting a low voltage provided by a low-voltage source to a higher voltage. Charge is inductively generated on a transfer rotor electrode during its transit past an inductor stator electrode and subsequently transferred by the rotating rotor to a collector stator electrode for storage or use. Repetition of the charge transfer process leads to a build-up of voltage on a charge-receiving device. Connection of multiple charge-pump voltage converters in series can generate higher voltages, and connection of multiple charge-pump voltage converters in parallel can generate higher currents. Microelectromechanical (MEMS) embodiments of this invention provide a small and compact high-voltage (several hundred V) voltage source starting with a few-V initial voltage source. The microscale size of many embodiments of this invention make it ideally suited for MEMS- and other micro-applications where integration of the voltage or charge source in a small package is highly desirable.

  12. Blue Thermally Activated Delayed Fluorescence Polymers with Nonconjugated Backbone and Through-Space Charge Transfer Effect.

    PubMed

    Shao, Shiyang; Hu, Jun; Wang, Xingdong; Wang, Lixiang; Jing, Xiabin; Wang, Fosong

    2017-12-13

    We demonstrate novel molecular design for thermally activated delayed fluorescence (TADF) polymers based on a nonconjugated polyethylene backbone with through-space charge transfer effect between pendant electron donor (D) and acceptor (A) units. Different from conventional conjugated D-A polymers with through-bond charge transfer effect, the nonconjugated architecture avoids direct conjugation between D and A units, enabling blue emission. Meanwhile, spatial π-π interaction between the physically separated D and A units results in both small singlet-triplet energy splitting (0.019 eV) and high photoluminescence quantum yield (up to 60% in film state). The resulting polymer with 5 mol % acceptor unit gives efficient blue electroluminescence with Commission Internationale de l'Eclairage coordinates of (0.176, 0.269), together with a high external quantum efficiency of 12.1% and low efficiency roll-off of 4.9% (at 1000 cd m -2 ), which represents the first example of blue TADF nonconjugated polymer.

  13. Are hot charge transfer states the primary cause of efficient free-charge generation in polymer:fullerene organic photovoltaic devices? A kinetic Monte Carlo study.

    PubMed

    Jones, Matthew L; Dyer, Reesha; Clarke, Nigel; Groves, Chris

    2014-10-14

    Kinetic Monte Carlo simulations are used to examine the effect of high-energy, 'hot' delocalised charge transfer (HCT) states for donor:acceptor and mixed:aggregate blends, the latter relating to polymer:fullerene photovoltaic devices. Increased fullerene aggregation is shown to enhance charge generation and short-circuit device current - largely due to the increased production of HCT states at the aggregate interface. However, the instances where HCT states are predicted to give internal quantum efficiencies in the region of 50% do not correspond to HCT delocalisation or electron mobility measured in experiments. These data therefore suggest that HCT states are not the primary cause of high quantum efficiencies in some polymer:fullerene OPVs. Instead it is argued that HCT states are responsible for the fast charge generation seen in spectroscopy, but that regional variation in energy levels are the cause of long-term, efficient free-charge generation.

  14. Charge transfer at organic-organic heterojunctions, and remote doping of a pentacene transistor

    NASA Astrophysics Data System (ADS)

    Zhao, Wei

    Organic-organic heterojunctions (OOHs) are the fundamental building blocks of organic devices, such as organic light-emitting diodes, organic photovoltaic cells, and photo detectors. Transport of free electrons and holes, exciton formation, recombination or dissociation, and various other physical processes all take place in OOHs. Understanding the electronic structures of OOH is critical for studying device physics and further improving the performance of organic devices. This work focuses on the electronic structure, i.e., the energy level alignment, at OOHs, investigated by ultraviolet and inverse photoemission spectroscopy (UPS and IPES). The weak interaction that generally prevails at OOH interfaces leads to small interface dipoles of 0˜0.5eV. The experimental observations on the majority of OOHs studied can be semi-quantitatively predicted by the model derived from the induced density of interface states and charge neutrality level (IDIS/CNL). However, we also find that the electronic structure of interfaces between two small-band-gap semiconductors, e.g., using copper phthalocyanine (CuPc) as the donor and a tris(thieno)-hexaazatriphenylene derivative (THAP) as the acceptor, is strongly influenced by changes in the substrate work function. In these cases, the charge transfer that takes place at the interface is governed by thermodynamic equilibrium, dominating any subtle interaction due to IDIS/CNL. The impact of doping on the energy level alignment of OOHs is also studied. The charges donated by the dopant molecules transfer from the parent doped layer to the adjacent undoped layer, taking advantage of the molecular level offset, and are then spatially separated from the dopant molecules. Remote doping, based on this charge transfer mechanism, is demonstrated with the heterojunction formed between pentacene and N,N'-diphenyl-N,N'-bis(1-naphthyl)-1,1'bisphenyl-4,4'diazine (alpha-NPD) p-doped with tris[1,2-bis(trifluoromethyl) ethane-1,2-dithiolene] (Mo

  15. Charge-transfer mechanism for electrophilic aromatic nitration and nitrosation via the convergence of (ab initio) molecular-orbital and Marcus-Hush theories with experiments.

    PubMed

    Gwaltney, Steven R; Rosokha, Sergiy V; Head-Gordon, Martin; Kochi, Jay K

    2003-03-19

    The highly disparate rates of aromatic nitrosation and nitration, despite the very similar (electrophilic) properties of the active species: NO(+) and NO(2)(+) in Chart 1, are quantitatively reconciled. First, the thorough mappings of the potential-energy surfaces by high level (ab initio) molecular-orbital methodologies involving extensive coupled-cluster CCSD(T)/6-31G optimizations establish the intervention of two reactive intermediates in nitration (Figure 8) but only one in nitrosation (Figure 7). Second, the same distinctive topologies involving double and single potential-energy minima (Figures 6 and 5) also emerge from the semiquantitative application of the Marcus-Hush theory to the transient spectral data. Such a striking convergence from quite different theoretical approaches indicates that the molecular-orbital and Marcus-Hush (potential-energy) surfaces are conceptually interchangeable. In the resultant charge-transfer mechanism, the bimolecular interactions of arene donors with both NO(+) and NO(2)(+) spontaneously lead (barrierless) to pi-complexes in which electron transfer is concurrent with complexation. Such a pi-complex in nitration is rapidly converted to the sigma-complex, whereas this Wheland adduct in nitrosation merely represents a high energy (transition-state) structure. Marcus-Hush analysis thus demonstrates how the strongly differentiated (arene) reactivities toward NO(+) and NO(2)(+) can actually be exploited in the quantitative development of a single coherent (electron-transfer) mechanism for both aromatic nitrosation and nitration.

  16. Chemical and charge transfer studies on interfaces of a conjugated polymer and ITO

    NASA Astrophysics Data System (ADS)

    David, Tanya M. S.; Arasho, Wondwosson; Smith, O'Neil; Hong, Kunlun; Bonner, Carl; Sun, Sam-Shajing

    2017-08-01

    Conjugated oligomers and polymers are very attractive for potential future plastic electronic and opto-electronic device applications such as plastic photo detectors and solar cells, thermoelectric devices, field effect transistors, and light emitting diodes. Understanding and optimizing charge transport between an active polymer layer and conductive substrate is critical to the optimization of polymer based electronic and opto-electronic devices. This study focused on the design, synthesis, self-assembly, and electron transfers and transports of a phosphonic acid end-functionalized polyphenylenevinylene (PPV) that was covalently attached and self-assembled onto an Indium Tin Oxide (ITO) substrate. This study demonstrated how atomic force microscopy (AFM) can be an effective characterization technique in conjunction with conventional electron transfer methods, including cyclic voltammetry (CV), towards determining electron transfer rates in polymer and polymer/conductor interface systems. This study found that the electron transfer rates of covalently attached and self-assembled films were much faster than the spin coated films. The knowledge from this study can be very useful for designing potential polymer based electronic and opto-electronic thin film devices.

  17. Hydrodynamically induced fluid transfer and non-convective double-diffusion in microgravity sliding solvent diffusion cells

    NASA Technical Reports Server (NTRS)

    Pollmann, Konrad W.; Stodieck, Louis S.; Luttges, Marvin W.

    1994-01-01

    Microgravity can provide a diffusion-dominated environment for double-diffusion and diffusion-reaction experiments otherwise disrupted by buoyant convection or sedimentation. In sliding solvent diffusion cells, a diffusion interface between two liquid columns is achieved by aligning two offset sliding wells. Fluid in contact with the sliding lid of the cavities is subjected to an applied shear stress. The momentum change by the start/stop action of the well creates an additional hydrodynamical force. In microgravity, these viscous and inertial forces are sufficiently large to deform the diffusion interface and induce hydrodynamic transfer between the wells. A series of KC-135 parabolic flight experiments were conducted to characterize these effects and establish baseline data for microgravity diffusion experiments. Flow visualizations show the diffusion interface to be deformed in a sinusoidal fashion following well alignment. After the wells were separated again in a second sliding movement, the total induced liquid transfer was determined and normalized by the well aspect ratio. The normalized transfer decreased linearly with Reynolds number from 3.3 to 4.0% (w/v) for Re = 0.4 (Stokes flow) to a minimum of 1.0% for Re = 23 to 30. Reynolds numbers that provide minimum induced transfers are characterized by an interface that is highly deformed and unsuitable for diffusion measurements. Flat diffusion interfaces acceptable for diffusion measurements are obtained with Reynolds numbers on the order of 7 to 10. Microgravity experiments aboard a sounding rocket flight verified counterdiffusion of different solutes to be diffusion dominated. Ground control experiments showed enhanced mixing by double-diffusive convection. Careful selection of experimental parameters improves initial conditions and minimizes induced transfer rates.

  18. Mutation induction by charged particles of defined linear energy transfer.

    PubMed

    Hei, T K; Chen, D J; Brenner, D J; Hall, E J

    1988-07-01

    The mutagenic potential of charged particles of defined linear energy transfer (LET) was assessed using the hypoxanthine-guanine phosphoribosyl transferase locus (HGPRT) in primary human fibroblasts. Exponentially growing cultures of early passaged fibroblasts were grown as monolayers on thin mylar sheets and were irradiated with accelerated protons, deuterons or helium-3 ions. The mutation rates were compared with those generated by 137Cs gamma-rays. LET values for charged particles accelerated at the Radiological Research Accelerator Facility, using the track segment mode, ranged from 10 to 150 keV/micron. After irradiation, cells were trypsinized, subcultured and assayed for both cytotoxicity and 6-thioguanine resistance. For gamma-rays, and for the charged particles of lower LET, the dose-response curves for cell survival were characterized by a marked initial shoulder, but approximated to an exponential function of dose for higher LETs. Mutation frequencies, likewise, showed a direct correlation to LET over the dose range examined. Relative biological effectiveness (RBE) for mutagenesis, based on the initial slopes of the dose-response curves, ranged from 1.30 for 10 keV/micron protons to 9.40 for 150 keV/micron helium-3 ions. Results of the present studies indicate that high-LET radiations, apart from being efficient inducers of cell lethality, are even more efficient in mutation induction as compared to low-LET ionizing radiation. These data are consistent with results previously obtained with both rodent and human fibroblast cell lines.

  19. Donation and back-donation analyzed through a charge transfer model based on density functional theory.

    PubMed

    Orozco-Valencia, Ulises; Gázquez, José L; Vela, Alberto

    2017-07-01

    The net charge transfer process that occurs between two species, A and B, interacting with each other, may be decomposed into two processes: one in which A receives charge from B, which can be identified as the electrophilic channel for A or the nucleophilic channel for B, and a second in which A donates charge to B, which can be identified as the nucleophilic channel for A or the electrophilic channel for B. By determining the amount of charge associated with both processes through the minimization of the interaction energy associated with each case, the expressions for the amount of charge involved in each case can be expressed in terms of the directional chemical potentials and the hardnesses of the interacting species. The correlation between the charges obtained for the interaction between phosphine ligands of the type PRR'R'' and Ni, and the A 1 carbonyl stretching frequency provides support for their interpretation as measures of the electrophilicity and nucleophilicity of a chemical species, and, at the same time, allows one to describe the donation and back-donation processes in terms of the density functional theory of chemical reactivity.

  20. Excited-State Charge Separation in the Photochemical Mechanism of the Light-Driven Enzyme Protochlorophyllide Oxidoreductase**

    PubMed Central

    Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

    2015-01-01

    The unique light-driven enzyme protochlorophyllide oxidoreductase (POR) is an important model system for understanding how light energy can be harnessed to power enzyme reactions. The ultrafast photochemical processes, essential for capturing the excitation energy to drive the subsequent hydride- and proton-transfer chemistry, have so far proven difficult to detect. We have used a combination of time-resolved visible and IR spectroscopy, providing complete temporal resolution over the picosecond–microsecond time range, to propose a new mechanism for the photochemistry. Excited-state interactions between active site residues and a carboxyl group on the Pchlide molecule result in a polarized and highly reactive double bond. This so-called “reactive” intramolecular charge-transfer state creates an electron-deficient site across the double bond to trigger the subsequent nucleophilic attack of NADPH, by the negatively charged hydride from nicotinamide adenine dinucleotide phosphate. This work provides the crucial, missing link between excited-state processes and chemistry in POR. Moreover, it provides important insight into how light energy can be harnessed to drive enzyme catalysis with implications for the design of light-activated chemical and biological catalysts. PMID:25488797