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

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1993-12-07

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, Stuart F.; Rauh, R. David

1990-01-01

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

Solid state electrochromic light modulator

DOEpatents

Cogan, S.F.; Rauh, R.D.

1990-07-03

An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counter electrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films. 4 figs.

High-potential perfluorinated phthalocyanine-fullerene dyads for generation of high-energy charge-separated states: formation and photoinduced electron-transfer studies.

PubMed

Das, Sushanta K; Mahler, Andrew; Wilson, Angela K; D'Souza, Francis

2014-08-25

High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

Photoinduced Dynamics of Charge Separation: From Photosynthesis to Polymer–Fullerene Bulk Heterojunctions

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

Niklas, Jens; Beaupré, Serge; Leclerc, Mario

2015-06-18

Understanding charge separation and charge transport is crucial for improving the efficiency of organic solar cells. Their active media are based on organic molecules and polymers, serving as both light-absorbing and transport layers. The charge-transfer (CT) states play an important role, being intermediate for free carrier generation and charge recombination. Here, we use light-induced electron paramagnetic resonance spectroscopy to study the CT dynamics in blends of the polymers P3HT, PCDTBT, and PTB7 with the fullerene derivative C-60-PCBM. Time-resolved EPR measurements show strong spin-polarization patterns for all polymer-fullerene blends, confirming predominant generation of singlet CT states and partial orientation ordering nearmore » the donor-acceptor interface. These observations allow a comparison with charge separation processes in molecular donor-acceptor systems and in natural and artificial photosynthetic assemblies, and thus the elucidation of the initial steps of sequential CT in organic photovoltaic materials.« less

Enhanced Internal Quantum Efficiency in Dye-Sensitized Solar Cells: Effect of Long-Lived Charge-Separated State of Sensitizers.

PubMed

Sun, Haiya; Liu, Dongzhi; Wang, Tianyang; Lu, Ting; Li, Wei; Ren, Siyao; Hu, Wenping; Wang, Lichang; Zhou, Xueqin

2017-03-22

Effective charge separation is one of the key determinants for the photovoltaic performance of the dye-sensitized solar cells (DSSCs). Herein, two charge-separated (CS) sensitizers, MTPA-Pyc and YD-Pyc, have been synthesized and applied in DSSCs to investigate the effect of the CS states of the sensitizers on the device's efficiency. The CS states with lifetimes of 64 and 177 ns for MTPA-Pyc and YD-Pyc, respectively, are formed via the photoinduced electron transfer (PET) from the 4-styryltriphenylamine (MTPA) or 4-styrylindoline (YD) donor to the pyrimidine cyanoacrylic acid (Pyc) acceptor. DSSCs based on MTPA-Pyc and YD-Pyc exhibit high internal quantum efficiency (IQE) values of over 80% from 400 to 600 nm. In comparison, the IQEs of the charge transfer (CT) sensitizer cells are 10-30% lower in the same wavelength range. The enhanced IQE values in the devices based on the CS sensitizers are ascribed to the higher electron injection efficiencies and slower charge recombination. The results demonstrate that taking advantage of the CS states in the sensitizers can be a promising strategy to improve the IQEs and further enhance the overall efficiencies of the DSSCs.

Steady-state and time-resolved studies on the photophysical properties of fullerene-pyropheophorbide a complexes in polar and nonpolar solvents

NASA Astrophysics Data System (ADS)

Ermilov, E. A.; Al-Omari, S.; Helmreich, M.; Jux, N.; Hirsch, A.; Röder, B.

2004-04-01

A novel monofullerene-bis(pyropheophorbide a) dyad has been photophysically characterized by steady-state as well as time-resolved techniques. It was revealed that in this complex strong and fast quenching of the first excited singlet state of the pyropheophorbide a (pyroPheo) molecule occurs by efficient photoinduced electron transfer to the fullerene moiety in both polar (DMF) and nonpolar (toluene) solvents. In DMF the energy of the charge-separated state is 0.94 eV and it undergoes directly transition to the ground state resulting in a very low value of photosensitized singlet oxygen generation. In contrast to the situation in a polar solvent, in toluene the charge-separated state lies above the exited triplet state of pyroPheo as well as that of C 60. It has been shown that in a nonpolar solvent a sufficient amount of singlet oxygen was generated by energy transfer from the excited triplet state of pyroPheo which has been populated via relaxation of the charge-separated state.

Extension of the charge separated-state lifetime by supramolecular association of a tetrathiafulvalene electron donor to a zinc/gold bisporphyrin.

PubMed

Boixel, Julien; Fortage, Jérôme; Blart, Errol; Pellegrin, Yann; Hammarström, Leif; Becker, Hans-Christian; Odobel, Fabrice

2010-02-14

Supramolecular triads were prepared by self-assembly of 4'-pyridyl-2-tetrathiafulvalene axially bound on ZnP-spacer-AuP(+) dyads; the lifetime of the charge separated state ((+)TTF-ZnP-Spacer-AuP ) formed upon light excitation of the triad is greatly increased with respect to that found in the parent dyad.

Energy gap law of electron transfer in nonpolar solvents.

PubMed

Tachiya, M; Seki, Kazuhiko

2007-09-27

We investigate the energy gap law of electron transfer in nonpolar solvents for charge separation and charge recombination reactions. In polar solvents, the reaction coordinate is given in terms of the electrostatic potentials from solvent permanent dipoles at solutes. In nonpolar solvents, the energy fluctuation due to solvent polarization is absent, but the energy of the ion pair state changes significantly with the distance between the ions as a result of the unscreened strong Coulomb potential. The electron transfer occurs when the final state energy coincides with the initial state energy. For charge separation reactions, the initial state is a neutral pair state, and its energy changes little with the distance between the reactants, whereas the final state is an ion pair state and its energy changes significantly with the mutual distance; for charge recombination reactions, vice versa. We show that the energy gap law of electron-transfer rates in nonpolar solvents significantly depends on the type of electron transfer.

Interaction of highly charged ions with carbon nano membranes

NASA Astrophysics Data System (ADS)

Gruber, Elisabeth; Wilhelm, Richard A.; Smejkal, Valerie; Heller, René; Facsko, Stefan; Aumayr, Friedrich

2015-09-01

Charge state and energy loss measurements of slow highly charged ions (HCIs) after transmission through nanometer and sub-nanometer thin membranes are presented. Direct transmission measurements through carbon nano membranes (CNMs) show an unexpected bimodal exit charge state distribution, accompanied by charge exchange dependent energy loss. The energy loss of ions in CNMs with large charge loss shows a quadratic dependency on the incident charge state, indicating charge state dependent stopping force values. Another access to the exit charge state distribution is given by irradiating stacks of CNMs and investigating each layer of the stack with high resolution imaging techniques like transmission electron microscopy (TEM) and helium ion microscopy (HIM) independently. The observation of pores created in all of the layers confirms the assumption derived from the transmission measurements that the two separated charge state distributions reflect two different impact parameter regimes, i.e. close collision with large charge exchange and distant collisions with weak ion-target interaction.

Guest and solvent modulated photo-driven charge separation and triplet generation in a perylene bisimide cyclophane

DOE PAGES

Spenst, Peter; Young, Ryan M.; Wasielewski, Michael R.; ...

2016-05-18

Cofacial positioning of two perylene bisimide (PBI) chromophores at a distance of 6.5 Å in a cyclophane structure prohibits the otherwise common excimer formation and directs photoexcited singlet state relaxation towards intramolecular symmetry-breaking charge separation (τ CS = 161 ± 4 ps) in polar CH 2Cl 2, which is thermodynamically favored with a Gibbs free energy of ΔG CS = –0.32 eV. The charges then recombine slowly in τ CR = 8.90 ± 0.06 ns to form the PBI triplet excited state, which can be used subsequently to generate singlet oxygen in 27% quantum yield. This sequence of events ismore » eliminated by dissolving the PBI cyclophane in non-polar toluene, where only excited singlet state decay occurs. In contrast, complexation of electron-rich aromatic hydrocarbons by the host PBI cyclophane followed by photoexcitation of PBI results in ultrafast electron transfer (<10 ps) from the guest to the PBI in CH 2Cl 2. As a result, the rate constants for charge separation and recombination increase as the guest molecules become easier to oxidize, demonstrating that charge separation occurs close to the peak of the Marcus curve and the recombination lies far into the Marcus inverted region.« less

Non-Faradaic Li + Migration and Chemical Coordination across Solid-State Battery Interfaces

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

Gittleson, Forrest S.; El Gabaly, Farid

Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at critical electrode–electrolyte interfaces have proven successful, yet interfacial chemistry and its impact on cell function remains poorly understood. Using X-ray photoelectron spectroscopy combined with electrochemical techniques, we elucidate chemical coordination near the LiCoO 2–LIPON interface, providing experimental validation of space-charge separation. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chemistry of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li+ ions from the electrode to themore » electrolyte, which reduces reversible cathodic capacity by ~15%. Inserting a thin, ion-conducting LiNbO 3 interlayer between the electrode and electrolyte, however, can reduce space-charge separation, mitigate the loss of Li+ from LiCoO 2, and return cathodic capacity to its theoretical value. This work illustrates the importance of interfacial chemistry in understanding and improving solid-state batteries.« less

Fast charge separation in a non-fullerene organic solar cell with a small driving force

NASA Astrophysics Data System (ADS)

Liu, Jing; Chen, Shangshang; Qian, Deping; Gautam, Bhoj; Yang, Guofang; Zhao, Jingbo; Bergqvist, Jonas; Zhang, Fengling; Ma, Wei; Ade, Harald; Inganäs, Olle; Gundogdu, Kenan; Gao, Feng; Yan, He

2016-07-01

Fast and efficient charge separation is essential to achieve high power conversion efficiency in organic solar cells (OSCs). In state-of-the-art OSCs, this is usually achieved by a significant driving force, defined as the offset between the bandgap (Egap) of the donor/acceptor materials and the energy of the charge transfer (CT) state (ECT), which is typically greater than 0.3 eV. The large driving force causes a relatively large voltage loss that hinders performance. Here, we report non-fullerene OSCs that exhibit ultrafast and efficient charge separation despite a negligible driving force, as ECT is nearly identical to Egap. Moreover, the small driving force is found to have minimal detrimental effects on charge transfer dynamics of the OSCs. We demonstrate a non-fullerene OSC with 9.5% efficiency and nearly 90% internal quantum efficiency despite a low voltage loss of 0.61 V. This creates a path towards highly efficient OSCs with a low voltage loss.

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Picosecond absorption studies of photoinduced charge separation in polyelectrolyte bound aromatic chromophores

NASA Astrophysics Data System (ADS)

Shand, M. A.; Rodgers, M. A. J.; Webber, S. E.

1991-02-01

Picosecond absorption studies of photoinduced electron transfer between aromatic chromophores bound to polymethacrylic acid (P) and methylviologen (MV 2+ have been carried out in aqueous solution. The diphenylanthracene copolymer/viologen system at pH 2.8 shows the corresponding redox products DPA + rad and MV + rad arising from the singlet state of DPA with a forward rate constant of electron transfer of 2.6 × 10 9 s -1. At pH 9.0 the quenching of the S 1 state of DPA occurs with no charge separated products being observed. The pyrene copolymer shows no evidence of charge separated products at any pH in the range 2.8-9.0. It is proposed that the differences in the radical pair kinetics arise from differences in the degree of binding of the ground state complexes formed by the donor and acceptor species.

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.

17 CFR 270.26a-2 - Exemptions from certain provisions of sections 26 and 27 for registered separate accounts and...

Code of Federal Regulations, 2010 CFR

2010-04-01

... deduction of certain fees and charges from the assets of such accounts. 270.26a-2 Section 270.26a-2... registered separate accounts and others regarding custodianship of and deduction of certain fees and charges... by any State or other governmental entity and, if the separate account is registered under the Act as...

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.

Long-lived charge carrier generation in ordered films of a covalent perylenediimide–diketopyrrolopyrrole–perylenediimide molecule

DOE PAGES

Hartnett, Patrick E.; Dyar, Scott M.; Margulies, Eric A.; ...

2015-07-31

The photophysics of a covalently linked perylenediimide–diketopyrrolopyrrole–perylenediimide acceptor–donor–acceptor molecule (PDI–DPP–PDI, 1) were investigated and found to be markedly different in solution versus in unannealed and solvent annealed films. Photoexcitation of 1 in toluene results in quantitative charge separation in τ = 3.1 ± 0.2 ps, with charge recombination in τ = 340 ± 10 ps, while in unannealed/disordered films of 1, charge separation occurs in τ < 250 fs, while charge recombination displays a multiexponential decay in ~6 ns. The absence of long-lived, charge separation in the disordered film suggests that few free charge carriers are generated. In contrast, uponmore » CH₂Cl₂ vapor annealing films of 1, grazing-incidence X-ray scattering shows that the molecules form a more ordered structure. Photoexcitation of the ordered films results in initial formation of a spin-correlated radical ion pair (electron–hole pair) as indicated by magnetic field effects on the formation of free charge carriers which live for ~4 μs. This result has significant implications for the design of organic solar cells based on covalent donor–acceptor systems and shows that long-lived, charge-separated states can be achieved by controlling intramolecular charge separation dynamics in well-ordered systems.« less

Equilibrium charge state distributions of Ni, Co, and Cu beams in molybdenum foil at 2 MeV/u

NASA Astrophysics Data System (ADS)

Gastis, Panagiotis; Perdikakis, George; Robertson, Daniel; Bauder, Will; Skulski, Michael; Collon, Phillipe; Anderson, Tyler; Ostdiek, Karen; Aprahamian, Ani; Lu, Wenting; Almus, Robert

2015-10-01

The charge states of heavy-ions are important for the study of nuclear reactions in inverse kinematics when electromagnetic recoil mass spectrometers are used. The passage of recoil products through a material, like the windows of gas cells or charge state boosters, results a charge state distribution (CSD) in the exit. This distribution must be known for the extraction of any cross section since only few charge-state can be transmitted through a magnetic separator separator for a given setting. The calculation of CSDs for heavy ions is challenging. Currently we rely on semi-empirical models with unknown accuracy for ion/target combinations in the Z > 20 region. In the present study were measured the CSDs of the stable 60Ni, 59Co, and 63Cu beams while passing through a 1 μm molybdenum foil. The beam energies were 1.84 MeV/u, 2.09 MeV/u, and 2.11 MeV/u for the 60Ni, 59Co, and 63Cu respectively. The results of this study mainly check the accuracy of the semi-empirical models used by the program LISE++, on calculating CSDs for ion/target combinations of Z > 20. In addition, other empirical models on calculating mean charge states were compared and checked.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

DOE PAGES

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.; ...

2017-09-13

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Charge Separation and Triplet Exciton Formation Pathways in Small Molecule Solar Cells as Studied by Time-resolved EPR Spectroscopy.

PubMed

Thomson, Stuart A J; Niklas, Jens; Mardis, Kristy L; Mallares, Christopher; Samuel, Ifor D W; Poluektov, Oleg G

2017-10-19

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2 ) 2 , DTS(F 2 BTTh 2 ) 2 , DTS(PTTh 2 ) 2 , DTG(FBTTh 2 ) 2 and DTG(F 2 BTTh 2 ) 2 ) with the fullerene derivative PC 61 BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2 ) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2 ) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. The higher BET triplet exciton population in the DTS(PTTh 2 ) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.

Charge Separation and Triplet Exciton Formation Pathways in Small-Molecule Solar Cells as Studied by Time-Resolved EPR Spectroscopy

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

Thomson, Stuart A. J.; Niklas, Jens; Mardis, Kristy L.

Organic solar cells are a promising renewable energy technology, offering the advantages of mechanical flexibility and solution processability. An understanding of the electronic excited states and charge separation pathways in these systems is crucial if efficiencies are to be further improved. Here we use light induced electron paramagnetic resonance (LEPR) spectroscopy and density functional theory calculations (DFT) to study the electronic excited states, charge transfer (CT) dynamics and triplet exciton formation pathways in blends of the small molecule donors (DTS(FBTTh 2) 2, DTS(F2BTTh 2) 2, DTS(PTTh 2) 2, DTG(FBTTh 2) 2 and DTG(F2BTTh 2) 2) with the fullerene derivative PCmore » 61BM. Using high frequency EPR the g-tensor of the positive polaron on the donor molecules was determined. The experimental results are compared with DFT calculations which reveal that the spin density of the polaron is distributed over a dimer or trimer. Time-resolved EPR (TR-EPR) spectra attributed to singlet CT states were identified and the polarization patterns revealed similar charge separation dynamics in the four fluorobenzothiadiazole donors, while charge separation in the DTS(PTTh 2) 2 blend is slower. Using TR-EPR we also investigated the triplet exciton formation pathways in the blend. The polarization patterns reveal that the excitons originate from both intersystem crossing (ISC) and back electron transfer (BET) processes. The DTS(PTTh 2) 2 blend was found to contain substantially more triplet excitons formed by BET than the fluorobenzothiadiazole blends. As a result, the higher BET triplet exciton population in the DTS(PTTh 2) 2 blend is in accordance with the slower charge separation dynamics observed in this blend.« less

Utilization of photoinduced charge-separated state of donor-acceptor-linked molecules for regulation of cell membrane potential and ion transport.

PubMed

Numata, Tomohiro; Murakami, Tatsuya; Kawashima, Fumiaki; Morone, Nobuhiro; Heuser, John E; Takano, Yuta; Ohkubo, Kei; Fukuzumi, Shunichi; Mori, Yasuo; Imahori, Hiroshi

2012-04-11

The control of ion transport across cell membranes by light is an attractive strategy that allows targeted, fast control of precisely defined events in the biological membrane. Here we report a novel general strategy for the control of membrane potential and ion transport by using charge-separation molecules and light. Delivery of charge-separation molecules to the plasma membrane of PC12 cells by a membranous nanocarrier and subsequent light irradiation led to depolarization of the membrane potential as well as inhibition of the potassium ion flow across the membrane. Photoregulation of the cell membrane potential and ion transport by using charge-separation molecules is highly promising for control of cell functions. © 2012 American Chemical Society

Optical excitations dynamics at hetero-interfaces fullerene/quantum dots

NASA Astrophysics Data System (ADS)

Righetto, Marcello; Privitera, Alberto; Franco, Lorenzo; Bozio, Renato

2017-08-01

Embedding Semiconductor Quantum Dots (QDs) into hybrid organic-inorganic solar cell holds promises for improving photovoltaic performances. Thanks to their strong coupling with electro-magnetic radiation field, QDs represent paradigmatic photon absorbers. Nevertheless, the quest for suitable charge separating hetero-interfaces is still an open challenge. Within this framework, the excited state interactions between QDs and fullerene derivatives are of great interest for ternary solar cells (polymer:QDs:fullerene). In this work, we investigated the exciton dynamics of core/shell CdSe/CdS QDs both in solution and in blends with fullerene derivative (PCBM). By means of transient optical techniques, we aimed to unveil the dynamics of the QDs-PCBM interaction. Indeed, the observed excited state depopulation of QDs in blends is compatible with an excited state interaction living on picosecond timescale. Through electron paramagnetic resonance, we delved into the nature of this interaction, identifying the presence of charge separated states. The concurrence of these observations suggest a fast electron transfer process, where QDs act as donors and PCBM molecules as acceptors, followed by effective charge separation. Therefore, our experimental results indicate the QDs-PCBM heterointerface as suitable exciton separating interface, paving the way for possible applications in photovoltaics.

How exciton-vibrational coherences control charge separation in the photosystem II reaction center.

PubMed

Novoderezhkin, Vladimir I; Romero, Elisabet; van Grondelle, Rienk

2015-12-14

In photosynthesis absorbed sun light produces collective excitations (excitons) that form a coherent superposition of electronic and vibrational states of the individual pigments. Two-dimensional (2D) electronic spectroscopy allows a visualization of how these coherences are involved in the primary processes of energy and charge transfer. Based on quantitative modeling we identify the exciton-vibrational coherences observed in 2D photon echo of the photosystem II reaction center (PSII-RC). We find that the vibrations resonant with the exciton splittings can modify the delocalization of the exciton states and produce additional states, thus promoting directed energy transfer and allowing a switch between the two charge separation pathways. We conclude that the coincidence of the frequencies of the most intense vibrations with the splittings within the manifold of exciton and charge-transfer states in the PSII-RC is not occurring by chance, but reflects a fundamental principle of how energy conversion in photosynthesis was optimized.

Investigations on the photoreactions of phenothiazine and phenoxazine in presence of 9-cyanoanthracene by using steady state and time resolved spectroscopic techniques.

PubMed

Bardhan, Munmun; Mandal, Paulami; Tzeng, Wen-Bih; Ganguly, Tapan

2010-09-01

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).

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

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

Kaufmann, K.J.

1980-12-01

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

Chiral perturbation theory and nucleon-pion-state contaminations in lattice QCD

NASA Astrophysics Data System (ADS)

Bär, Oliver

2017-05-01

Multiparticle states with additional pions are expected to be a non-negligible source of excited-state contamination in lattice simulations at the physical point. It is shown that baryon chiral perturbation theory can be employed to calculate the contamination due to two-particle nucleon-pion-states in various nucleon observables. Leading order results are presented for the nucleon axial, tensor and scalar charge and three Mellin moments of parton distribution functions (quark momentum fraction, helicity and transversity moment). Taking into account phenomenological results for the charges and moments the impact of the nucleon-pion-states on lattice estimates for these observables can be estimated. The nucleon-pion-state contribution results in an overestimation of all charges and moments obtained with the plateau method. The overestimation is at the 5-10% level for source-sink separations of about 2 fm. The source-sink separations accessible in contemporary lattice simulations are found to be too small for chiral perturbation theory to be directly applicable.

Versatile organic (fullerene)-inorganic (CdTe nanoparticle) nanoensembles.

PubMed

Guldi, Dirk M; Zilbermann, Israel; Anderson, Greg; Kotov, Nicholas A; Tagmatarchis, Nikos; Prato, Maurizio

2004-11-10

Novel organic (positively charged fullerene)-inorganic (negatively charged CdTe nanoparticle) nanoensembles were devised through electrostatic interactions and probed as versatile donor-acceptor hybrids. Photoirradiation of their homogeneous solutions, containing the electrostatically packed components, let to very long-lived (1.3 ms) charge separated states.

The nature of the excited state of the reaction center of photosystem II of green plants: A high-resolution fluorescence spectroscopy study

PubMed Central

Peterman, Erwin J. G.; van Amerongen, Herbert; van Grondelle, Rienk; Dekker, Jan P.

1998-01-01

We studied the electronically excited state of the isolated reaction center of photosystem II with high-resolution fluorescence spectroscopy at 5 K and compared the obtained spectral features with those obtained earlier for the primary electron donor. The results show that there is a striking resemblance between the emitting and charge-separating states in the photosystem II reaction center, such as a very similar shape of the phonon wing with characteristic features at 19 and 80 cm−1, almost identical frequencies of a number of vibrational modes, a very similar double-Gaussian shape of the inhomogeneous distribution function, and relatively strong electron-phonon coupling for both states. We suggest that the emission at 5 K originates either from an exciton state delocalized over the inactive branch of the photosystem or from a fraction of the primary electron donor that is long-lived at 5 K. The latter possibility can be explained by a distribution of the free energy difference of the primary charge separation reaction around zero. Both possibilities are in line with the idea that the state that drives primary charge separation in the reaction center of photosystem II is a collective state, with contributions from all chlorophyll molecules in the central part of the complex. PMID:9600929

Ultrafast photoinduced charge transport in Pt(II) donor-acceptor assembly bearing naphthalimide electron acceptor and phenothiazine electron donor.

PubMed

Sazanovich, Igor V; Best, Jonathan; Scattergood, Paul A; Towrie, Michael; Tikhomirov, Sergei A; Bouganov, Oleg V; Meijer, Anthony J H M; Weinstein, Julia A

2014-12-21

Visible light-induced charge transfer dynamics were investigated in a novel transition metal triad acceptor-chromophore-donor, (NDI-phen)Pt(II)(-C≡C-Ph-CH2-PTZ)2 (1), designed for photoinduced charge separation using a combination of time-resolved infrared (TRIR) and femtosecond electronic transient absorption (TA) spectroscopy. In 1, the electron acceptor is 1,4,5,8-naphthalene diimide (NDI), and the electron donor is phenothiazine (PTZ), and [(phen)Pt(-C≡C-Ph-)], where phen is 1,10-phenanthroline, represents the chromophoric core. The first excited state observed in 1 is a (3)MLCT/LL'CT, with {Pt(II)-acetylide}-to-phen character. Following that, charge transfer from the phen-anion onto the NDI subunit to form NDI(-)-phen-[Pt-(C≡C)2](+)-PTZ2 occurs with a time constant of 2.3 ps. This transition is characterised by appearance of the prominent NDI-anion features in both TRIR and TA spectra. The final step of the charge separation in 1 proceeds with a time constant of ∼15 ps during which the hole migrates from the [Pt-(C≡C)2] subunit to one of the PTZ groups. Charge recombination in 1 then occurs with two distinct time constants of 36 ns and 107 ns, corresponding to the back electron transfer to each of the two donor groups; a rather rare occurrence which manifests that the hole in the final charge-separated state is localised on one of the two donor PTZ groups. The assignment of the nature of the excited states and dynamics in 1 was assisted by TRIR investigations of the analogous previously reported ((COOEt)2bpy)Pt(C≡C-Ph-CH2-PTZ)2 (2), (J. E. McGarrah and R. Eisenberg, Inorg. Chem., 2003, 42, 4355; J. E. McGarrah, J. T. Hupp and S. N. Smirnov, J. Phys. Chem. A, 2009, 113, 6430) as well as (bpy)Pt(C≡C-Ph-C7H15)2, which represent the acceptor-free dyad, and the chromophoric core, respectively. Thus, the step-wise formation of the full charge-separated state on the picosecond time scale and charge recombination via tunnelling have been established; and the presence of two distinct charge recombination pathways has been observed.

Exploring Photoinduced Excited State Evolution in Heterobimetallic Ru(II)-Co(III) Complexes.

PubMed

Kuhar, Korina; Fredin, Lisa A; Persson, Petter

2015-06-18

Quantum chemical calculations provide detailed theoretical information concerning key aspects of photoinduced electron and excitation transfer processes in supramolecular donor-acceptor systems, which are particularly relevant to fundamental charge separation in emerging molecular approaches for solar energy conversion. Here we use density functional theory (DFT) calculations to explore the excited state landscape of heterobimetallic Ru-Co systems with varying degrees of interaction between the two metal centers, unbound, weakly bound, and tightly bound systems. The interplay between structural and electronic factors involved in various excited state relaxation processes is examined through full optimizations of multiple charge/spin states of each of the investigated systems. Low-energy relaxed heterobimetallic states of energy transfer and excitation transfer character are characterized in terms of energy, structure, and electronic properties. These findings support the notion of efficient photoinduced charge separation from a Ru(II)-Co(III) ground state, via initial optical excitation of the Ru-center, to low-energy Ru(III)-Co(II) states. The strongly coupled system has significant involvement of the conjugated bridge, qualitatively distinguishing it from the other two weakly coupled systems. Finally, by constructing potential energy surfaces for the three systems where all charge/spin state combinations are projected onto relevant reaction coordinates, excited state decay pathways are explored.

Multipulse spectroscopy on the wild-type and YM210W Bacterial Reaction Centre uncovers a new intermediate state in the special pair excited state

NASA Astrophysics Data System (ADS)

Cohen Stuart, T. A.; van Grondelle, R.

2009-06-01

The Bacterial Reaction Centre (BRC) has a complex electronic excited state, P ∗, that evolves into subsequent charge separated product states P +H - and P +B -. Pump-dump-probe spectroscopy on the wild-type BRC and on YM210W, a mutant with a stabilized, long-lived P ∗ excited state, has uncovered a new charge-separated state in both BRC's. When P ∗ is dumped, a fraction of its population is transferred to this state that has a strong Stark shift in the accessory bacteriochlorophyll (B M) region which serves as a signature for P + and a lifetime highly comparable to the slow phase of P ∗ decay. This lead us propose this intermediate to be P +/P -.

Hot kinetic model as a guide to improve organic photovoltaic materials.

PubMed

Sosorev, Andrey Yu; Godovsky, Dmitry Yu; Paraschuk, Dmitry Yu

2018-01-31

The modeling of organic solar cells (OSCs) can provide a roadmap for their further improvement. Many OSC models have been proposed in recent years; however, the impact of the key intermediates from photons to electricity-hot charge-transfer (CT) states-on the OSC efficiency is highly ambiguous. In this study, we suggest an analytical kinetic model for OSC that considers a two-step charge generation via hot CT states. This hot kinetic model allowed us to evaluate the impact of different material parameters on the OSC performance: the driving force for charge separation, optical bandgap, charge mobility, geminate recombination rate, thermalization rate, average electron-hole separation distance in the CT state, dielectric permittivity, reorganization energy and charge delocalization. In contrast to a widespread trend of lowering the material bandgap, the model predicts that this approach is only efficient along with improvement of the other material properties. The most promising ways to increase the OSC performance are decreasing the reorganization energy, i.e., an energy change accompanying CT from the donor molecule to the acceptor, increasing the dielectric permittivity and charge delocalization. The model suggests that there are no fundamental limitations that can prevent achieving the OSC efficiency above 20%.

Protein separation using an electrically tunable membrane

NASA Astrophysics Data System (ADS)

Jou, Ining; Melnikov, Dmitriy; Gracheva, Maria

Separation of small proteins by charge with a solid-state porous membrane requires control over the protein's movement. Semiconductor membrane has this ability due to the electrically tunable electric potential profile inside the nanopore. In this work we investigate the possibility to separate the solution of two similar sized proteins by charge. As an example, we consider two small globular proteins abundant in humans: insulin (negatively charged) and ubiquitin (neutral). We find that the localized electric field inside the pore either attracts or repels the charged protein to or from the pore wall which affects the delay time before a successful translocation of the protein through the nanopore. However, the motion of the uncharged ubiquitin is unaffected. The difference in the delay time (and hence the separation) can be further increased by the application of the electrolyte bias which induces an electroosmotic flow in the pore. NSF DMR and CBET Grant No. 1352218.

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

PubMed

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

2007-01-18

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

Magnetic Control of the Charge-Separated State Lifetime Realized by Covalent Attachment of a Platinum Complex.

PubMed

Miura, Tomoaki; Fujiwara, Dai; Akiyama, Kimio; Horikoshi, Takafumi; Suzuki, Shuichi; Kozaki, Masatoshi; Okada, Keiji; Ikoma, Tadaaki

2017-02-02

Dynamics of the photogenerated charge-separated (CS) state is studied for a newly synthesized molecular triad, in which the donor (D) dimethoxytriphenylamine, 1,3-bis(2-pyridylimino)isoindolate platinum (BPIPt), and the acceptor (A) naphthaldiimide are linked with a triethynylbenzene unit (BPIPt-DA). Photoexcitation of BPIPt gives rise to generation of a long-lived (∼4 μs) CS state BPIPt-D + A - , of which the lifetime is considerably increased by an applied magnetic field of 270 mT. The positive magnetic field effect (MFE) is in contrast to the negative MFE for the reference DA molecule, which indicates successful switching of the initial spin state of the CS state from singlet to triplet. Simulations of the MFE and time-resolved electron paramagnetic resonance show that spin-selective charge recombination and spin relaxation are unaffected by attachment of BPIPt. The minimum impact of heavy atom substitution on the electronic and magnetic properties has been realized by the small electronic coupling mediated by the rigid meta-triethynylbenzene.

Inherent Driving Force for Charge Separation in Curved Stacks of Oligothiophenes

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

Wu, Qin

Coexistence of high local charge mobility and an energy gradient can lead to efficient free charge carrier generation from geminate charge transfer states at the donor–acceptor interface in bulk heterojunction organic photovoltaics. It is, however, not clear what polymer microstructures can support such coexistence. Using recent methods from density functional theory, we propose that a stack of similarly curved oligothiophene chains can deliver the requirements for efficient charge separation. Curved stacks are stable because of the polymer’s strong π-stacking ability and because backbone torsions are flexible in neutral chains. However, energy of a charge in a polymer chain has remarkablymore » stronger dependence on torsions. The trend of increasing planarity in curved stacks effectively creates an energy gradient that drives charge in one direction. The curvature of these partially ordered stacks is found to beneficially interact with fullerenes for charge separation. The curved stacks, therefore, are identified as possible building blocks for interfacial structures that lead to efficient free carrier generation in high-performing organic photovoltaic systems.« less

Inherent Driving Force for Charge Separation in Curved Stacks of Oligothiophenes

DOE PAGES

Wu, Qin

2015-01-30

Coexistence of high local charge mobility and an energy gradient can lead to efficient free charge carrier generation from geminate charge transfer states at the donor–acceptor interface in bulk heterojunction organic photovoltaics. It is, however, not clear what polymer microstructures can support such coexistence. Using recent methods from density functional theory, we propose that a stack of similarly curved oligothiophene chains can deliver the requirements for efficient charge separation. Curved stacks are stable because of the polymer’s strong π-stacking ability and because backbone torsions are flexible in neutral chains. However, energy of a charge in a polymer chain has remarkablymore » stronger dependence on torsions. The trend of increasing planarity in curved stacks effectively creates an energy gradient that drives charge in one direction. The curvature of these partially ordered stacks is found to beneficially interact with fullerenes for charge separation. The curved stacks, therefore, are identified as possible building blocks for interfacial structures that lead to efficient free carrier generation in high-performing organic photovoltaic systems.« less

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.

Multi-hadron-state contamination in nucleon observables from chiral perturbation theory

NASA Astrophysics Data System (ADS)

Bär, Oliver

2018-03-01

Multi-particle states with additional pions are expected to be a non-negligible source of the excited-state contamination in lattice simulations at the physical point. It is shown that baryon chiral perturbation theory (ChPT) can be employed to calculate the contamination due to two-particle nucleon-pion states in various nucleon observables. Results to leading order are presented for the nucleon axial, tensor and scalar charge and three Mellin moments of parton distribution functions: the average quark momentum fraction, the helicity and the transversity moment. Taking into account experimental and phenomenological results for the charges and moments the impact of the nucleon-pionstates on lattice estimates for these observables can be estimated. The nucleon-pion-state contribution leads to an overestimation of all charges and moments obtained with the plateau method. The overestimation is at the 5-10% level for source-sink separations of about 2 fm. Existing lattice data is not in conflict with the ChPT predictions, but the comparison suggests that significantly larger source-sink separations are needed to compute the charges and moments with few-percent precision. Talk given at the 35th International Symposium on Lattice Field Theory, 18 - 24 June 2017, Granada, Spain.

Charge separation related to photocatalytic H 2 production from a Ru–apoflavodoxin–Ni biohybrid

DOE PAGES

Soltau, Sarah R.; Niklas, Jens; Dahlberg, Peter D.; ...

2016-12-27

The direct creation of a fuel from sunlight and water via photochemical energy conversion provides a sustainable method for producing a clean source of energy. Here we report the preparation of a solar fuel biohybrid that embeds a nickel diphosphine hydrogen evolution catalyst into the cofactor binding pocket of the electron shuttle protein, flavodoxin (Fld). The system is made photocatalytic by linking a cysteine residue in Fld to a ruthenium photosensitizer. Importantly, the protein environment enables the otherwise insoluble Ni catalyst to perform photocatalysis in aqueous solution over a pH range of 3.5–12.0, with optimal turnover frequency 410 ± 30more » h –1 and turnover number 620 ± 80 mol H 2/mol hybrid observed at pH 6.2. For the first time, a reversible light-induced charge-separated state involving a Ni(I) intermediate was directly monitored by electron paramagnetic resonance spectroscopy. As a result, transient optical measurements reflect two conformational states, with a Ni(I) state formed in ~1.6 or ~185 μs that persists for several milliseconds as a long-lived charge-separated state facilitated by the protein matrix.« less

Spectroscopic Analysis of a Biomimetic Model of Tyr(Z) Function in PSII.

PubMed

Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; Kodis, Gerdenis; Megiatto, Jackson D; Méndez-Hernández, Dalvin D; Frese, Raoul N; van Grondelle, Rienk; Moore, Thomas A; Moore, Ana L; Gust, Devens; Kennis, John T M

2015-09-17

Using natural photosynthesis as a model, bio-inspired constructs for fuel generation from sunlight are being developed. Here we report the synthesis and time-resolved spectroscopic analysis of a molecular triad in which a porphyrin electron donor is covalently linked to both a cyanoporphyrin electron acceptor and a benzimidazole-phenol model for the TyrZ-D1His190 pair of PSII. A dual-laser setup enabled us to record the ultrafast kinetics and long-living species in a single experiment. From this data, the photophysical relaxation pathways were elucidated for the triad and reference compounds. For the triad, quenching of the cyanoporphyrin singlet excited state lifetime was interpreted as photoinduced electron transfer from the porphyrin to the excited cyanoporphyrin. In contrast to a previous study of a related molecule, we were unable to observe subsequent formation of a long-lived charge separated state involving the benzimidazole-phenol moiety. The lack of detection of a long-lived charge separated state is attributed to a change in energetic landscape for charge separation/recombination due to small differences in structure and solvation of the new triad.

Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

NASA Astrophysics Data System (ADS)

Kwon, Ha-Kyung; Olvera de La Cruz, Monica

2015-03-01

Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

Core/shell colloidal quantum dot exciplex states for the development of highly efficient quantum-dot-sensitized solar cells.

PubMed

Wang, Jin; Mora-Seró, Iván; Pan, Zhenxiao; Zhao, Ke; Zhang, Hua; Feng, Yaoyu; Yang, Guang; Zhong, Xinhua; Bisquert, Juan

2013-10-23

Searching suitable panchromatic QD sensitizers for expanding the light-harvesting range, accelerating charge separation, and retarding charge recombination is an effective way to improve power conversion efficiency (PCE) of quantum-dot-sensitized solar cells (QDSCs). One possible way to obtain a wide absorption range is to use the exciplex state of a type-II core/shell-structured QDs. In addition, this system could also provide a fast charge separation and low charge-recombination rate. Herein, we report on using a CdTe/CdSe type-II core/shell QD sensitizer with an absorption range extending into the infrared region because of its exciplex state, which is covalently linked to TiO2 mesoporous electrodes by dropping a bifunctional linker molecule mercaptopropionic acid (MPA)-capped QD aqueous solution onto the film electrode. High loading and a uniform distribution of QD sensitizer throughout the film electrode thickness have been confirmed by energy dispersive X-ray (EDX) elemental mapping. The accelerated electron injection and retarded charge-recombination pathway in the built CdTe/CdSe QD cells in comparison with reference CdSe QD-based cells have been confirmed by impedance spectroscopy, fluorescence decay, and intensity-modulated photocurrent/photovoltage spectroscopy (IMPS/IMVS) analysis. With the combination of the high QD loading and intrinsically superior optoelectronic properties of type-II core/shell QD (wide absorption range, fast charge separation, and slow charge recombination), the resulting CdTe/CdSe QD-based regenerative sandwich solar cells exhibit a record PCE of 6.76% (J(sc) = 19.59 mA cm(-2), V(oc) = 0.606 V, and FF = 0.569) with a mask around the active film under a full 1 sun illumination (simulated AM 1.5), which is the highest reported to date for liquid-junction QDSCs.

Polaron pair mediated triplet generation in polymer/fullerene blends

PubMed Central

Dimitrov, Stoichko D.; Wheeler, Scot; Niedzialek, Dorota; Schroeder, Bob C.; Utzat, Hendrik; Frost, Jarvist M.; Yao, Jizhong; Gillett, Alexander; Tuladhar, Pabitra S.; McCulloch, Iain; Nelson, Jenny; Durrant, James R.

2015-01-01

Electron spin is a key consideration for the function of organic semiconductors in light-emitting diodes and solar cells, as well as spintronic applications relying on organic magnetoresistance. A mechanism for triplet excited state generation in such systems is by recombination of electron-hole pairs. However, the exact charge recombination mechanism, whether geminate or nongeminate and whether it involves spin-state mixing is not well understood. In this work, the dynamics of free charge separation competing with recombination to polymer triplet states is studied in two closely related polymer-fullerene blends with differing polymer fluorination and photovoltaic performance. Using time-resolved laser spectroscopic techniques and quantum chemical calculations, we show that lower charge separation in the fluorinated system is associated with the formation of bound electron-hole pairs, which undergo spin-state mixing on the nanosecond timescale and subsequent geminate recombination to triplet excitons. We find that these bound electron-hole pairs can be dissociated by electric fields. PMID:25735188

Elucidating the Ultrafast Dynamics of Photoinduced Charge Separation in Metalloporphyrin-Fullerene Dyads Across the Electromagnetic Spectrum

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

Zhang, J.; Pápai, M.; Hirsch, A.

Metalloporphyrins are prominent building blocks in the synthetic toolbox of advanced photodriven molecular devices. When the central ion is paramagnetic, the relaxation pathways within the manifold of excited states are highly intricate so that unravelling the intramolecular energy and electron transfer processes is usually a very complex task. This fact is critically hampering the development of applications based on the enhanced coupling offered by the electronic exchange interaction. In this work, the dynamics of charge separation in a copper porphyrin-fullerene are studied with several complementary spectroscopic tools across the electromagnetic spectrum (from near infra-red to X-ray wavelengths), each of themmore » providing specific diagnostics. Correlating the various rates clearly demonstrates that the lifetime of the photoinduced charge-separated state exceeds by about 10 fold that of the isolated photoexcited CuII porphyrin. As revealed by the spectral modifications in the XANES region, this stabilization is accompanied by a transient change in covalency around the CuII center, which is induced by an enhanced interaction with the C60 moiety. This experimental finding is further confirmed by state-of-the art calculations using DFT and TD-DFT including dispersion effects that explain the electrostatic and structural origins of this interaction, as the CuIIP cation becomes ruffled and approaches closer to the fullerene in the charge-separated state. From a methodological point of view, these results exemplify the potential of multielectron excitation features in transient X-ray spectra as future diagnostics of sub-femtosecond electronic dynamics. From a practical point of view, this work is paving the way for elucidating out-of-equilibrium electron transfer events coupled to magnetic interaction processes on their intrinsic time-scales.« less

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

NASA Astrophysics Data System (ADS)

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

2017-12-01

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

Z-M in Lightning Forecasting

DTIC Science & Technology

2009-03-01

hydrometers create a charge separation. Inductive processes rely on a preexisting external electric field to induce charges on polarized particles, which...frozen hydrometers . A. FLORIDA CLIMATE Florida is often referred to as the lightning capital of the United States (Hodanish et al. 1997) or

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.

Persistence time of charge carriers in defect states of molecular semiconductors.

PubMed

McMahon, David P; Troisi, Alessandro

2011-06-07

Charge carriers in organic crystals are often trapped in point defects. The persistence time of the charge in these defect states is evaluated by computing the escape rate from this state using non-adiabatic rate theory. Two cases are considered (i) the hopping between separate identical defect states and (ii) the hopping between a defect state and the bulk (delocalized) states. We show that only the second process is likely to happen with realistic defect concentrations and highlight that the inclusion of an effective quantum mode of vibration is essential for accurate computation of the rate. The computed persistence time as a function of the trap energy indicates that trap states shallower than ∼0.3 eV cannot be effectively investigated with some slow spectroscopic techniques such as THz spectroscopy or EPR commonly used to study the nature of excess charge in semiconductors.

Femtosecond Visible Transient Absorption Spectroscopy of Chlorophyll f-Containing Photosystem I.

PubMed

Kaucikas, Marius; Nürnberg, Dennis; Dorlhiac, Gabriel; Rutherford, A William; van Thor, Jasper J

2017-01-24

Photosystem I (PSI) from Chroococcidiopsis thermalis PCC 7203 grown under far-red light (FRL; >725 nm) contains both chlorophyll a and a small proportion of chlorophyll f. Here, we investigated excitation energy transfer and charge separation using this FRL-grown form of PSI (FRL-PSI). We compared femtosecond transient visible absorption changes of normal, white-light (WL)-grown PSI (WL-PSI) with those of FRL-PSI using excitation at 670 nm, 700 nm, and (in the case of FRL-PSI) 740 nm. The possibility that chlorophyll f participates in energy transfer or charge separation is discussed on the basis of spectral assignments. With selective pumping of chlorophyll f at 740 nm, we observe a final ∼150 ps decay assigned to trapping by charge separation, and the amplitude of the resulting P700 +• A 1 -• charge-separated state indicates that the yield is directly comparable to that of WL-PSI. The kinetics shows a rapid 2 ps time constant for almost complete transfer to chlorophyll f if chlorophyll a is pumped with a wavelength of 670 nm or 700 nm. Although the physical role of chlorophyll f is best supported as a low-energy radiative trap, the physical location should be close to or potentially within the charge-separating pigments to allow efficient transfer for charge separation on the 150 ps timescale. Target models can be developed that include a branching in the formation of the charge separation for either WL-PSI or FRL-PSI. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Apparatus for molecular weight separation

DOEpatents

Smith, Richard D.; Liu, Chuanliang

2001-01-01

The present invention relates generally to an apparatus and method for separating high molecular weight molecules from low molecular weight molecules. More specifically, the invention relates to the use of microdialysis for removal of the salt (low molecular weight molecules) from a nucleotide sample (high molecular weight molecules) for ESI-MS analysis. The dialysis or separation performance of the present invention is improved by (1) increasing dialysis temperature thereby increasing desalting efficiency and improving spectrum quality; (2) adding piperidine and imidazole to the dialysis buffer solution and reducing charge states and further increasing detection sensitivity for DNA; (3) using low concentrations (0-2.5 mM NH4OAc) of dialysis buffer and shifting the DNA negative ions to higher charge states, producing a nearly 10-fold increase in detection sensitivity and a slightly decreased desalting efficiency, (4) conducting a two-stage separation or (5) any combination of (1), (2), (3) and (4).

Influence of Crystallinity and Energetics on Charge Separation in Polymer–Inorganic Nanocomposite Films for Solar Cells

PubMed Central

Bansal, Neha; Reynolds, Luke X.; MacLachlan, Andrew; Lutz, Thierry; Ashraf, Raja Shahid; Zhang, Weimin; Nielsen, Christian B.; McCulloch, Iain; Rebois, Dylan G.; Kirchartz, Thomas; Hill, Michael S.; Molloy, Kieran C.; Nelson, Jenny; Haque, Saif A.

2013-01-01

The dissociation of photogenerated excitons and the subsequent spatial separation of the charges are of crucial importance to the design of efficient donor-acceptor heterojunction solar cells. While huge progress has been made in understanding charge generation at all-organic junctions, the process in hybrid organic:inorganic systems has barely been addressed. Here, we explore the influence of energetic driving force and local crystallinity on the efficiency of charge pair generation at hybrid organic:inorganic semiconductor heterojunctions. We use x-ray diffraction, photoluminescence quenching, transient absorption spectroscopy, photovoltaic device and electroluminescence measurements to demonstrate that the dissociation of photogenerated polaron pairs at hybrid heterojunctions is assisted by the presence of crystalline electron acceptor domains. We propose that such domains encourage delocalization of the geminate pair state. The present findings suggest that the requirement for a large driving energy for charge separation is relaxed when a more crystalline electron acceptor is used. PMID:23524906

Spontaneous Charge Separation and Sublimation Processes are Ubiquitous in Nature and in Ionization Processes in Mass Spectrometry

NASA Astrophysics Data System (ADS)

Trimpin, Sarah; Lu, I.-Chung; Rauschenbach, Stephan; Hoang, Khoa; Wang, Beixi; Chubatyi, Nicholas D.; Zhang, Wen-Jing; Inutan, Ellen D.; Pophristic, Milan; Sidorenko, Alexander; McEwen, Charles N.

2018-02-01

Ionization processes have been discovered by which small and large as well as volatile and nonvolatile compounds are converted to gas-phase ions when associated with a matrix and exposed to sub-atmospheric pressure. Here, we discuss experiments further defining these simple and unexpected processes. Charge separation is found to be a common process for small molecule chemicals, solids and liquids, passed through an inlet tube from a higher to a lower pressure region, with and without heat applied. This charge separation process produces positively- and negatively-charged particles with widely different efficiencies depending on the compound and its physical state. Circumstantial evidence is presented suggesting that in the new ionization process, charged particles carry analyte into the gas phase, and desolvation of these particles produce the bare ions similar to electrospray ionization, except that solid particles appear likely to be involved. This mechanistic proposition is in agreement with previous theoretical work related to ion emission from ice.

Charge recombination in organic photovoltaic devices with high open-circuit voltages.

PubMed

Westenhoff, Sebastian; Howard, Ian A; Hodgkiss, Justin M; Kirov, Kiril R; Bronstein, Hugo A; Williams, Charlotte K; Greenham, Neil C; Friend, Richard H

2008-10-15

A detailed charge recombination mechanism is presented for organic photovoltaic devices with a high open-circuit voltage. In a binary blend comprised of polyfluorene copolymers, the performance-limiting process is found to be the efficient recombination of tightly bound charge pairs into neutral triplet excitons. We arrive at this conclusion using optical transient absorption (TA) spectroscopy with visible and IR probes and over seven decades of time resolution. By resolving the polarization of the TA signal, we track the movement of polaronic states generated at the heterojunction not only in time but also in space. It is found that the photogenerated charge pairs are remarkably immobile at the heterojunction during their lifetime. The charge pairs are shown to be subject to efficient intersystem crossing and terminally recombine into F8BT triplet excitons within approximately 40 ns. Long-range charge separation competes rather unfavorably with intersystem crossing--75% of all charge pairs decay into triplet excitons. Triplet exciton states are thermodynamically accessible in polymer solar cells with high open circuit voltage, and we therefore suggest this loss mechanism to be general. We discuss guidelines for the design of the next generation of organic photovoltaic materials where separating the metastable interfacial charge pairs within approximately 40 ns is paramount.

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.

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

Generation Dependent Ultrafast Charge Separation and Recombination in a Pyrene-Viologen Family of Dendrons.

PubMed

Gong, Zheng; Bao, Jianhua; Nagai, Keiji; Iyoda, Tomokazu; Kawauchi, Takehiro; Piotrowiak, Piotr

2016-05-12

The ability of a dendritic network to intercept electrons and extend the lifetime of a short-lived photoinduced charge separated (CS) state was investigated in a homologous family of methyl viologen (MV(2+)) dendrons spanning four generations, G0 through G3. The CS state in the parent pyrene-methylene-viologen G0 system with a single acceptor exhibits an extremely short lifetime of τ = 0.72 ps. The expansion of the viologen network introduces slower components to the recombination kinetics by allowing the injected electron to migrate further away from the donor. The long-lived fraction of the population increases monotonically in the order G3 > G2 > G1 > G0, while the respective recombination rates decrease. In the highest generation of the dendron ∼14% of the CS state population experiences a 10-fold or greater lifetime extension. Long range tunneling across multiple viologen units and sequential site-to-site hopping both contribute to the overall effect. The large excess energy deposited in the apical viologen upon charge separation and the presence of an extended network of low lying π-orbitals likely facilitate shuttling the electron further down the dendron.

The effect of solvent relaxation time constants on free energy gap law for ultrafast charge recombination following photoinduced charge separation.

PubMed

Mikhailova, Valentina A; Malykhin, Roman E; Ivanov, Anatoly I

2018-05-16

To elucidate the regularities inherent in the kinetics of ultrafast charge recombination following photoinduced charge separation in donor-acceptor dyads in solutions, the simulations of the kinetics have been performed within the stochastic multichannel point-transition model. Increasing the solvent relaxation time scales has been shown to strongly vary the dependence of the charge recombination rate constant on the free energy gap. In slow relaxing solvents the non-equilibrium charge recombination occurring in parallel with solvent relaxation is very effective so that the charge recombination terminates at the non-equilibrium stage. This results in a crucial difference between the free energy gap laws for the ultrafast charge recombination and the thermal charge transfer. For the thermal reactions the well-known Marcus bell-shaped dependence of the rate constant on the free energy gap is realized while for the ultrafast charge recombination only a descending branch is predicted in the whole area of the free energy gap exceeding 0.2 eV. From the available experimental data on the population kinetics of the second and first excited states for a series of Zn-porphyrin-imide dyads in toluene and tetrahydrofuran solutions, an effective rate constant of the charge recombination into the first excited state has been calculated. The obtained rate constant being very high is nearly invariable in the area of the charge recombination free energy gap from 0.2 to 0.6 eV that supports the theoretical prediction.

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 impact of the attachment position of the spacer on the porphyrin on the electron transfer rate, and this strategy can represent a useful approach to develop molecular photonic devices for long-range charge separations.

Analysis of Native-Like Proteins and Protein Complexes Using Cation to Anion Proton Transfer Reactions (CAPTR)

NASA Astrophysics Data System (ADS)

Laszlo, Kenneth J.; Bush, Matthew F.

2015-12-01

Mass spectra of native-like protein complexes often exhibit narrow charge-state distributions, broad peaks, and contributions from multiple, coexisting species. These factors can make it challenging to interpret those spectra, particularly for mixtures with significant heterogeneity. Here we demonstrate the use of ion/ion proton transfer reactions to reduce the charge states of m/ z-selected, native-like ions of proteins and protein complexes, a technique that we refer to as cation to anion proton transfer reactions (CAPTR). We then demonstrate that CAPTR can increase the accuracy of charge state assignments and the resolution of interfering species in native mass spectrometry. The CAPTR product ion spectra for pyruvate kinase exhibit ~30 peaks and enable unambiguous determination of the charge state of each peak, whereas the corresponding precursor spectra exhibit ~6 peaks and the assigned charge states have an uncertainty of ±3%. 15+ bovine serum albumin and 21+ yeast enolase dimer both appear near m/ z 4450 and are completely unresolved in a mixture. After a single CAPTR event, the resulting product ions are baseline resolved. The separation of the product ions increases dramatically after each subsequent CAPTR event; 12 events resulted in a 3000-fold improvement in separation relative to the precursor ions. Finally, we introduce a framework for interpreting and predicting the figures of merit for CAPTR experiments. More generally, these results suggest that CAPTR strongly complements other mass spectrometry tools for analyzing proteins and protein complexes, particularly those in mixtures.

Theoretical investigation of the electron transfer dynamics and photodegradation pathways in a hydrogen-evolving ruthenium-palladium photocatalyst.

PubMed

Staniszewska, Magdalena; Kupfer, Stephan; Guthmuller, Julien

2018-05-16

Time-dependent density functional theory calculations combined with the Marcus theory of electron transfer (ET) were applied on the molecular photocatalyst [(tbbpy)2Ru(tpphz)PdCl2]2+ in order to elucidate the light-induced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational results show that after the initial excitation, metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are energetically accessible, but that an ET toward the catalytic center (PdCl2) from these states is a slow process, with estimated time constants above 1 ns. Instead, the calculations predict that low-lying Pd-centered states are efficiently populated - associated to an energy transfer toward the catalytic center. Thus, it is postulated that these states lead to the dissociation of a Cl- and are consequently responsible for the experimentally observed degradation of the catalytic center. Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated states are significantly increased (i.e. 10^5-10^6 times larger). This demonstrates that alteration of the catalytic center generates efficient charge separation. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

First-principles studies of interfacial charge separation in nano-materials photovoltaic heterojunction

NASA Astrophysics Data System (ADS)

Kanai, Yosuke

2009-03-01

Charge separation is a crucial process that must be understood in order to make substantial improvements in nano-materials based PV cells. In our work, first principles quantum mechanical calculations are employed to shed light on this process for some important nano-material heterojunctions. I will first present our work on the interfacial charge separation in Fullerene/P3HT and CNT/P3HT heterojunctions. Our findings indicate that in the fullerene system a two-step process is operative, involving an adiabatic electron transfer and an exciton dissociation via quasi-degenerate states localized on the fullerene. For the nanotubes, on the other hand, while such a two-step process is not necessary for efficient charge separation, the presence of metallic nanotubes lead to undesirable charge traps. Secondly, I will discuss how we are addressing the difficulty in employing standard DFT approaches for investigating inorganic-organic PV interfaces, which are composed of two distinct materials with very different electronic environments. I will discuss a QMC scheme for obtaining many-body corrections to the Kohn-Sham level alignments and its application to a CdSe/Oligothiophene hybrid PV interface, with the aim of tailoring its behavior by controlling the conjugation length.

Mirror Charge Radii and the Neutron Equation of State

NASA Astrophysics Data System (ADS)

Brown, B. Alex

2017-09-01

The differences in the charge radii of mirror nuclei are shown to be proportional to the derivative of the neutron equation of state and the symmetry energy at nuclear matter saturation density. This derivative is important for constraining the neutron equation of state for use in astrophysics. The charge radii of several neutron-rich nuclei are already measured to the accuracy of about 0.005 fm. Experiments at isotope-separator and radioactive-beam facilities are needed to measure the charge radii of the corresponding proton-rich mirror nuclei to a similar accuracy. It is also shown that neutron skins of nuclei with N =Z depend upon the value of the symmetry energy at a density of 0.10 nucleons /fm3 .

Separation of rat pituitary secretory granules by continuous flow electrophoresis

NASA Technical Reports Server (NTRS)

Hayes, Daniel; Exton, Carrie; Salada, Thomas; Shellenberger, Kathy; Waddle, Jenny; Hymer, W. C.

1990-01-01

The separation of growth hormone-containing cytoplasmic secretory granules from the rat pituitary gland by continuous flow electrophoresis is described. The results are consistent with the hypothesis that granule subpopulations can be separated due to differences in surface charge; these, in turn, may be related to the oligomeric state of the hormone.

Inner-shell excitation and ionic fragmentation of molecules

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

Hitchcock, A.P.; Tyliszczak, T.; Cavell, R.G.

1997-04-01

Inner-shell excitation and associated decay spectroscopies are site specific probes of electronic and geometrical structure and photoionization dynamics. X-ray absorption probes the geometric and electronic structure, while time-of-flight mass spectrometry with multi-coincidence detection provides information on the photofragmentation dynamics of the initially produced inner-shell state. Auger decay of inner-shell excited and ionised states is an efficient source of multiply charged ions. The charge separation and fragmentation of these species, studied by photoelectron-photoion-photoion coincidence (also called charge separation mass spectrometry) gives insights into bonding and electronic structure. In molecules, the dependence of the fragmentation process on the X-ray energy can revealmore » cases of site and/or state selective fragmentation. At the ALS the authors have examined the soft X-ray spectroscopy and ionic fragmentation of a number of molecules, including carboranes, silylenes, phosphorus halides, SF{sub 6} and CO{sub 2}. Their work is illustrated using results from the carborane and PF{sub 3} studies.« less

Ultrafast Photoinduced Symmetry-Breaking Charge Separation and Electron Sharing in Perylenediimide Molecular Triangles.

PubMed

Wu, Yilei; Young, Ryan M; Frasconi, Marco; Schneebeli, Severin T; Spenst, Peter; Gardner, Daniel M; Brown, Kristen E; Würthner, Frank; Stoddart, J Fraser; Wasielewski, Michael R

2015-10-21

We report on a visible-light-absorbing chiral molecular triangle composed of three covalently linked 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) (PDI) units. The rigid triangular architecture reduces the electronic coupling between the PDIs, so ultrafast symmetry-breaking charge separation is kinetically favored over intramolecular excimer formation, as revealed by femtosecond transient absorption spectroscopy. Photoexcitation of the PDI triangle dissolved in CH2Cl2 gives PDI(+•)-PDI(-•) in τCS = 12.0 ± 0.2 ps. Fast subsequent intramolecular electron/hole hopping can equilibrate the six possible energetically degenerate ion-pair states, as suggested by electron paramagnetic resonance/electron-nuclear double resonance spectroscopy, which shows that one-electron reduction of the PDI triangle results in complete electron sharing among the three PDIs. Charge recombination of PDI(+•)-PDI(-•) to the ground state occurs in τCR = 1.12 ± 0.01 ns with no evidence of triplet excited state formation.

Rotatingwall Technique and Centrifugal Separation

NASA Astrophysics Data System (ADS)

Anderegg, François

This chapter describes the "rotating wall" technique which enables essentially unlimited confinement time of 109-1010 charged particles in a Penning trap. The applied rotating wall electric field provides a positive torque that counteracts background drags, resulting in radial compression or steady-state confinement in near-thermal equilibrium states. The last part of the chapter discusses centrifugal separation in a rotating multi-species non-neutral plasma. Separation occurs when the centrifugal energy is larger than the mixing due to thermal energy.

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

NASA Astrophysics Data System (ADS)

Yang, Kun

2017-12-01

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

Ultrafast Exciton Dissociation and Long-Lived Charge Separation in a Photovoltaic Pentacene-MoS2 van der Waals Heterojunction.

PubMed

Bettis Homan, Stephanie; Sangwan, Vinod K; Balla, Itamar; Bergeron, Hadallia; Weiss, Emily A; Hersam, Mark C

2017-01-11

van der Waals heterojunctions between two-dimensional (2D) layered materials and nanomaterials of different dimensions present unique opportunities for gate-tunable optoelectronic devices. Mixed-dimensional p-n heterojunction diodes, such as p-type pentacene (0D) and n-type monolayer MoS 2 (2D), are especially interesting for photovoltaic applications where the absorption cross-section and charge transfer processes can be tailored by rational selection from the vast library of organic molecules and 2D materials. Here, we study the kinetics of excited carriers in pentacene-MoS 2 p-n type-II heterojunctions by transient absorption spectroscopy. These measurements show that the dissociation of MoS 2 excitons occurs by hole transfer to pentacene on the time scale of 6.7 ps. In addition, the charge-separated state lives for 5.1 ns, up to an order of magnitude longer than the recombination lifetimes from previously reported 2D material heterojunctions. By studying the fractional amplitudes of the MoS 2 decay processes, the hole transfer yield from MoS 2 to pentacene is found to be ∼50%, with the remaining holes undergoing trapping due to surface defects. Overall, the ultrafast charge transfer and long-lived charge-separated state in pentacene-MoS 2 p-n heterojunctions suggest significant promise for mixed-dimensional van der Waals heterostructures in photovoltaics, photodetectors, and related optoelectronic technologies.

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.

Cascading electron and hole transfer dynamics in a CdS/CdTe core-shell sensitized with bromo-pyrogallol red (Br-PGR): slow charge recombination in type II regime.

PubMed

Maity, Partha; Debnath, Tushar; Chopra, Uday; Ghosh, Hirendra Nath

2015-02-14

Ultrafast cascading hole and electron transfer dynamics have been demonstrated in a CdS/CdTe type II core-shell sensitized with Br-PGR using transient absorption spectroscopy and the charge recombination dynamics have been compared with those of CdS/Br-PGR composite materials. Steady state optical absorption studies suggest that Br-PGR forms strong charge transfer (CT) complexes with both the CdS QD and CdS/CdTe core-shell. Hole transfer from the photo-excited QD and QD core-shell to Br-PGR was confirmed by both steady state and time-resolved emission spectroscopy. Charge separation was also confirmed by detecting electrons in the conduction band of the QD and the cation radical of Br-PGR as measured from femtosecond transient absorption spectroscopy. Charge separation in the CdS/Br-PGR composite materials was found to take place in three different pathways, by transferring the photo-excited hole of CdS to Br-PGR, electron injection from the photo-excited Br-PGR to the CdS QD, and direct electron transfer from the HOMO of Br-PGR to the conduction band of the CdS QD. However, in the CdS/CdTe/Br-PGR system hole transfer from the photo-excited CdS to Br-PGR and electron injection from the photo-excited Br-PGR to CdS take place after cascading through the CdTe shell QD. Charge separation also takes place via direct electron transfer from the Br-PGR HOMO to the conduction band of CdS/CdTe. Charge recombination (CR) dynamics between the electron in the conduction band of the CdS QD and the Br-PGR cation radical were determined by monitoring the bleach recovery kinetics. The CR dynamics were found to be much slower in the CdS/CdTe/Br-PGR system than in the CdS/Br-PGR system. The formation of the strong CT complex and the separation of charges cascading through the CdTe shell help to slow down charge recombination in the type II regime.

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.

Ion transport restriction in mechanically strained separator membranes

NASA Astrophysics Data System (ADS)

Cannarella, John; Arnold, Craig B.

2013-03-01

We use AC impedance methods to investigate the effect of mechanical deformation on ion transport in commercial separator membranes and lithium-ion cells as a whole. A Bruggeman type power law relationship is found to provide an accurate correlation between porosity and tortuosity of deformed separators, which allows the impedance of a separator membrane to be predicted as a function of deformation. By using mechanical compression to vary the porosity of the separator membranes during impedance measurements it is possible to determine both the α and γ parameters from the modified Bruggeman relation for individual separator membranes. From impedance testing of compressed pouch cells it is found that separator deformation accounts for the majority of the transport restrictions arising from compressive stress in a lithium-ion cell. Finally, a charge state dependent increase in the impedance associated with charge transfer is observed with increasing cell compression.

Ru–protein–Co biohybrids designed for solar hydrogen production: understanding electron transfer pathways related to photocatalytic function† †Electronic supplementary information (ESI) available: Time traces of photocatalysis, additional EPR spectra and parameters, UV-visible spectroscopy data, and kinetic fits of TA traces. See DOI: 10.1039/c6sc03121h Click here for additional data file.

PubMed Central

Soltau, Sarah R.; Dahlberg, Peter D.; Niklas, Jens; Poluektov, Oleg G.; Mulfort, Karen L.

2016-01-01

A series of Ru–protein–Co biohybrids have been prepared using the electron transfer proteins ferredoxin (Fd) and flavodoxin (Fld) as scaffolds for photocatalytic hydrogen production. The light-generated charge separation within these hybrids has been monitored by transient optical and electron paramagnetic resonance spectroscopies. Two distinct electron transfer pathways are observed. The Ru–Fd–Co biohybrid produces up to 650 turnovers of H2 utilizing an oxidative quenching mechanism for Ru(ii)* and a sequential electron transfer pathway via the native [2Fe–2S] cluster to generate a Ru(iii)–Fd–Co(i) charge separated state that lasts for ∼6 ms. In contrast, a direct electron transfer pathway occurs for the Ru–ApoFld–Co biohybrid, which lacks an internal electron relay, generating Ru(i)–ApoFld–Co(i) charge separated state that persists for ∼800 μs and produces 85 turnovers of H2 by a reductive quenching mechanism for Ru(ii)*. This work demonstrates the utility of protein architectures for linking donor and catalytic function via direct or sequential electron transfer pathways to enable stabilized charge separation which facilitates photocatalysis for solar fuel production. PMID:28451142

Basic statistical analyses of candidate nickel-hydrogen cells for the Space Station Freedom

NASA Technical Reports Server (NTRS)

Maloney, Thomas M.; Frate, David T.

1993-01-01

Nickel-Hydrogen (Ni/H2) secondary batteries will be implemented as a power source for the Space Station Freedom as well as for other NASA missions. Consequently, characterization tests of Ni/H2 cells from Eagle-Picher, Whittaker-Yardney, and Hughes were completed at the NASA Lewis Research Center. Watt-hour efficiencies of each Ni/H2 cell were measured for regulated charge and discharge cycles as a function of temperature, charge rate, discharge rate, and state of charge. Temperatures ranged from -5 C to 30 C, charge rates ranged from C/10 to 1C, discharge rates ranged from C/10 to 2C, and states of charge ranged from 20 percent to 100 percent. Results from regression analyses and analyses of mean watt-hour efficiencies demonstrated that overall performance was best at temperatures between 10 C and 20 C while the discharge rate correlated most strongly with watt-hour efficiency. In general, the cell with back-to-back electrode arrangement, single stack, 26 percent KOH, and serrated zircar separator and the cell with a recirculating electrode arrangement, unit stack, 31 percent KOH, zircar separators performed best.

Magnetic susceptibility as a direct measure of oxidation state in LiFePO4 batteries and cyclic water gas shift reactors.

PubMed

Kadyk, Thomas; Eikerling, Michael

2015-08-14

The possibility of correlating the magnetic susceptibility to the oxidation state of the porous active mass in a chemical or electrochemical reactor was analyzed. The magnetic permeability was calculated using a hierarchical model of the reactor. This model was applied to two practical examples: LiFePO4 batteries, in which the oxidation state corresponds with the state-of-charge, and cyclic water gas shift reactors, in which the oxidation state corresponds to the depletion of the catalyst. In LiFePO4 batteries phase separation of the lithiated and delithiated phases in the LiFePO4 particles in the positive electrode gives rise to a hysteresis effect, i.e. the magnetic permeability depends on the history of the electrode. During fast charge or discharge, non-uniform lithium distributionin the electrode decreases the hysteresis effect. However, the overall sensitivity of the magnetic response to the state-of-charge lies in the range of 0.03%, which makes practical measurement challenging. In cyclic water gas shift reactors, the sensitivity is 4 orders of magnitude higher and without phase separation, no hysteresis occurs. This shows that the method is suitable for such reactors, in which large changes of the magnetic permeability of the active material occurs.

Microdialysis unit for molecular weight separation

DOEpatents

Smith, Richard D.; Liu, Chuanliang

1999-01-01

The present invention relates generally to an apparatus and method for separating high molecular weight molecules from low molecular weight molecules. More specifically, the invention relates to the use of microdialysis for removal of the salt (low molecular weight molecules) from a nucleotide sample (high molecular weight molecules) for ESI-MS analysis. The dialysis or separation performance of the present invention is improved by (1) increasing dialysis temperature thereby increasing desalting efficiency and improving spectrum quality; (2) adding piperidine and imidazole to the dialysis buffer solution and reducing charge states and further increasing detection sensitivity for DNA; (3) using low concentrations (0-2.5 mM NH4OAc) of dialysis buffer and shifting the DNA negative ions to higher charge states, producing a nearly 10-fold increase in detection sensitivity and a slightly decreased desalting efficiency, or (4) any combination of (1), (2), and (3).

Trypsin treatment of reaction centers from Rhodobacter sphaeroides in the dark and under illumination: protein structural changes follow charge separation.

PubMed

Brzezinski, P; Andréasson, L E

1995-06-06

Reaction centers from Rhodobacter sphaeroides R-26 were treated with trypsin in the dark and during illumination (in the charge-separated state). Trypsination resulted in a time-dependent modification of the reaction centers, reflected in changes in the charge recombination rate, in the inhibition of QA- to QB electron transfer, and eventually to inhibition of charge separation. Comparisons of centers with ubiquinone or anthraquinone in the QA site, in which the charge recombination pathways are different, indicate that trypsination affects charges close to the QA(-)-binding site. Studies of light-induced voltage changes from moving charges in reaction centers incorporated in lipid layers on a Teflon film, a technique which allows the discrimination of effects on donor and acceptor sides, indicate that the acceptor side is preferentially degraded by trypsin in the dark. Tryptic digestion during illumination generally resulted in a marked strengthening and acceleration of the effects seen already during dark treatment, but new effects were also detected in gel electrophoretic peptide patterns, in optical spectra, and in the kinetic measurements. Optical kinetic measurements revealed that the donor side of the reaction centers became susceptible to modification by trypsin during illumination as seen in the value of the binding constant for soluble cytochrome c2 which increased by a factor of 2, whereas it was much less affected after trypsination of reaction centers in the dark. The influence of illumination on the rate and mode by which trypsin acts on reaction centers indicates that changes in the protein conformation follow charge separation.(ABSTRACT TRUNCATED AT 250 WORDS)

Predictions for isobaric collisions at √{sN N}=200 GeV from a multiphase transport model

NASA Astrophysics Data System (ADS)

Deng, Wei-Tian; Huang, Xu-Guang; Ma, Guo-Liang; Wang, Gang

2018-04-01

The isobaric collisions of Ru9644+Ru9644 and Zr9640+Zr9640 have recently been proposed to discern the charge separation signal of the chiral magnetic effect (CME). In this article, we employ the string melting version of a multiphase transport model to predict various charged-particle observables, including d N /d η ,pT spectra, elliptic flow (v2), and particularly possible CME signals in Ru + Ru and Zr + Zr collisions at √{sNN}=200 GeV . Two sets of the nuclear structure parametrization have been explored, and the difference between the two isobaric collisions appears to be small, in terms of d N /d η ,pT spectra, and v2 for charged particles. We mimic the CME by introducing an initial charge separation that is proportional to the magnetic field produced in the collision, and study how the final-state interactions affect the CME observables. The relative difference in the CME signal between the two isobaric collisions is found to be robust, insensitive to the final-state interactions.

Relationship between composition of mixture charged and that in circulation in an auto refrigerant cascade and a J-T refrigerator operating in liquid refrigerant supply mode

NASA Astrophysics Data System (ADS)

Sreenivas, Bura; Nayak, H. Gurudath; Venkatarathnam, G.

2017-01-01

The composition of the refrigerant mixture in circulation during steady state operation of J-T and allied refrigerators is not the same as that charged due to liquid hold up in the heat exchangers and phase separators, as well as the differential solubility of different refrigerant components in the compressor lubricating oil. The performance of refrigerators/liquefiers operating on mixed refrigerant cycles is dependent on the mixture composition. It is therefore important to charge the right mixture that results in an optimum composition in circulation during steady state operation. The relationship between the charged and circulating composition has been experimentally studied in a J-T refrigerator operating in the liquid refrigerant supply (LRS) mode and an auto refrigerant cascade refrigerator (with a phase separator) operating in the gas refrigerant supply (GRS) mode. The results of the study are presented in this work. The results show that the method presented earlier for J-T refrigerators operating in GRS mode is also applicable in the case of refrigerators studied in this work.

Nucleon matrix elements from lattice QCD with all-mode-averaging and a domain-decomposed solver: An exploratory study

NASA Astrophysics Data System (ADS)

von Hippel, Georg; Rae, Thomas D.; Shintani, Eigo; Wittig, Hartmut

2017-01-01

We study the performance of all-mode-averaging (AMA) when used in conjunction with a locally deflated SAP-preconditioned solver, determining how to optimize the local block sizes and number of deflation fields in order to minimize the computational cost for a given level of overall statistical accuracy. We find that AMA enables a reduction of the statistical error on nucleon charges by a factor of around two at the same cost when compared to the standard method. As a demonstration, we compute the axial, scalar and tensor charges of the nucleon in Nf = 2 lattice QCD with non-perturbatively O(a)-improved Wilson quarks, using O(10,000) measurements to pursue the signal out to source-sink separations of ts ∼ 1.5 fm. Our results suggest that the axial charge is suffering from a significant amount (5-10%) of excited-state contamination at source-sink separations of up to ts ∼ 1.2 fm, whereas the excited-state contamination in the scalar and tensor charges seems to be small.

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.

Trapping Dynamics in Photosystem I-Light Harvesting Complex I of Higher Plants Is Governed by the Competition Between Excited State Diffusion from Low Energy States and Photochemical Charge Separation.

PubMed

Molotokaite, Egle; Remelli, William; Casazza, Anna Paola; Zucchelli, Giuseppe; Polli, Dario; Cerullo, Giulio; Santabarbara, Stefano

2017-10-26

The dynamics of excited state equilibration and primary photochemical trapping have been investigated in the photosystem I-light harvesting complex I isolated from spinach, by the complementary time-resolved fluorescence and transient absorption approaches. The combined analysis of the experimental data indicates that the excited state decay is described by lifetimes in the ranges of 12-16 ps, 32-36 ps, and 64-77 ps, for both detection methods, whereas faster components, having lifetimes of 550-780 fs and 4.2-5.2 ps, are resolved only by transient absorption. A unified model capable of describing both the fluorescence and the absorption dynamics has been developed. From this model it appears that the majority of excited state equilibration between the bulk of the antenna pigments and the reaction center occurs in less than 2 ps, that the primary charge separated state is populated in ∼4 ps, and that the charge stabilization by electron transfer is completed in ∼70 ps. Energy equilibration dynamics associated with the long wavelength absorbing/emitting forms harbored by the PSI external antenna are also characterized by a time mean lifetime of ∼75 ps, thus overlapping with radical pair charge stabilization reactions. Even in the presence of a kinetic bottleneck for energy equilibration, the excited state dynamics are shown to be principally trap-limited. However, direct excitation of the low energy chlorophyll forms is predicted to lengthen significantly (∼2-folds) the average trapping time.

A more than six orders of magnitude UV-responsive organic field-effect transistor utilizing a benzothiophene semiconductor and Disperse Red 1 for enhanced charge separation.

PubMed

Smithson, Chad S; Wu, Yiliang; Wigglesworth, Tony; Zhu, Shiping

2015-01-14

A more than six orders of magnitude UV-responsive organic field-effect transistor is developed using a benzothiophene (BTBT) semiconductor and strong donor-acceptor Disperse Red 1 as the traps to enhance charge separation. The device can be returned to its low drain current state by applying a short gate bias, and is completely reversible with excellent stability under ambient conditions. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mixing of Exciton and Charge-Transfer States in Photosystem II Reaction Centers: Modeling of Stark Spectra with Modified Redfield Theory

PubMed Central

Novoderezhkin, Vladimir I.; Dekker, Jan P.; van Grondelle, Rienk

2007-01-01

We propose an exciton model for the Photosystem II reaction center (RC) based on a quantitative simultaneous fit of the absorption, linear dichroism, circular dichroism, steady-state fluorescence, triplet-minus-singlet, and Stark spectra together with the spectra of pheophytin-modified RCs, and so-called RC5 complexes that lack one of the peripheral chlorophylls. In this model, the excited state manifold includes a primary charge-transfer (CT) state that is supposed to be strongly mixed with the pure exciton states. We generalize the exciton theory of Stark spectra by 1), taking into account the coupling to a CT state (whose static dipole cannot be treated as a small parameter in contrast to usual excited states); and 2), expressing the line shape functions in terms of the modified Redfield approach (the same as used for modeling of the linear responses). This allows a consistent modeling of the whole set of experimental data using a unified physical picture. We show that the fluorescence and Stark spectra are extremely sensitive to the assignment of the primary CT state, its energy, and coupling to the excited states. The best fit of the data is obtained supposing that the initial charge separation occurs within the special-pair PD1PD2. Additionally, the scheme with primary electron transfer from the accessory chlorophyll to pheophytin gave a reasonable quantitative fit. We show that the effectiveness of these two pathways is strongly dependent on the realization of the energetic disorder. Supposing a mixed scheme of primary charge separation with a disorder-controlled competition of the two channels, we can explain the coexistence of fast sub-ps and slow ps components of the Phe-anion formation as revealed by different ultrafast spectroscopic techniques. PMID:17526589

Charge separation at disordered semiconductor heterojunctions from random walk numerical simulations.

PubMed

Mandujano-Ramírez, Humberto J; González-Vázquez, José P; Oskam, Gerko; Dittrich, Thomas; Garcia-Belmonte, Germa; Mora-Seró, Iván; Bisquert, Juan; Anta, Juan A

2014-03-07

Many recent advances in novel solar cell technologies are based on charge separation in disordered semiconductor heterojunctions. In this work we use the Random Walk Numerical Simulation (RWNS) method to model the dynamics of electrons and holes in two disordered semiconductors in contact. Miller-Abrahams hopping rates and a tunnelling distance-dependent electron-hole annihilation mechanism are used to model transport and recombination, respectively. To test the validity of the model, three numerical "experiments" have been devised: (1) in the absence of constant illumination, charge separation has been quantified by computing surface photovoltage (SPV) transients. (2) By applying a continuous generation of electron-hole pairs, the model can be used to simulate a solar cell under steady-state conditions. This has been exploited to calculate open-circuit voltages and recombination currents for an archetypical bulk heterojunction solar cell (BHJ). (3) The calculations have been extended to nanostructured solar cells with inorganic sensitizers to study, specifically, non-ideality in the recombination rate. The RWNS model in combination with exponential disorder and an activated tunnelling mechanism for transport and recombination is shown to reproduce correctly charge separation parameters in these three "experiments". This provides a theoretical basis to study relevant features of novel solar cell technologies.

Secondary Structures of Ubiquitin Ions Soft-Landed onto Self-Assembled Monolayer Surfaces

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

Hu, Qichi; Laskin, Julia

2016-06-09

The secondary structures of multiply charged ubiquitin ions soft-landed onto self-assembled monolayer (SAM) surfaces were studied using in situ infrared reflection-absorption spectroscopy (IRRAS). Two charge states of ubiquitin, 5+ and 13+, were mass selected separately from a mixture of different charge states produced by electrospray ionization (ESI). The low 5+ charge state represents a native-like folded state of ubiquitin, while the high 13+ charge state assumes an extended, almost linear conformation. Each of the two charge states was soft-landed onto a CH 3- and COOH-terminated SAM of alkylthiols on gold (HSAM and COOH-SAM). HSAM is a hydrophobic surface known tomore » stabilize helical conformations of soft-landed protonated peptides, whereas COOH-SAM is a hydrophilic surface that preferentially stabilizes β-sheet conformations. IRRAS spectra of the soft-landed ubiquitin ions were acquired as a function of time during and after ion soft-landing. Similar to smaller peptide ions, helical conformations of ubiquitin are found to be more abundant on HSAM, while the relative abundance of β-sheet conformations increases on COOH-SAM. The initial charge state of ubiquitin also has a pronounced effect on its conformation on the surface. Specifically, on both surfaces, a higher relative abundance of helical conformations and lower relative abundance of β-sheet conformations is observed for the 13+ charge state compared to the 5+ charge state. Time-resolved experiments indicate that the α-helical band in the spectrum of the 13+ charge state slowly increases with time on the HSAM surface and decreases in the spectrum of the 13+ charge state on COOH-SAM. These results further support the preference of the hydrophobic HSAM surface toward helical conformations and demonstrate that soft-landed protein ions may undergo slow conformational changes during and after deposition.« less

Electronic Interactions of Michler's Ketone with DNA Bases in Synthetic Hairpins.

PubMed

Jalilov, Almaz S; Young, Ryan M; Eaton, Samuel W; Wasielewski, Michael R; Lewis, Frederick D

2015-01-01

The mechanism and dynamics of photoinduced electron transfer in two families of DNA hairpins possessing Michler's ketone linkers have been investigated by means of steady state and time-resolved transient absorption and emission spectroscopies. The excited state behavior of the diol linker employed in hairpin synthesis is similar to that of Michler's ketone in methanol solution. Hairpins possessing only a Michler's ketone linker undergo fast singlet state charge separation and charge recombination with an adjacent purine base, attributed to well-stacked ground state conformations, and intersystem crossing to the triplet state, attributed to poorly stacked ground state conformations. The failure of the triplet to undergo electron transfer reactions on the 7 ns time scale of our measurements is attributed to the low triplet energy and reduction potential of the twisted triplet state. Hairpins possessing both a Michler's ketone linker and a perylenediimide base surrogate separated by four base pairs undergo photoinduced hole transport from the diimide to Michler's ketone upon excitation of the diimide. The efficiency of hole transport is dependent upon the sequence of the intervening purine bases. © 2014 The American Society of Photobiology.

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.

Role of B800 in carotenoid-bacteriochlorophyll energy and electron transfer in LH2 complexes from the purple bacterium Rhodobacter sphaeroides.

PubMed

Polívka, Tomas; Niedzwiedzki, Dariusz; Fuciman, Marcel; Sundström, Villy; Frank, Harry A

2007-06-28

The role of the B800 in energy and electron transfer in LH2 complexes has been studied using femtosecond time-resolved transient absorption spectroscopy. The B800 site was perturbed by application of lithium dodecyl sulfate (LDS), and comparison of treated and untreated LH2 complexes from Rhodobacter sphaeroides incorporating carotenoids neurosporene, spheroidene, and spheroidenone was used to explore the role of B800 in carotenoid to bacteriochlorophyll-a (BChla) energy transfer and carotenoid radical formation. Efficiencies of the S1-mediated energy transfer in the LDS-treated complexes were 86, 61, and 57% in the LH2 complexes containing neurosporene, spheroidene, and spheroidenone, respectively. Analysis of the carotenoid S1 lifetimes in solution, LDS-treated, and untreated LH2 complexes allowed determination of B800/B850 branching ratio in the S1-mediated energy transfer. It is shown that B800 is a major acceptor, as approximately 60% of the energy from the carotenoid S1 state is accepted by B800. This value is nearly independent of conjugation length of the carotenoid. In addition to its role in energy transfer, the B800 BChla is the only electron acceptor in the event of charge separation between carotenoid and BChla in LH2 complexes, which is demonstrated by prevention of carotenoid radical formation in the LDS-treated LH2 complexes. In the untreated complexes containing neurosporene and spheroidene, the carotenoid radical is formed with a time constant of 300-400 fs. Application of different excitation wavelengths and intensity dependence of the carotenoid radical formation showed that the carotenoid radical can be formed only after excitation of the S2 state of carotenoid, although the S2 state itself is not a precursor of the charge-separated state. Instead, either a hot S1 state or a charge-transfer state lying between S2 and S1 states of the carotenoid are discussed as potential precursors of the charge-separated state.

A simple model of electron beam initiated dielectric breakdown

NASA Technical Reports Server (NTRS)

Beers, B. L.; Daniell, R. E.; Delmer, T. N.

1985-01-01

A steady state model that describes the internal charge distribution of a planar dielectric sample exposed to a uniform electron beam was developed. The model includes the effects of charge deposition and ionization of the beam, separate trap-modulated mobilities for electrons and holes, electron-hole recombination, and pair production by drifting thermal electrons. If the incident beam current is greater than a certain critical value (which depends on sample thickness as well as other sample properties), the steady state solution is non-physical.

Quark charge retention in final state hadrons from deep inelastic muon scattering

NASA Astrophysics Data System (ADS)

Albanese, J. P.; Arneodo, M.; Arvidson, A.; Aubert, J. J.; Becks, K. H.; Bee, C.; Benchouk, C.; Bird, I.; Blum, D.; Böhm, E.; de Bouard, X.; Brasse, F. W.; Braun, H.; Broll, C.; Brown, S.; Brück, H.; Calen, H.; Callebaut, D.; Carr, J.; Chima, J. S.; Clifft, R.; Cobb, J. H.; Coignet, G.; Combley, F.; Coughlan, J.; Court, G. R.; D'Agostini, G.; Dahlgren, S.; Davies, J. K.; Dau, W. D.; Dengler, F.; Derado, I.; Dobinson, R. W.; Dosselli, U.; Dreyer, T.; Drees, J.; Dumont, J. J.; Düren, M.; Eckardt, V.; Edwards, A.; Edwards, M.; Ernst, T.; Eszes, G.; Favier, J.; Ferrero, M. I.; Figiel, J.; Flauger, W.; Foster, J.; Gabathuler, E.; Gamet, R.; Gayler, J.; Geddes, N.; Giubellino, P.; Gössling, C.; Grafström, P.; Grard, F.; Gustafsson, L.; Haas, J.; Hagberg, E.; Hasert, F. J.; Hayman, P.; Heusse, P.; Hoppe, C.; Jaffré, M.; Jachołkowska, A.; Janata, F.; Jancso, G.; Johnson, A. S.; Kabuss, E. M.; Kellner, G.; Korbel, V.; Krüger, J.; Kullander, S.; Landgraf, U.; Lanske, D.; Loken, J.; Long, K.; Maire, M.; Manz, A.; Mohr, W.; Montanet, F.; Montgomery, H. E.; Mount, R. P.; Nagy, E.; Nassalski, J.; Norton, P. R.; Oakham, F. G.; Osborne, A. M.; Pascaud, C.; Paul, L.; Payre, P.; Peroni, C.; Pessard, H.; Pettingale, J.; Pönsgen, B.; Pötsch, M.; Preissner, H.; Renton, P.; Ribarics, P.; Rith, K.; Rondio, E.; Schlagböhmer, A.; Schmitz, N.; Schneegans, M.; Schröder, T.; Schultze, K.; Shiers, J.; Sloan, T.; Stier, H. E.; Stockhausen, W.; Studt, M.; Taylor, G.; Thénard, J. M.; Thompson, J. C.; de la Torre, A.; Toth, J.; Urban, L.; Wahlen, H.; Wallucks, W.; Whalley, M.; Williams, W. S. C.; Wheeler, S.; Wimpenny, S.; Windmolders, R.; Wolf, G.; Zank, P.; European Muon Collaboration

1984-08-01

The net charge of final state hadrons in both the current and target fragmentation regions has been measured in 280 GeV/ c muon-proton scattering experiment. A clean kinematic separation of the two regions in the centre-of-mass rapidity is demonstrated. The dependence on xBj of the mean net charges is found to be consistent with a large contribution of sea quarks at small xBj and with the dominance of valence quarks at large xBj thus giving clear confirmation of the quarck- parton model. It is also shown that the lending forward hadron has a high probability of containing the struck quark.

Digital modulation of the nickel valence state in a cuprate-nickelate heterostructure

NASA Astrophysics Data System (ADS)

Wrobel, F.; Geisler, B.; Wang, Y.; Christiani, G.; Logvenov, G.; Bluschke, M.; Schierle, E.; van Aken, P. A.; Keimer, B.; Pentcheva, R.; Benckiser, E.

2018-03-01

Layer-by-layer oxide molecular-beam epitaxy has been used to synthesize cuprate-nickelate multilayer structures of composition (La2CuO4)m/LaO /(LaNiO3)n . In a combined experimental and theoretical study, we show that these structures allow a clean separation of dopant and doped layers. Specifically, the LaO layer separating cuprate and nickelate blocks provides an additional charge that, according to density-functional theory calculations, is predominantly accommodated in the interfacial nickelate layers. This is reflected in an elongation of bond distances and changes in valence state, as observed by scanning transmission electron microscopy and x-ray absorption spectroscopy. Moreover, the predicted charge disproportionation in the nickelate interface layers leads to a metal-to-insulator transition when the thickness is reduced to n =2 , as observed in electrical transport measurements. The results exemplify the perspectives of charge transfer in metal-oxide multilayers to induce doping without introducing chemical and structural disorder.

Statistical mechanics of light elements at high pressure. VI - Liquid-state calculations with Thomas-Fermi-Dirac theory

NASA Technical Reports Server (NTRS)

Macfarlane, J. J.

1984-01-01

A model free energy is developed for hydrogen-helium mixtures based on solid-state Thomas-Fermi-Dirac calculations at pressures relevant to the interiors of giant planets. Using a model potential similar to that for a two-component plasma, effective charges for the nuclei (which are in general smaller than the actual charges because of screening effects) are parameterized, being constrained by calculations at a number of densities, compositions, and lattice structures. These model potentials are then used to compute the equilibrium properties of H-He fluids using a charged hard-sphere model. The results find critical temperatures of about 0 K, 500 K, and 1500 K, for pressures of 10, 100, and 1000 Mbar, respectively. These phase separation temperatures are considerably lower (approximately 6,000-10,000 K) than those found from calculations using free electron perturbation theory, and suggest that H-He solutions should be stable against phase separation in the metallic zones of Jupiter and Saturn.

Application of the bounds-analysis approach to arsenic and gallium antisite defects in gallium arsenide

DOE PAGES

Wright, A. F.; Modine, N. A.

2015-01-23

The As antisite in GaAs (AsGa) has been the subject of numerous experimental and theoretical studies. Recent density-functional-theory (DFT) studies report results in good agreement with experimental data for the +2, +1, and 0 charge states of the stable EL2 structure, the 0 charge state of the metastable EL2* structure, and the activation energy to transform from EL2* to EL2 in the 0 charge state. However, these studies did not report results for EL2* in the -1 charge state. In this paper, we report new DFT results for the +2, +1, 0, and -1 charge states of AsGa, obtained usingmore » a semilocal exchange-correlation functional and interpreted using a bounds-analysis approach. In good agreement with experimental data, we find a -1/0 EL2* level 0.06 eV below the conduction-band edge and an activation energy of 0.05 eV to transform from EL2* to EL2 in the -1 charge state. While the Ga antisite in GaAs (GaAs) has not been studied as extensively as AsGa, experimental studies report three charge states (-2, -1, 0) and two levels (-2/-1, -1/0) close to the valence-band edge. Recent DFT studies report the same charge states, but the levels are found to be well-separated from the valence-band edge. To resolve this disagreement, we performed new DFT calculations for GaAs and interpreted them using a bounds analysis. The analysis identified the -1 and 0 charge states as hole states weakly bound to a highly-localized -2 charge state. Moreover, the -2/-1, -1/0 levels were found to be near the valence-band edge, in good agreement with the experimental data.« less

Photoinduced charge separation in a colloidal system of exfoliated layered semiconductor controlled by coexisting aluminosilicate clay.

PubMed

Nakato, Teruyuki; Yamada, Yoshimi; Miyamoto, Nobuyoshi

2009-02-05

We investigated photoinduced charge separation occurring in a multicomponent colloidal system composed of oxide nanosheets of photocatalytically active niobate and photochemically inert clay and electron accepting methylviologen dications (MV2+). The inorganic nanosheets were obtained by exfoliation of layered hexaniobate and hectorite clay. The niobate and clay nanosheets were spatially separated in the colloidally dispersed state, and the MV2+ molecules were selectively adsorbed on the clay platelets. UV irradiation of the colloids led to electron transfer from the niobate nanosheets to the MV2+ molecules adsorbed on clay. The photoinduced electron transfer produced methylviologen radical cations (MV*+), which was characterized by high yield and long lifetime. The yield and stability of the MV*+ species were found to depend strongly on the clay content of the colloid: from a few mol % to approximately 70 mol % of the yield and several tens of minutes to more than 40 h of the lifetime. The contents of the niobate nanosheets and MV2+ molecules and the aging of the colloid also affected the photoinduced charge separation. In the absence of MV2+ molecules in the colloid, UV irradiation induced electron accumulation in the niobate nanosheets. The stability of the electron-accumulated state also depended on the clay content. The variation in the photochemical behavior is discussed in relation to the viscosity of the colloid.

Multi-modular, tris(triphenylamine) zinc porphyrin-zinc phthalocyanine-fullerene conjugate as a broadband capturing, charge stabilizing, photosynthetic 'antenna-reaction center' mimic.

PubMed

Kc, Chandra B; Lim, Gary N; D'Souza, Francis

2015-04-21

A broadband capturing, charge stabilizing, photosynthetic antenna-reaction center model compound has been newly synthesized and characterized. The model compound is comprised of a zinc porphyrin covalently linked to three units of triphenylamine entities and a zinc phthalocyanine entity. The absorption and fluorescence spectra of zinc porphyrin complemented that of zinc phthalocyanine offering broadband coverage. Stepwise energy transfer from singlet excited triphenylamine to zinc porphyrin, and singlet excited zinc porphyrin to zinc phthalocyanine (kENT ∼ 10(11) s(-1)) was established from spectroscopic and time-resolved transient absorption techniques. Next, an electron acceptor, fullerene was introduced via metal-ligand axial coordination to both zinc porphyrin and zinc phthalocyanine centers, and they were characterized by spectroscopic and electrochemical techniques. An association constant of 4.9 × 10(4) M(-1) for phenylimidazole functionalized fullerene binding to zinc porphyrin, and 5.1 × 10(4) M(-1) for it binding to zinc phthalocyanine was obtained. An energy level diagram for the occurrence of different photochemical events within the multi-modular donor-acceptor conjugate was established from spectral and electrochemical data. Unlike the previous zinc porphyrin-zinc phthalocyanine-fullerene conjugates, the newly assembled donor-acceptor conjugate has been shown to undergo the much anticipated initial charge separation from singlet excited zinc porphyrin to the coordinated fullerene followed by a hole shift process to zinc phthalocyanine resulting in a long-lived charge separated state as revealed by femto- and nanosecond transient absorption spectroscopic techniques. The lifetime of the final charge separated state was about 100 ns.

Energetics and kinetics of primary charge separation in bacterial photosynthesis.

PubMed

LeBard, David N; Kapko, Vitaliy; Matyushov, Dmitry V

2008-08-21

We report the results of molecular dynamics (MD) simulations and formal modeling of the free-energy surfaces and reaction rates of primary charge separation in the reaction center of Rhodobacter sphaeroides. Two simulation protocols were used to produce MD trajectories. Standard force-field potentials were employed in the first protocol. In the second protocol, the special pair was made polarizable to reproduce a high polarizability of its photoexcited state observed by Stark spectroscopy. The charge distribution between covalent and charge-transfer states of the special pair was dynamically adjusted during the simulation run. We found from both protocols that the breadth of electrostatic fluctuations of the protein/water environment far exceeds previous estimates, resulting in about 1.6 eV reorganization energy of electron transfer in the first protocol and 2.5 eV in the second protocol. Most of these electrostatic fluctuations become dynamically frozen on the time scale of primary charge separation, resulting in much smaller solvation contributions to the activation barrier. While water dominates solvation thermodynamics on long observation times, protein emerges as the major thermal bath coupled to electron transfer on the picosecond time of the reaction. Marcus parabolas were obtained for the free-energy surfaces of electron transfer by using the first protocol, while a highly asymmetric surface was obtained in the second protocol. A nonergodic formulation of the diffusion-reaction electron-transfer kinetics has allowed us to reproduce the experimental results for both the temperature dependence of the rate and the nonexponential decay of the population of the photoexcited special pair.

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

NASA Astrophysics Data System (ADS)

Pillay, Jason C.; McCulloch, Ian P.

2018-05-01

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

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.

Ab initio modeling of excitonic and charge-transfer states in organic semiconductors: the PTB1/PCBM low band gap system.

PubMed

Borges, Itamar; Aquino, Adélia J A; Köhn, Andreas; Nieman, Reed; Hase, William L; Chen, Lin X; Lischka, Hans

2013-12-11

A detailed quantum chemical simulation of the excitonic and charge-transfer (CT) states of a bulk heterojunction model containing poly(thieno[3,4-b]thiophene benzodithiophene) (PTB1)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is reported. The largest molecular model contains two stacked PTB1 trimer chains interacting with C60 positioned on top of and lateral to the (PTB1)3 stack. The calculations were performed using the algebraic diagrammatic construction method to second order (ADC(2)). One main result of the calculations is that the CT states are located below the bright inter-chain excitonic state, directly accessible via internal conversion processes. The other important aspects of the calculations are the formation of discrete bands of CT states originating from the lateral C60's and the importance of inter-chain charge delocalization for the stability of the CT states. A simple model for the charge separation step is also given, revealing the energetic feasibility of the overall photovoltaic process.

Local Intermolecular Order Controls Photoinduced Charge Separation at Donor/Acceptor Interfaces in Organic Semiconductors

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

Feier, Hilary M.; Reid, Obadiah G.; Pace, Natalie A.

2016-03-23

How free charge is generated at organic donor-acceptor interfaces is an important question, as the binding energy of the lowest energy (localized) charge transfer states should be too high for the electron and hole to escape each other. Recently, it has been proposed that delocalization of the electronic states participating in charge transfer is crucial, and aggregated or otherwise locally ordered structures of the donor or the acceptor are the precondition for this electronic characteristic. The effect of intermolecular aggregation of both the polymer donor and fullerene acceptor on charge separation is studied. In the first case, the dilute electronmore » acceptor triethylsilylhydroxy-1,4,8,11,15,18,22,25-octabutoxyphthalocyaninatosilicon(IV) (SiPc) is used to eliminate the influence of acceptor aggregation, and control polymer order through side-chain regioregularity, comparing charge generation in 96% regioregular (RR-) poly(3-hexylthiophene) (P3HT) with its regiorandom (RRa-) counterpart. In the second case, ordered phases in the polymer are eliminated by using RRa-P3HT, and phenyl-C61-butyric acid methyl ester (PC61BM) is used as the acceptor, varying its concentration to control aggregation. Time-resolved microwave conductivity, time-resolved photoluminescence, and transient absorption spectroscopy measurements show that while ultrafast charge transfer occurs in all samples, long-lived charge carriers are only produced in films with intermolecular aggregates of either RR-P3HT or PC61BM, and that polymer aggregates are just as effective in this regard as those of fullerenes.« less

Negative differential electrolyte resistance in a solid-state nanopore resulting from electroosmotic flow bistability.

PubMed

Luo, Long; Holden, Deric A; White, Henry S

2014-03-25

A solid-state nanopore separating two aqueous solutions containing different concentrations of KCl is demonstrated to exhibit negative differential resistance (NDR) when a constant pressure is applied across the nanopore. NDR refers to a decrease in electrical current when the voltage applied across the nanopore is increased. NDR results from the interdependence of solution flow (electroosmotic and pressure-engendered) with the distributions of K+ and Cl- within the nanopore. A switch from a high-conductivity state to a low-conductivity state occurs over a very narrow voltage window (<2 mV) that depends on the nanopore geometry, electrolyte concentration, and nanopore surface charge density. Finite element simulations based on a simultaneous solution of the Navier-Stokes, Poisson, and Nernst-Planck equations demonstrate that NDR results from a positive feedback mechanism between the ion distributions and electroosmotic flow, yielding a true bistability in fluid flow and electrical current at a critical applied voltage, i.e., the NDR "switching potential". Solution pH and Ca2+ were separately employed as chemical stimuli to investigate the dependence of the NDR on the surface charge density. The NDR switching potential is remarkably sensitive to the surface charge density, and thus to pH and the presence of Ca2+, suggesting possible applications in chemical sensing.

Protein Separation by Electrophoretic-Electroosmotic Focusing on Supported Lipid Bilayers

PubMed Central

Liu, Chunming; Monson, Christopher F.; Yang, Tinglu; Pace, Hudson; Cremer, Paul S.

2011-01-01

An electrophoretic-electroosmotic focusing (EEF) method was developed and used to separate membrane-bound proteins and charged lipids based on their charge-to-size ratio from an initially homogeneous mixture. EEF uses opposing electrophoretic and electroosmotic forces to focus and separate proteins and lipids into narrow bands on supported lipid bilayers (SLBs). Membrane-associated species were focused into specific positions within the SLB in a highly repeatable fashion. The steady-state focusing positions of the proteins could be predicted and controlled by tuning experimental conditions, such as buffer pH, ionic strength, electric field and temperature. Careful tuning of the variables should enable one to separate mixtures of membrane proteins with only subtle differences. The EEF technique was found to be an effective way to separate protein mixtures with low initial concentrations, and it overcame diffusive peak broadening to allow four bands to be separated simultaneously within a 380 μm wide isolated supported membrane patch. PMID:21958061

High-Power Collective Charging of a Solid-State Quantum Battery

NASA Astrophysics Data System (ADS)

Ferraro, Dario; Campisi, Michele; Andolina, Gian Marcello; Pellegrini, Vittorio; Polini, Marco

2018-03-01

Quantum information theorems state that it is possible to exploit collective quantum resources to greatly enhance the charging power of quantum batteries (QBs) made of many identical elementary units. We here present and solve a model of a QB that can be engineered in solid-state architectures. It consists of N two-level systems coupled to a single photonic mode in a cavity. We contrast this collective model ("Dicke QB"), whereby entanglement is genuinely created by the common photonic mode, to the one in which each two-level system is coupled to its own separate cavity mode ("Rabi QB"). By employing exact diagonalization, we demonstrate the emergence of a quantum advantage in the charging power of Dicke QBs, which scales like √{N } for N ≫1 .

Charge instabilities due to local charge conjugation symmetry in /2+1 dimensions

NASA Astrophysics Data System (ADS)

Bais, F. A.; Striet, J.

2003-08-01

Alice electrodynamics (AED) is a theory of electrodynamics in which charge conjugation is a local gauge symmetry. In this paper we investigate a charge instability in alice electrodynamics in 2+1 dimensions due to this local charge conjugation. The instability manifests itself through the creation of a pair of alice fluxes. The final state is one in which the charge is completely delocalized, i.e., it is carried as cheshire charge by the flux pair that gets infinitely separated. We determine the decay rate in terms of the parameters of the model. The relation of this phenomenon with other salient features of 2-dimensional compact QED, such as linear confinement due to instantons/monopoles, is discussed.

Convergent Synthesis and Photoinduced Processes in Multi-Chromophoric Rotaxanes1

PubMed Central

Megiatto, Jackson D.; Li, Ke; Schuster, David I.; Palkar, Amit; Herranz, M. Ángeles; Echegoyen, Luis; Abwandner, Silke; de Miguel, Gustavo; Guldi, Dirk M.

2010-01-01

A series of [2]rotaxane materials, in which [60]fullerene is linked to a macrocycle and ferrocene (Fc) moieties are placed at the termini of a thread, both of which possess a central Cu(I)-1,10-phenanthroline [Cu(phen)2]+ complex, were synthesized by self-assembly using Sauvage metal template methodology. Two types of threads were constructed, one with terminal ester linkages, and a second with terminal 1,2,3-triazole linkages derived from Cu(I)-catalyzed “click” 1,3-cycloaddition reactions. Model compounds lacking the fullerene moiety were prepared in an analogous manner. The ability of the interlocked Fc-[Cu(phen)2]+-C60 hybrids to undergo electron transfer upon photoexcitation was investigated by means of time-resolved fluorescence and transient absorption spectroscopy, using excitation wavelengths directed at the fullerene and [Cu(phen)2]+ subunits. The energies of the electronic excited states and charge separated (CS) states that might be formed upon photoexcitation were determined from spectroscopic and electrochemical data. These studies showed that MLCT excited states of the copper complex in the fullerenerotaxanes were quenched by electron transfer to the fullerene, resulting in charge separated states with oxidized copper and reduced fullerene moieties, (Fc)2-[Cu(phen)2]2+-C60•−. Even though electron transfer from Fc to the oxidized copper complex is predicted to be exergonic by 0.18 eV, no unequivocal evidence in support of such a process was obtained. The conclusion that Fc plays no role in the photoinduced processes in our systems rests on the lack of enhancement of the lifetime of the charge separated state as measured by decay of C60•− at ~ 1000 nm, since one-electron oxidized Fc is very difficult to detect spectroscopically in the 500–800 nm spectral region. PMID:20518479

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.

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

NASA Astrophysics Data System (ADS)

Kohno, Masanori

2018-04-01

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

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

The rates of charge separation and energy destructive charge recombination processes within an organic dyad in presence of metal-semiconductor core shell nanocomposites.

PubMed

Mandal, Gopa; Bhattacharya, Sudeshna; Das, Subrata; Ganguly, Tapan

2012-01-01

Steady state and time resolved spectroscopic measurements were made at the ambient temperature on an organic dyad, 1-(4-Chloro-phenyl)-3-(4-methoxy-naphthalen-1-yl)-propenone (MNCA), where the donor 1-methoxynaphthalene (1 MNT) is connected with the acceptor p-chloroacetophenone (PCA) by an unsaturated olefinic bond, in presence of Ag@TiO2 nanoparticles. Time resolved fluorescence and absorption measurements reveal that the rate parameters associated with charge separation, k(CS), within the dyad increases whereas charge recombination rate k(CR) reduces significantly when the surrounding medium is changed from only chloroform to mixture of chloroform and Ag@TiO2 (noble metal-semiconductor) nanocomposites. The observed results indicate that the dyad being combined with core-shell nanocomposites may form organic-inorganic nanocomposite system useful for developing light energy conversion devices. Use of metal-semiconductor nanoparticles may provide thus new ways to modulate charge recombination processes in light energy conversion devices. From comparison with the results obtained in our earlier investigations with only TiO2 nanoparticles, it is inferred that much improved version of light energy conversion device, where charge-separated species could be protected for longer period of time of the order of millisecond, could be designed by using metal-semiconductor core-shell nanocomposites rather than semiconductor nanoparticles only.

Ion Mobility Separation of Variant Histone Tails Extending to the “Middle-down” Range

PubMed Central

Shvartsburg, Alexandre A.; Zheng, Yupeng; Smith, Richard D.; Kelleher, Neil L.

2012-01-01

Differential ion mobility spectrometry (FAIMS) can baseline-resolve multiple variants of post-translationally modified peptides extending to the 3 - 4 kDa range, which differ in the localization of a PTM as small as acetylation. Essentially orthogonal separations for different charge states expand the total peak capacity in proportion to the number of observed states that increases for longer polypeptides. This might enable resolving localization variants for yet larger peptides and even intact proteins. PMID:22559289

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions.

PubMed

Williams, Peggy E; Marshall, David L; Poad, Berwyck L J; Narreddula, Venkateswara R; Kirk, Benjamin B; Trevitt, Adam J; Blanksby, Stephen J

2018-06-04

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions. Graphical Abstract.

Comparing Positively and Negatively Charged Distonic Radical Ions in Phenylperoxyl Forming Reactions

NASA Astrophysics Data System (ADS)

Williams, Peggy E.; Marshall, David L.; Poad, Berwyck L. J.; Narreddula, Venkateswara R.; Kirk, Benjamin B.; Trevitt, Adam J.; Blanksby, Stephen J.

2018-06-01

In the gas phase, arylperoxyl forming reactions play a significant role in low-temperature combustion and atmospheric processing of volatile organic compounds. We have previously demonstrated the application of charge-tagged phenyl radicals to explore the outcomes of these reactions using ion trap mass spectrometry. Here, we present a side-by-side comparison of rates and product distributions from the reaction of positively and negatively charge tagged phenyl radicals with dioxygen. The negatively charged distonic radical ions are found to react with significantly greater efficiency than their positively charged analogues. The product distributions of the anion reactions favor products of phenylperoxyl radical decomposition (e.g., phenoxyl radicals and cyclopentadienone), while the comparable fixed-charge cations yield the stabilized phenylperoxyl radical. Electronic structure calculations rationalize these differences as arising from the influence of the charged moiety on the energetics of rate-determining transition states and reaction intermediates within the phenylperoxyl reaction manifold and predict that this influence could extend to intra-molecular charge-radical separations of up to 14.5 Å. Experimental observations of reactions of the novel 4-(1-carboxylatoadamantyl)phenyl radical anion confirm that the influence of the charge on both rate and product distribution can be modulated by increasing the rigidly imposed separation between charge and radical sites. These findings provide a generalizable framework for predicting the influence of charged groups on polarizable radicals in gas phase distonic radical ions.

Spin-orbit induced electronic spin separation in semiconductor nanostructures.

PubMed

Kohda, Makoto; Nakamura, Shuji; Nishihara, Yoshitaka; Kobayashi, Kensuke; Ono, Teruo; Ohe, Jun-ichiro; Tokura, Yasuhiro; Mineno, Taiki; Nitta, Junsaku

2012-01-01

The demonstration of quantized spin splitting by Stern and Gerlach is one of the most important experiments in modern physics. Their discovery was the precursor of recent developments in spin-based technologies. Although electrical spin separation of charged particles is fundamental in spintronics, in non-uniform magnetic fields it has been difficult to separate the spin states of charged particles due to the Lorentz force, as well as to the insufficient and uncontrollable field gradients. Here we demonstrate electronic spin separation in a semiconductor nanostructure. To avoid the Lorentz force, which is inevitably induced when an external magnetic field is applied, we utilized the effective non-uniform magnetic field which originates from the Rashba spin-orbit interaction in an InGaAs-based heterostructure. Using a Stern-Gerlach-inspired mechanism, together with a quantum point contact, we obtained field gradients of 10(8) T m(-1) resulting in a highly polarized spin current.

Spin–orbit induced electronic spin separation in semiconductor nanostructures

PubMed Central

Kohda, Makoto; Nakamura, Shuji; Nishihara, Yoshitaka; Kobayashi, Kensuke; Ono, Teruo; Ohe, Jun-ichiro; Tokura, Yasuhiro; Mineno, Taiki; Nitta, Junsaku

2012-01-01

The demonstration of quantized spin splitting by Stern and Gerlach is one of the most important experiments in modern physics. Their discovery was the precursor of recent developments in spin-based technologies. Although electrical spin separation of charged particles is fundamental in spintronics, in non-uniform magnetic fields it has been difficult to separate the spin states of charged particles due to the Lorentz force, as well as to the insufficient and uncontrollable field gradients. Here we demonstrate electronic spin separation in a semiconductor nanostructure. To avoid the Lorentz force, which is inevitably induced when an external magnetic field is applied, we utilized the effective non-uniform magnetic field which originates from the Rashba spin–orbit interaction in an InGaAs-based heterostructure. Using a Stern–Gerlach-inspired mechanism, together with a quantum point contact, we obtained field gradients of 108 T m−1 resulting in a highly polarized spin current. PMID:23011136

Electron teleportation via Majorana bound states in a mesoscopic superconductor.

PubMed

Fu, Liang

2010-02-05

Zero-energy Majorana bound states in superconductors have been proposed to be potential building blocks of a topological quantum computer, because quantum information can be encoded nonlocally in the fermion occupation of a pair of spatially separated Majorana bound states. However, despite intensive efforts, nonlocal signatures of Majorana bound states have not been found in charge transport. In this work, we predict a striking nonlocal phase-coherent electron transfer process by virtue of tunneling in and out of a pair of Majorana bound states. This teleportation phenomenon only exists in a mesoscopic superconductor because of an all-important but previously overlooked charging energy. We propose an experimental setup to detect this phenomenon in a superconductor-quantum-spin-Hall-insulator-magnetic-insulator hybrid system.

Fission Fragment Studies by Gamma-Ray Spectrometry with the Mass Separator Lohengrin

NASA Astrophysics Data System (ADS)

Materna, T.; Amouroux, C.; Bail, A.; Bideau, A.; Chabod, S.; Faust, H.; Capellan, N.; Kessedjian, G.; Köster, U.; Letourneau, A.; Litaize, O.; Martin, F.; Mathieu, L.; Méplan, O.; Panebianco, S.; Régis, J.-M.; Rudigier, M.; Sage, C.; Serot, O.; Urban, W.

2014-09-01

A gamma spectrometric technique was implemented at the exit of the fission fragment separator of the ILL. It allows a precise measurement of isotopic yields of most important actinides in the heavy fragment region by an unambiguous identification of the nuclear charge of the fragments selected by the mass spectrometer. The status of the project and last results are reviewed. A spin-off of this activity is the identification of unknown nanosecond isomers in exotic nuclei through the observation of a disturbed ionic charge distribution. This technique has been improved to provide an estimation of the lifetime of the isomeric state.

Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer

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

Reslan, Randa; Lopata, Kenneth; Arntsen, Christopher

2012-12-14

We use time-dependent density functional theory and time-dependent ZINDO (a semi-empirical method) to study transfer of an extra electron between a pair of pentacene molecules. A measure of the electronic transfer integral is computed in a dynamic picture via the vertical excitation energy from a delocalized anionic ground state. With increasing dimer separation, this dynamical measurement of charge transfer is shown to be significantly larger than the commonly used static approximation (i.e., LUMO+1–LUMO of the neutral dimer, or HOMO–LUMO of the charged dimer), up to an order of magnitude higher at 6 Å. These results offer a word of cautionmore » for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer.« less

Electron transfer beyond the static picture: A TDDFT/TD-ZINDO study of a pentacene dimer

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

Reslan, Randa; Lopata, Kenneth A.; Arntsen, Christopher D.

2012-12-14

We use time-dependent density functional theory and time-dependent ZINDO (a semi-empirical method) to study transfer of an extra electron between a pair of pentacene dimers. A measure of the electronic transfer integral is computed in a dynamic picture via the vertical excitation energy from a delocalized anionic ground state. With increasing dimer separation, this dynamical measurement of charge transfer is shown to be significantly larger than the commonly used static approximation (i.e., LUMO+1 - LUMO of the neutral dimer, or HOMO - LUMO of the charged dimer), up to an order of magnitude higher at 6 Å. These results offermore » a word of caution for calculations involving large separations, as in organic photovoltaics, where care must be taken when using a static picture to model charge transfer.« less

Accumulative charge separation for solar fuels production: coupling light-induced single electron transfer to multielectron catalysis.

PubMed

Hammarström, Leif

2015-03-17

The conversion and storage of solar energy into a fuel holds promise to provide a significant part of the future renewable energy demand of our societies. Solar energy technologies today generate heat or electricity, while the large majority of our energy is used in the form of fuels. Direct conversion of solar energy to a fuel would satisfy our needs for storable energy on a large scale. Solar fuels can be generated by absorbing light and converting its energy to chemical energy by electron transfer leading to separation of electrons and holes. The electrons are used in the catalytic reduction of a cheap substrate with low energy content into a high-energy fuel. The holes are filled by oxidation of water, which is the only electron source available for large scale solar fuel production. Absorption of a single photon typically leads to separation of a single electron-hole pair. In contrast, fuel production and water oxidation are multielectron, multiproton reactions. Therefore, a system for direct solar fuel production must be able to accumulate the electrons and holes provided by the sequential absorption of several photons in order to complete the catalytic reactions. In this Account, the process is termed accumulative charge separation. This is considerably more complicated than charge separation on a single electron level and needs particular attention. Semiconductor materials and molecular dyes have for a long time been optimized for use in photovoltaic devices. Efforts are made to develop new systems for light harvesting and charge separation that are better optimized for solar fuel production than those used in the early devices presented so far. Significant progress has recently been made in the discovery and design of better homogeneous and heterogeneous catalysts for solar fuels and water oxidation. While the heterogeneous ones perform better today, molecular catalysts based on transition metal complexes offer much greater tunability of electronic and structural properties, they are typically more amenable to mechanistic analysis, and they are small and therefore require less material. Therefore, they have arguably greater potential as future efficient catalysts but must be efficiently coupled to accumulative charge separation. This Account discusses accumulative charge separation with focus on molecular and molecule-semiconductor hybrid systems. The coupling between charge separation and catalysis involves many challenges that are often overlooked, and they are not always apparent when studying water oxidation and fuel formation as separate half-reactions with sacrificial agents. Transition metal catalysts, as well as other multielectron donors and acceptors, cycle through many different states that may quench the excited sensitizer by nonproductive pathways. Examples where this has been shown, often with ultrafast rates, are reviewed. Strategies to avoid these competing energy-loss reactions and still obtain efficient coupling of charge separation to catalysis are discussed. This includes recent examples of dye-sensitized semiconductor devices with molecular catalysts and dyes that realize complete water splitting, albeit with limited efficiency.

Transition from the diamagnetic insulator to ferromagnetic metal in La1-xSrxCoO3

NASA Astrophysics Data System (ADS)

Knížek, Karel; Jirák, Zdeněk; Hejtmánek, Jiří; Novák, Pavel

2010-05-01

We have analyzed, using the theoretical GGA+U calculations, different configurations of spin states (low-spin, LS; intermediate-spin, IS and high-spin, HS Co) and proposed a model that accounts for magnetic and electric transport properties of perovskite cobaltites upon doping by charge carriers. In particular, it appears that the compositional transition from the diamagnetic LS phase of LaCoO3 to the ferromagnetic metallic IS phase in La1-xSrxCoO3 ( x>0.2) involves the same mechanisms as the high-temperature transition in pure LaCoO3. The process occurs gradually via a phase-separated state, where metallic IS domains stabilized through a charge transfer between Co and Co neighbors coexist with the Co poor regions in the LS ground state (or at higher temperatures, in mixed LS/HS state). This phase separation vanishes when doping in La1-xSrxCoO3 reaches x˜0.2, and a uniform IS phase, analogous to that in pure LaCoO3 in the high-temperature limit, is established.

Modulating interactions between ligand-coated nanoparticles and phase-separated lipid bilayers by varying the ligand density and the surface charge.

PubMed

Chen, Xiaojie; Tieleman, D Peter; Liang, Qing

2018-02-01

The interactions between nanoparticles and lipid bilayers are critical in applications of nanoparticles in nanomedicine, cell imaging, toxicology, and elsewhere. Here, we investigate the interactions between nanoparticles coated with neutral and/or charged ligands and phase-separated lipid bilayers using coarse-grained molecular dynamics simulation. Both penetration and adsorption processes as well as the final distribution of the nanoparticles can be readily modulated by varying the ligand density and the surface charge of the nanoparticles. Completely hydrophobic (neutral) nanoparticles with larger size initially preferentially penetrate into the liquid-disordered region of the lipid bilayer and finally transfer into the liquid-ordered region; partially hydrophilic nanoparticles with low or moderate surface charge tend to either distribute in the liquid-disordered region or be adsorbed on the surface of the lipid bilayer, while strongly hydrophilic nanoparticles with high surface charge always reside on the surface of the lipid bilayer. Interactions of the nanoparticles with the lipid bilayers are affected by the surface charge of nanoparticles, hydrophobic mismatch, bending of the ligands, and the packing state of the lipids. Insight in these factors can be used to improve the efficiency of designing nanoparticles for specific applications.

One-dimension modeling on the parallel-plate ion extraction process based on a non-electron-equilibrium fluid model

NASA Astrophysics Data System (ADS)

Li, He-Ping; Chen, Jian; Guo, Heng; Jiang, Dong-Jun; Zhou, Ming-Sheng; Department of Engineering Physics Team

2017-10-01

Ion extraction from a plasma under an externally applied electric field involve multi-particle and multi-field interactions, and has wide applications in the fields of materials processing, etching, chemical analysis, etc. In order to develop the high-efficiency ion extraction methods, it is indispensable to establish a feasible model to understand the non-equilibrium transportation processes of the charged particles and the evolutions of the space charge sheath during the extraction process. Most of the previous studies on the ion extraction process are mainly based on the electron-equilibrium fluid model, which assumed that the electrons are in the thermodynamic equilibrium state. However, it may lead to some confusions with neglecting the electron movement during the sheath formation process. In this study, a non-electron-equilibrium model is established to describe the transportation of the charged particles in a parallel-plate ion extraction process. The numerical results show that the formation of the Child-Langmuir sheath is mainly caused by the charge separation. And thus, the sheath shielding effect will be significantly weakened if the charge separation is suppressed during the extraction process of the charged particles.

Temperature evolution of polar states in GdMn2O5 and Gd0.8Ce0.2Mn2O5

NASA Astrophysics Data System (ADS)

Sanina, V. A.; Golovenchits, E. I.; Khannanov, B. Kh.; Scheglov, M. P.; Zalesskii, V. G.

2014-11-01

The polar order along the c axis is revealed in GdMn2O5 and Gd0.8Ce0.2Mn2O5 at T ≤ T C1 ≈ 160 K for the first time. This polar order is induced by the charge disproportion in the 2D superstructures emerged due to phase separation. The dynamic state with restricted polar domains of different sizes is found at T > T C1 which is typical of the diffuse ferroelectric phase transition. At the lowest temperatures ( T < 40 K) two polar orders of different origins with perpendicular orientations (along the b and c axes) coexist. The 1D superlattices studied by us earlier in the set of RMn2O5 multiferroics are the charged domain walls which separate of these polar order domains.

Effective Tuning of Ketocyanine Derivatives through Acceptor Substitution.

PubMed

Poe, Ambata; Della Pelle, Andrea; Byrnes, Sean; Thayumanavan, S

2015-05-18

A series of ketocyanine derivatives possessing bis(diarylamino)fluorenyl donors and variable acceptors installed at the bridging carbon atom were synthesized to investigate how the electronic structure of the dye can be systemically tuned through stabilization of the cyanine-like character of the donor by increasing the acceptor strength. Analysis of the (1) H NMR spectra indicates that the "charge-separated" species dominates in these dyes, given that carbons possessing a positive or negative charge in the resonance structures of this state purposefully shift downfield or upfield, respectively, depending on the strength of the acceptor moiety. In DAA-Fl-PI, the acceptor strength and the gain of acceptor aromaticity indicates a predisposition of the separated state, indicated by asymmetry in the (1) H NMR spectrum, as well as uneven distribution of the HOMO on the fluorenyl donor. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscale ferromagnetism in phase-separated manganites

NASA Astrophysics Data System (ADS)

Mori, S.; Horibe, Y.; Asaka, T.; Matsui, Y.; Chen, C. H.; Cheong, S. W.

2007-03-01

Magnetic domain structures in phase-separated manganites were investigated by low-temperature Lorentz electron microscopy, in order to understand some unusual physical properties such as a colossal magnetoresistance (CMR) effect and a metal-to-insulator transition. In particular, we examined a spatial distribution of the charge/orbital-ordered (CO/OO) insulator state and the ferromagnetic (FM) metallic one in phase-separated manganites; Cr-doped Nd0.5Ca0.5MnO3 and ( La1-xPrx)CaMnO3 with x=0.375, by obtaining both the dark-field images and Lorentz electron microscopic ones. It is found that an unusual coexistence of the CO/OO and FM metallic states below a FM transition temperature in the two compounds. The present experimental results clearly demonstrated the coexisting state of the two distinct ground states in manganites.

The influence of charge and the distribution of charge in the polar region of phospholipids on the activity of UDP-glucuronosyltransferase.

PubMed

Zakim, D; Eibl, H

1992-07-05

Studies of the mechanism of lipid-induced regulation of the microsomal enzyme UDP-glucuronosyltransferase have been extended by examining the influence of charge within the polar region on the ability of lipids to activate delipidated pure enzyme. The effects of net negative charge, of charge separation in phosphocholine, and of the distribution of charge in the polar region of lipids were studied using the GT2p isoform isolated from pig liver. Prior experiments have shown that lipids with net negative charge inhibit the enzyme (Zakim, D., Cantor, M., and Eibl, H. (1988) J. Biol. Chem. 263, 5164-5169). The current experiments show that the extent of inhibition on a molar basis increases as the net negative charge increases from -1 to -2. The inhibitory effect of negatively charged lipids is on the functional state of the enzyme and is not due to electrostatic repulsion of negatively charged substrates of the enzyme. Although the inhibitory effect of net negative charge is removed when negative charge is balanced by a positive charge due to a quaternary nitrogen, neutrality of the polar region is not a sufficient condition for activation of the enzyme. In addition to a balance of charge between Pi and the quaternary nitrogen, the distance between the negative and positive charges and the orientation of the dipole created by them are critical for activation of GT2p. The negative and positive charges must be separated by the equivalent of three -CH2- groups for optimal activation by a lipid. Shortening this distance by one -CH2- unit leads to a lipid that is ineffective in activating the enzyme. Reversal of the orientation of the dipole in which the negative charge is on the polymethylene side of the lipid-water interface and the positive charge extends into water also produces a lipid that is not effective for activating GT2p. On the other hand, lipids with phosphoserine as the polar region, which has the "normal" P-N distance but carries a net negative charge, do not inhibit GT2p. This result again illustrates the importance of the dipole of phosphocholine for modulating the functional state of GT2p.

The Charging Events in Contact-Separation Electrification.

PubMed

Musa, Umar G; Cezan, S Doruk; Baytekin, Bilge; Baytekin, H Tarik

2018-02-06

Contact electrification (CE)-charging of surfaces that are contacted and separated, is a common phenomenon, however it is not completely understood yet. Recent studies using surface imaging techniques and chemical analysis revealed a 'spatial' bipolar distribution of charges at the nano dimension, which made a paradigm shift in the field. However, such analyses can only provide information about the charges that remained on the surface after the separation, providing limited information about the actual course of the CE event. Tapping common polymers and metal surfaces to each other and detecting the electrical potential produced on these surfaces 'in-situ' in individual events of contact and separation, we show that, charges are generated and transferred between the surfaces in both events; the measured potential is bipolar in contact and unipolar in separation. We show, the 'contact-charges' on the surfaces are indeed the net charges that results after the separation process, and a large contribution to tribocharge harvesting comes, in fact, from the electrostatic induction resulting from the generated CE charges. Our results refine the mechanism of CE providing information for rethinking the conventional ranking of materials' charging abilities, charge harvesting, and charge prevention.

AC-impedance measurements during thermal runaway process in several lithium/polymer batteries

NASA Astrophysics Data System (ADS)

Uchida, I.; Ishikawa, H.; Mohamedi, M.; Umeda, M.

In this work, we present a set of thermal characterization experiments of charged prismatic polymer lithium-ion battery (PLB) comparatively with those of a lithium-ion battery (LIB). These cells at different state of charge (SOC) were tested inside an accelerated rate calorimeter (ARC) to determine the onset-of-thermal runaway (OTR) temperatures. In addition, the thermally activated components of these cells were followed by monitoring the impedance (at 1 kHz) and the open-circuit voltage (OCV) as a function of temperature. An increase in the impedance was observed at around 133 °C corresponding to the polyethylene separator shutdown. Above 140 °C, the OCV dropped to zero indicating an internal short-circuit due the separator meltdown suggesting that the pinholes created in the separator at meltdown are large enough to create an internal short-circuit.

Stability and charge separation of different CH3NH3SnI3/TiO2 interface: A first-principles study

NASA Astrophysics Data System (ADS)

Yang, Zhenzhen; Wang, Yuanxu; Liu, Yunyan

2018-05-01

Interface has an important effect on charge separation of perovskite solar cells. Using first-principles calculations, we studied several different interfaces between CH3NH3SnI3 and TiO2. The interfacial structure and electronic structure of these interfaces are thoroughly explored. We found that the SnI2/anatase (SnI2/A) system is more stable than the other three systems, because an anatase surface can make Snsbnd I bond faster restore to the pristine value than a rutile surface, and SnI2/A system has a smaller standard deviation. The calculated plane-averaged electrostatic potential and the density of states suggest that SnI2/anatase interface has a better separation of photo-generated electron-hole pairs.

Probing Supramolecular Interactions between a Crown Ether Appended Zinc Phthalocyanine and an Ammonium Group Appended to a C60 Derivative.

PubMed

Lederer, Marcus; Hahn, Uwe; Strub, Jean-Marc; Cianférani, Sarah; Van Dorsselaer, Alain; Nierengarten, Jean-François; Torres, Tomas; Guldi, Dirk M

2016-02-01

Self-assembly driven by crown ether complexation of zinc phthalocyanines equipped with one 18-crown-6 moiety and fullerenes bearing an ammonium head group afforded a novel donor-acceptor hybrid. In reference experiments, fullerenes containing a Boc-protected amine functionality have been probed. The circumvention of zinc phthalocyanine aggregation is important for the self-assembly, which required the addition of pyridine. From absorption and fluorescence titration assays, which provided sound and unambiguous evidence for mutual interactions between the electron donor and the electron acceptor within the hybrids, association constants in the order of 8.0×10 5  m -1 have been derived. The aforementioned is based on 1:1 stoichiometries, which have been independently confirmed by Job's plot measurements. In the excited state, which has been examined by transient absorption experiments, intermolecular charge separation evolves from the photoexcited zinc phthalocyanine to the fullerene subunit and leads to short-lived charge-separated states. Interestingly, photoexcitation of zinc phthalocyanine dimers/aggregates can also be followed by an intermolecular charge separation between vicinal phthalocyanines. These multicomponent supramolecular ensembles have also been shown by in-depth electrospray ionization mass spectrometry (ESI-MS) studies, giving rise to the formation and detection of a variety of non-covalently linked species. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

van der Heide, P. A. W.

2005-02-01

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

Structural Variations in β-(BDA-TTP)2FeCl4 at Low Temperature and under Pressure: Charge-Ordered State with a Two-Fold Crystal Structure

NASA Astrophysics Data System (ADS)

Sasamori, Kota; Takahashi, Kazuyuki; Kodama, Takeshi; Fujita, Wataru; Kikuchi, Koichi; Yamada, Jun-ichi

2013-05-01

The pressure-induced organic superconductor β-(BDA-TTP)2FeCl4 [BDA-TTP = 2,5-bis(1,3-dithian-2-ylidene)-1,3,4,6-tetrathiapentalene], which shows a metal--insulator (MI) transition at TMI = 113 K under ambient pressure, has been found by X-ray study to have a two-fold crystal structure along the c-axis in the insulating state at 10 K. In the donor layer, there are four independent BDA-TTP molecules, which are divided into two charge-poor ones and two charge-rich ones on the basis of the folding dihedral angles around the intramolecular sulfur-to-sulfur axes of two outer dithiane rings in BDA-TTP. The charge separation leads to the formation of two types of dimers: a dimer consisting of two charge-poor donors and a dimer consisting of two charge-rich ones. The tight-binding band calculation revealed a band gap of 5.3 meV in the energy dispersion. The MI transition can be therefore accounted for by the charge separation. In addition, we investigated the crystal and electronic structures of β-(BDA-TTP)2FeCl4 at different pressures up to 21 kbar, and found that the application of pressures causes variations in both the conformation of donor molecule and the donor arrangement, which are responsible for almost uniform interaction in the donor stacking and for an increase in bandwidth (W). As a result, the suppression of MI transition and subsequent occurrence of superconductivity in β-(BDA-TTP)2FeCl4 would be observed with increasing pressure.

Calibration of BAS-TR image plate response to high energy (3-300 MeV) carbon ions

NASA Astrophysics Data System (ADS)

Doria, D.; Kar, S.; Ahmed, H.; Alejo, A.; Fernandez, J.; Cerchez, M.; Gray, R. J.; Hanton, F.; MacLellan, D. A.; McKenna, P.; Najmudin, Z.; Neely, D.; Romagnani, L.; Ruiz, J. A.; Sarri, G.; Scullion, C.; Streeter, M.; Swantusch, M.; Willi, O.; Zepf, M.; Borghesi, M.

2015-12-01

The paper presents the calibration of Fuji BAS-TR image plate (IP) response to high energy carbon ions of different charge states by employing an intense laser-driven ion source, which allowed access to carbon energies up to 270 MeV. The calibration method consists of employing a Thomson parabola spectrometer to separate and spectrally resolve different ion species, and a slotted CR-39 solid state detector overlayed onto an image plate for an absolute calibration of the IP signal. An empirical response function was obtained which can be reasonably extrapolated to higher ion energies. The experimental data also show that the IP response is independent of ion charge states.

Calibration of BAS-TR image plate response to high energy (3-300 MeV) carbon ions.

PubMed

Doria, D; Kar, S; Ahmed, H; Alejo, A; Fernandez, J; Cerchez, M; Gray, R J; Hanton, F; MacLellan, D A; McKenna, P; Najmudin, Z; Neely, D; Romagnani, L; Ruiz, J A; Sarri, G; Scullion, C; Streeter, M; Swantusch, M; Willi, O; Zepf, M; Borghesi, M

2015-12-01

The paper presents the calibration of Fuji BAS-TR image plate (IP) response to high energy carbon ions of different charge states by employing an intense laser-driven ion source, which allowed access to carbon energies up to 270 MeV. The calibration method consists of employing a Thomson parabola spectrometer to separate and spectrally resolve different ion species, and a slotted CR-39 solid state detector overlayed onto an image plate for an absolute calibration of the IP signal. An empirical response function was obtained which can be reasonably extrapolated to higher ion energies. The experimental data also show that the IP response is independent of ion charge states.

Theoretical study of dynamic electron-spin-polarization via the doublet-quartet quantum-mixed state and time-resolved ESR spectra of the quartet high-spin state.

PubMed

Teki, Yoshio; Matsumoto, Takafumi

2011-04-07

The mechanism of the unique dynamic electron polarization of the quartet (S = 3/2) high-spin state via a doublet-quartet quantum-mixed state and detail theoretical calculations of the population transfer are reported. By the photo-induced electron transfer, the quantum-mixed charge-separate state is generated in acceptor-donor-radical triad (A-D-R). This mechanism explains well the unique dynamic electron polarization of the quartet state of A-D-R. The generation of the selectively populated quantum-mixed state and its transfer to the strongly coupled pure quartet and doublet states have been treated both by a perturbation approach and by exact numerical calculations. The analytical solutions show that generation of the quantum-mixed states with the selective populations after de-coherence and/or accompanying the (complete) dephasing during the charge-recombination are essential for the unique dynamic electron polarization. Thus, the elimination of the quantum coherence (loss of the quantum information) is the key process for the population transfer from the quantum-mixed state to the quartet state. The generation of high-field polarization on the strongly coupled quartet state by the charge-recombination process can be explained by a polarization transfer from the quantum-mixed charge-separate state. Typical time-resolved ESR patterns of the quantum-mixed state and of the strongly coupled quartet state are simulated based on the generation mechanism of the dynamic electron polarization. The dependence of the spectral pattern of the quartet high-spin state has been clarified for the fine-structure tensor and the exchange interaction of the quantum-mixed state. The spectral pattern of the quartet state is not sensitive towards the fine-structure tensor of the quantum-mixed state, because this tensor contributes only as a perturbation in the population transfer to the spin-sublevels of the quartet state. Based on the stochastic Liouville equation, it is also discussed why the selective population in the quantum-mixed state is generated for the "finite field" spin-sublevels. The numerical calculations of the elimination of the quantum coherence (de-coherence and/or dephasing) are demonstrated. A new possibility of the enhanced intersystem crossing pathway in solution is also proposed.

Simplified charge separation energetics in a two-dimensional model for polymer-based photovoltaic cells.

PubMed

Sylvester-Hvid, Kristian O; Ratner, Mark A

2005-01-13

An extension of our two-dimensional working model for photovoltaic behavior in binary polymer and/or molecular photoactive blends is presented. The objective is to provide a more-realistic description of the charge generation and charge separation processes in the blend system. This is achieved by assigning an energy to each of the possible occupation states, describing the system according to a simple energy model for exciton and geminate electron-hole pair configurations. The energy model takes as primary input the ionization potential, electron affinity and optical gap of the components of the blend. The underlying photovoltaic model considers a nanoscopic subvolume of a photoactive blend and represents its p- and n-type domain morphology, in terms of a two-dimensional network of donor and acceptor sites. The nearest-neighbor hopping of charge carriers in the illuminated system is described in terms of transitions between different occupation states. The equations governing the dynamics of these states are cast into a linear master equation, which can be solved for arbitrary two-dimensional donor-acceptor networks, assuming stationary conditions. The implications of incorporating the energy model into the photovoltaic model are illustrated by simulations of the short circuit current versus thickness of the photoactive blend layer for different choices of energy parameters and donor-acceptor topology. The results suggest the existence of an optimal thickness of the photoactive film in bulk heterojunctions, based on kinetic considerations alone, and that this optimal thickness is very sensitive to the choice of energy parameters. The results also indicate space-charge limiting effects for interpenetrating donor-acceptor networks with characteristic domain sizes in the nanometer range and high driving force for the photoinduced electron transfer across the donor-acceptor internal interface.

Study of talcum charging status in parallel plate electrostatic separator based on particle trajectory analysis

NASA Astrophysics Data System (ADS)

Yunxiao, CAO; Zhiqiang, WANG; Jinjun, WANG; Guofeng, LI

2018-05-01

Electrostatic separation has been extensively used in mineral processing, and has the potential to separate gangue minerals from raw talcum ore. As for electrostatic separation, the particle charging status is one of important influence factors. To describe the talcum particle charging status in a parallel plate electrostatic separator accurately, this paper proposes a modern images processing method. Based on the actual trajectories obtained from sequence images of particle movement and the analysis of physical forces applied on a charged particle, a numerical model is built, which could calculate the charge-to-mass ratios represented as the charging status of particle and simulate the particle trajectories. The simulated trajectories agree well with the experimental results obtained by images processing. In addition, chemical composition analysis is employed to reveal the relationship between ferrum gangue mineral content and charge-to-mass ratios. Research results show that the proposed method is effective for describing the particle charging status in electrostatic separation.

Optoelectronic Properties of Conjugated Block Copolymer with Flexible Linking Group

NASA Astrophysics Data System (ADS)

Hu, Zhiqi; Verduzco, Rafael

State-of-the-art organic photovoltaics (OPVs) are prepared by depositing a disordered, co-continuous donor and acceptor blend. While optimization of material processing has produced significant improvements in performance, a fundamental understanding of charge separation and recombination at the donor/acceptor interface is lacking. Block copolymers with donor and acceptor polymer blocks provide an opportunity for controlling the donor-accepter interfacial structure and understanding its relationship to charge separation and photovoltaic performance. Here, we report the synthesis and characterization of donor-linker-acceptor block copolymers for use in OPVs. A series of poly(3-hexylthiophene)-block- poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(thiophen-5-yl)-2,1,3-benzothiadiazole]-2',2''-diyl) (P3HT-linkerPFTBT) are synthesized with flexible oligo-ethylene glycol (PEG) linkers. Photoluminescence measurements demonstrate that the insertion of a non-conjugated linker has a significant impact on energy transfer between the two blocks, and the block copolymers are used as additives for bulk heterojunction OPVs. This work provides insight into the charge separation process and demonstrates a technique for tailoring the donor-accepter interface in OPVs.

Application of ion mobility-mass spectrometry to microRNA analysis.

PubMed

Takebayashi, Kosuke; Hirose, Kenji; Izumi, Yoshihiro; Bamba, Takeshi; Fukusaki, Eiichiro

2013-03-01

Liquid chromatography/mass spectrometry is widely used for studying sequence determination and modification analysis of small RNAs. However, the efficiency of liquid chromatography-based separation of intact small RNA species is insufficient, since the physiochemical properties among small RNAs are very similar. In this study, we focused on ion mobility-mass spectrometry (IM-MS), which is a gas-phase separation technique coupled with mass spectrometry; we have evaluated the utility of IM-MS for microRNA (miRNA) analysis. A multiply charged deprotonated ion derived from an 18-24-nt-long miRNA was formed by electrospray ionization, and then the time, called the "drift time", taken by each ion to migrate through a buffer gas was measured. Each multivalent ion was temporally separated on the basis of the charge state and structural formation; 3 types of unique mass-mobility correlation patterns (i.e., chainlike-form, hairpin-form, and dimer-form) were present on the two-dimensional mobility-mass spectrum. Moreover, we found that the ion size (sequence length) and the secondary structures of the small RNAs strongly contributed to the IM-MS-based separation, although solvent conditions such as pH had no effect. Therefore, sequence isomers could also be discerned by the selection of each specific charged ion, i.e., the 6(-) charged ion reflected a majority among chainlike-, hairpin-, and other structures. We concluded that the IM-MS provides additional capability for separation; thus, this analytical method will be a powerful tool for comprehensive small RNA analysis. Copyright © 2012. Published by Elsevier B.V.

Multiple exciton dissociation in CdSe quantum dots by ultrafast electron transfer to adsorbed methylene blue.

PubMed

Huang, Jier; Huang, Zhuangqun; Yang, Ye; Zhu, Haiming; Lian, Tianquan

2010-04-07

Multiexciton generation in quantum dots (QDs) may provide a new approach for improving the solar-to-electric power conversion efficiency in QD-based solar cells. However, it remains unclear how to extract these excitons before the ultrafast exciton-exciton annihilation process. In this study we investigate multiexciton dissociation dynamics in CdSe QDs adsorbed with methylene blue (MB(+)) molecules by transient absorption spectroscopy. We show that excitons in QDs dissociate by ultrafast electron transfer to MB(+) with an average time constant of approximately 2 ps. The charge separated state is long-lived (>1 ns), and the charge recombination rate increases with the number of dissociated excitons. Up to three MB(+) molecules per QD can be reduced by exciton dissociation. Our result demonstrates that ultrafast interfacial charge separation can effectively compete with exciton-exciton annihilation, providing a viable approach for utilizing short-lived multiple excitons in QDs.

On the nature of liquid junction and membrane potentials.

PubMed

Perram, John W; Stiles, Peter J

2006-09-28

Whenever a spatially inhomogeneous electrolyte, composed of ions with different mobilities, is allowed to diffuse, charge separation and an electric potential difference is created. Such potential differences across very thin membranes (e.g. biomembranes) are often interpreted using the steady state Goldman equation, which is usually derived by assuming a spatially constant electric field. Through the fundamental Poisson equation of electrostatics, this implies the absence of free charge density that must provide the source of any such field. A similarly paradoxical situation is encountered for thick membranes (e.g. in ion-selective electrodes) for which the diffusion potential is normally interpreted using the Henderson equation. Standard derivations of the Henderson equation appeal to local electroneutrality, which is also incompatible with sources of electric fields, as these require separated charges. We analyse self-consistent solutions of the Nernst-Planck-Poisson equations for a 1 : 1-univalent electrolyte to show that the Goldman and Henderson steady-state membrane potentials are artefacts of extraneous charges created in the reservoirs of electrolyte solution on either side of the membrane, due to the unphysical nature of the usual (Dirichlet) boundary conditions assumed to apply at the membrane-electrolyte interfaces. We also show, with the aid of numerical simulations, that a transient electric potential difference develops in any confined, but initially non-uniform, electrolyte solution. This potential difference ultimately decays to zero in the real steady state of the electrolyte, which corresponds to thermodynamic equilibrium. We explain the surprising fact that such transient potential differences are well described by the Henderson equation by using a computer algebra system to extend previous steady-state singular perturbation theories to the time-dependent case. Our work therefore accounts for the success of the Henderson equation in analysing experimental liquid-junction potentials.

Use of a mixture of n-dodecyl-beta-D-maltoside and sodium dodecyl sulfate in poly(dimethylsiloxane) microchips to suppress adhesion and promote separation of proteins.

PubMed

Huang, Bo; Kim, Samuel; Wu, Hongkai; Zare, Richard N

2007-12-01

Dynamic modification of poly(dimethylsiloxane) channels using a mixture of n-dodecyl-beta-D-maltoside (DDM) and sodium dodecyl sulfate (SDS) is able to suppress analyte adsorption and control electroosmotic flow (EOF). In this mixed surfactant system, the nonionic surfactant DDM functions as a surface blocking reagent, whereas the anionic surfactant SDS introduces negative charges to the channel walls. Changing the DDM/SDS mixing ratio tunes the surface charge density and the strength of EOF. Using 0.1% (w/v) DDM and 0.03% (w/v) SDS, Alexa Fluor 647 labeled streptavidin can be analyzed according to the charges added by the fluorophores. Protein molecules with different numbers of fluorophores are well resolved. DDM and SDS also form negatively charged mixed micelles, which act as a separation medium. The low critical micellar concentration of DDM/SDS mixed micelles also allows the use of SDS at a nondenaturing concentration, which enables the analysis of proteins in their native state. The immunocomplex between a membrane protein, beta2 adrenergic receptor, and anti-FLAG antibody has been fully separated using 0.1% (w/v) DDM and 0.03% (w/v) SDS. We have also analyzed the composition of light-harvesting protein-chromophore complexes in cyanobacteria.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry.

PubMed

Haler, Jean R N; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-11-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. Graphical Abstract ᅟ.

Multiple Gas-Phase Conformations of a Synthetic Linear Poly(acrylamide) Polymer Observed Using Ion Mobility-Mass Spectrometry

NASA Astrophysics Data System (ADS)

Haler, Jean R. N.; Far, Johann; Aqil, Abdelhafid; Claereboudt, Jan; Tomczyk, Nick; Giles, Kevin; Jérôme, Christine; De Pauw, Edwin

2017-08-01

Ion mobility-mass spectrometry (IM-MS) has emerged as a powerful separation and identification tool to characterize synthetic polymer mixtures and topologies (linear, cyclic, star-shaped,…). Electrospray coupled to IM-MS already revealed the coexistence of several charge state-dependent conformations for a single charge state of biomolecules with strong intramolecular interactions, even when limited resolving power IM-MS instruments were used. For synthetic polymers, the sample's polydispersity allows the observation of several chain lengths. A unique collision cross-section (CCS) trend is usually observed when increasing the degree of polymerization (DP) at constant charge state, allowing the deciphering of different polymer topologies. In this paper, we report multiple coexisting CCS trends when increasing the DP at constant charge state for linear poly(acrylamide) PAAm in the gas phase. This is similar to observations on peptides and proteins. Biomolecules show in addition population changes when collisionally heating the ions. In the case of synthetic PAAm, fragmentation occurred before reaching the energy for conformation conversion. These observations, which were made on two different IM-MS instruments (SYNAPT G2 HDMS and high resolution multi-pass cyclic T-Wave prototype from Waters), limit the use of ion mobility for synthetic polymer topology interpretations to polymers where unique CCS values are observed for each DP at constant charge state. [Figure not available: see fulltext.

Convergent synthesis and photoinduced processes in multi-chromophoric rotaxanes.

PubMed

Megiatto, Jackson D; Li, Ke; Schuster, David I; Palkar, Amit; Herranz, M Ángeles; Echegoyen, Luis; Abwandner, Silke; de Miguel, Gustavo; Guldi, Dirk M

2010-11-18

A series of [2]rotaxane materials, in which [60]fullerene is linked to a macrocycle and ferrocene (Fc) moieties are placed at the termini of a thread, both of which possess a central Cu(I)-1,10-phenanthroline [Cu(phen)(2)](+) complex, were synthesized by self-assembly using Sauvage metal template methodology. Two types of threads were constructed, one with terminal ester linkages, and a second with terminal 1,2,3-triazole linkages derived from Cu(I)-catalyzed "click" 1,3-cycloaddition reactions. Model compounds lacking the fullerene moiety were prepared in an analogous manner. The ability of the interlocked Fc-[Cu(phen)(2)](+)-C(60) hybrids to undergo electron transfer upon photoexcitation in benzonitrile, dichloromethane, and ortho-dichlorobenzene was investigated by means of time-resolved fluorescence and transient absorption spectroscopy, using excitation wavelengths directed at the fullerene and [Cu(phen)(2)](+) subunits. The energies of the electronic excited states and charge separated (CS) states that might be formed upon photoexcitation were determined from spectroscopic and electrochemical data. These studies showed that MLCT excited states of the copper complex in the fullerenerotaxanes were quenched by electron transfer to the fullerene in benzonitrile, resulting in charge separated states with oxidized copper and reduced fullerene moieties, (Fc)(2)-[Cu(phen)(2)](2+)-C(60)(•-). Even though electron transfer from Fc to the oxidized copper complex is predicted to be exergonic by 0.16 to 0.20 eV, no unequivocal evidence in support of such a process was obtained. The conclusion that Fc plays no role in the photoinduced processes in our systems rests on the lack of enhancement of the lifetime of the charge separated state, as measured by decay of C(60)(•-) at ∼1000 nm, since one-electron oxidized Fc is very difficult to detect spectroscopically in the 500-800 nm spectral region.

Structural and dynamical properties of recombining ultracold neutral plasma

NASA Astrophysics Data System (ADS)

Tiwari, Sanat Kumar; Shaffer, Nathaniel R.; Baalrud, Scott D.

2017-10-01

An ultracold plasma (UCP) is an evolving collection of free charges and bound charges (Rydberg atoms). Over time, bound species concentration increases due to recombination. We present the structural and dynamical properties of an evolving UCP using classical molecular dynamics simulation. Coulomb collapse is avoided using a repulsive core with the attractive Coulomb potential. The repulsive core size controls the concentration of bound states, as it determines the depth of the potential well between opposite charges. We vary the repulsive core size to emulate the quasi-static state of plasma at different time during the evolution. Binary, chain and ring-like bound states are observed in the simulation carried out at different coupling strengths and repulsive core size. The effect of bound states can be seen as molecular peaks in the radial distribution function (RDF). The thermodynamic properties associated with the free charges can be analyzed from RDF by separating free from bound states. These bound states also change the dynamical properties of the plasma. The electron velocity auto-correlation displays oscillations due to the orbital motion in bound states. These bound states act like a neutral species, damping electron plasmon modes and broadening the ion acoustic mode. This work is supported by AFOSR Grant Number FA9550-16-1-0221. It used computational resources by XSEDE, which is supported by NSF Grant Number ACI-1053575.

New Estimates of Inferred Ionic Charge States for Solar Energetic Particle Events with ACE and STEREO

NASA Astrophysics Data System (ADS)

Labrador, A. W.; Sollitt, L. S.; Cohen, C. M.; Cummings, A. C.; Leske, R. A.; Mason, G. M.; Mewaldt, R. A.; Stone, E.; von Rosenvinge, T. T.; Wiedenbeck, M. E.

2012-12-01

Solar energetic particle (SEP) mean ionic charge states can depend on source temperatures and populations (e.g. seed populations) and conditions during acceleration and transport such as stripping. Multi-spacecraft observations of charge states from widely separated spacecraft may reveal evidence for seed populations that vary with longitude. In this presentation, we report new estimates of inferred high energy ionic charge states using the Sollitt et al. (2008) method that fits SEP energy-dependent decay times for SEP event elements to derive mean charge states. In the method, intensity decay times during SEP events are fitted for each element for various energies, and then the energy dependence of the decay times is fitted for each element. Finally, charge-to-mass ratios relative to that of a calibration element (carbon in this case) are obtained, and when Q(C)=5.9 is assumed for calibration, mean charge states for other elements can be inferred. Previously, ACE/SIS and ACE/ULEIS data were applied to three SEP events (Nov. 6, 1997; Nov. 4, 2001; Apr. 21, 2002) with this method, and last year, we reported new results for the Dec. 6, 2006 SEP event compatible with SAMPEX/MAST results. Additional work continues to generalize and extend the software to use publicly available online data from ACE and the two STEREO spacecraft. Energy ranges are those covered by the instruments on ACE (e.g. reference element C at <.1 MeV/nuc from ULEIS to ~64 MeV/nuc from SIS) and on STEREO (e.g. C at 3.2 - 33 MeV/nuc from LET). Initial candidate SEP events for multi-spacecraft charge state estimates are those of Mar. 8, 2011, Mar. 21, 2011, Jan. 24, 2012, and Mar. 4, 2012. Results from events observed by single spacecraft may also be reported.

1,3-Diphenylisobenzofuran: a Model Chromophore for Singlet Fission

DOE PAGES

Johnson, Justin C.; Michl, Josef

2017-09-11

In this review we first provide an introductory description of the singlet fission phenomenon and then describe the ground and electronically excited states of the parent 1,3-diphenylisobenzofuran chromophore (1) and about a dozen of its derivatives. A discussion of singlet fission in thin polycrystalline layers of these materials follows. The highest quantum yield of triplet formation by singlet fission, 200% at 80 K, is found in one of the two known crystal modification of the parent. In the other modification and in many derivatives, excimer formation competes successfully and triplet yields are low. A description of solution photophysics of covalentmore » dimers is described in the next section. Triplet yields are very low, but interesting phenomena are uncovered. One is an observation of a separated-charges (charge-transfer) intermediate in highly polar solvents. The other is an observation of excitation isomerism in both singlet and triplet states, where in one isomer the excitation is delocalized over both halves of the covalent dimer, whereas in the other it is localized on one of the halves. Finally, in the last section we present the operation of a simple device illustrating the use of triplets generated by singlet fission for charge separation.« less

Local Time-Dependent Charging in a Perovskite Solar Cell.

PubMed

Bergmann, Victor W; Guo, Yunlong; Tanaka, Hideyuki; Hermes, Ilka M; Li, Dan; Klasen, Alexander; Bretschneider, Simon A; Nakamura, Eiichi; Berger, Rüdiger; Weber, Stefan A L

2016-08-03

Efficient charge extraction within solar cells explicitly depends on the optimization of the internal interfaces. Potential barriers, unbalanced charge extraction, and interfacial trap states can prevent cells from reaching high power conversion efficiencies. In the case of perovskite solar cells, slow processes happening on time scales of seconds cause hysteresis in the current-voltage characteristics. In this work, we localized and investigated these slow processes using frequency-modulation Kelvin probe force microscopy (FM-KPFM) on cross sections of planar methylammonium lead iodide (MAPI) perovskite solar cells. FM-KPFM can map the charge density distribution and its dynamics at internal interfaces. Upon illumination, space charge layers formed at the interfaces of the selective contacts with the MAPI layer within several seconds. We observed distinct differences in the charging dynamics at the interfaces of MAPI with adjacent layers. Our results indicate that more than one process is involved in hysteresis. This finding is in agreement with recent simulation studies claiming that a combination of ion migration and interfacial trap states causes the hysteresis in perovskite solar cells. Such differences in the charging rates at different interfaces cannot be separated by conventional device measurements.

Charge Separation Mechanisms in Ordered Films of Self-Assembled Donor–Acceptor Dyad Ribbons

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

Logsdon, Jenna L.; Hartnett, Patrick E.; Nelson, Jordan N.

2017-04-21

Orthogonal attachment of polar and nonpolar side-chains to a zinc porphyrin-perylenediimide dyad (ZnP-PDI, 1a) is shown to result in self-assembly of ordered supramolecular ribbons in which the ZnP and PDI molecules form segregated π-stacked columns. Following photoexcitation of the ordered ribbons, ZnP+•-PDI–• radical ion pairs form in <200 fs and subsequently produce a 30 ± 3% yield of free charge carriers that live for about 100 μs. Elongating the side chains on ZnP and PDI in 1b enhances the order of the films, but does not result in an increase in free charge carrier yield. In addition, this yield ismore » independent of temperature, free energy of reaction, and the ZnP-PDI distance in the covalent dyad. These results suggest that the free charge carrier yield in this system is not limited by a bound charge transfer (CT) state or promoted by a vibronically hot CT state. Instead, it is likely that π-stacking of the segregated donors and acceptors within the ribbons results in delocalization of the charges following photoexcitation, allowing them to overcome Coulombic attraction and generate free charge carriers.« less

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

PubMed

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

2013-08-15

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

Theory and practical understanding of the migration behavior of proteins and peptides in CE and related techniques.

PubMed

Freitag, Ruth; Hilbrig, Frank

2007-07-01

CEC is defined as an analytical method, where the analytes are separated on a chromatographic column in the presence of an applied voltage. The separation of charged analytes in CEC is complex, since chromatographic interaction, electroosmosis and electrophoresis contribute to the experimentally observed behavior. The putative contribution of effects such as surface electrodiffusion has been suggested. A sound theoretical treatment incorporating all effects is currently not available. The question of whether the different effects contribute in an independent or an interdependent manner is still under discussion. In this contribution, the state-of-the-art in the theoretical description of the individual contributions as well as models for the retention behavior and in particular possible dimensionless 'retention factors' is discussed, together with the experimental database for the separation of charged analytes, in particular proteins and peptides, by CEC and related techniques.

Thermodynamics of Polaronic States in Artificial Spin Ice

NASA Astrophysics Data System (ADS)

Farhan, Alan

Artificial spin ices represent a class of systems consisting of lithographically patterned nanomagnets arranged in two-dimensional geometries. They were initially introduced as a two-dimensional analogue to geometrically frustrated pyrochlore spin ice, and the most recent introduction of artificial spin ice systems with thermally activated moment fluctuations not only delivered the possibility to directly investigate geometrical frustration and emergent phenomena with real space imaging, but also paved the way to design and investigate new two-dimensional magnetic metamaterials, where material properties can be directly manipulated giving rise to properties that do not exist in nature. Here, taking advantage of cryogenic photoemission electron microscopy, and using the concept of emergent magnetic charges, we are able to directly visualize the creation and annihilation of screened emergent magnetic monopole defects in artificial spin ice. We observe that these polaronic states arise as intermediate states, separating an energetically excited out-of-equilibrium state and low-energy equilibrium configurations. They appear as a result of a local screening effect between emergent magnetic charge defects and their neighboring magnetic charges, thus forming a transient minimum, before the system approaches a global minimum with the least amount of emergent magnetic charge defects. This project is funded by the Swiss National Science Foundation.

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2

NASA Astrophysics Data System (ADS)

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-02-01

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO2) via the observation of a positive absorption signal (at λ pr  >  610 nm) at later delay times. An electron transfer rate of 7  ×  1010 s-1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO2.

Enhanced Drug Photosafety by Interchromophoric Interaction Owing to Intramolecular Charge Separation.

PubMed

Li, Ming-De; Yan, Zhiping; Zhu, Ruixue; Phillips, David Lee; Aparici-Espert, Isabel; Lhiaubet-Vallet, Virginie; Miranda, Miguel A

2018-05-02

Imatinib is a synthetic tyrosinase inhibitor that is employed for the treatment of some kinds of human cancer. This drug has a low phototoxicity towards DNA, but its pyridylpyrimidine (1) fragment by itself exhibits significant phototoxicitiy. The intrinsic mechanism that leads to the enhanced photosafety of Imatinib is not yet known. Here, the properties of the excited state and interchromophoric interactions of Imatinib have been explored by using ultrafast laser flash photolysis and agarose electrophoresis studies. An intramolecular charge separation was directly observed for the irradiated Imatinib, which accounts for the relaxation of its excited state. An anionic form of pyridylpyrimidine (1) was deduced from the results of time-resolved resonance Raman spectra and by quenching experimental studies on compound 1 and diaminotoluene. In contrast, compound 1 efficiently transformed into triplet excited states with a long lifetime, which explained the phototoxicity associated with this fragment. This work provides insight into how to design drugs with lower phototoxicitiy or improved photostability by using interchromophoric interactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ultrafast dynamics of differently aligned COOH-DTE-BODIPY conjugates linked to the surface of TiO2.

PubMed

Schweighöfer, Felix; Yüce, Imanuel; Dworak, Lars; Guo, Peng; Zastrow, Marc; Mayer, Kerstin; Barta, Christoph; Liebmann, Diana; Ziebart, Nandor; Rück-Braun, Karola; Wachtveitl, Josef

2018-01-05

The photoinduced dynamics of two DTE-BODIPY conjugates A, B with carboxylic acid anchoring groups coupled to the surface of TiO 2 were studied by ultrafast transient absorption spectroscopy. For compound A, with an orthogonal orientation of the BODIPY chromophore and the photoswitchable DTE unit, a charge separated state could not be reliably detected. Nevertheless, besides the energy transfer from the BODIPY to the ring-closed DTE-c, indications for an electron transfer reaction were found by analyzing fluorescence quenching on TiO 2 in steady state fluorescence measurements. For compound B with a parallel orientation of chromophore and photoswitch, a charge separated state was conclusively identified for the coupled dyad (TiO 2 ) via the observation of a positive absorption signal (at λ pr   >  610 nm) at later delay times. An electron transfer rate of 7  ×  10 10 s -1 can be extracted, indicating slower processes in the dyads in comparison to previously published electron transfer reactions of DTE compounds coupled to TiO 2 .

Artificial Photosynthetic Reaction Center Exhibiting Acid-Responsive Regulation of Photoinduced Charge Separation

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

Pahk, Ian; Kodis, Gerdenis; Fleming, Graham R.

Charge separation (CS) is the primary light-driven reaction in photosynthesis whereas onphotochemical quenching (NPQ) is a photoprotective regulatory mechanism employed by many photosynthetic organisms to dynamically modulate energy flow within the photosynthetic apparatus in response to fluctuating light conditions. Activated by decreases in lumen pH produced during periods of high photon flux, NPQ induces rapid thermal dissipation of excess excitation energy. As a result, the rate of CS decreases, thereby limiting the accumulation of potentially deleterious reactive intermediates and byproducts. In this article, a molecular triad that functionally mimics the effects of NPQ associated with an artificial photosynthetic reaction centermore » is described. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies have been used to demonstrate a 1 order of magnitude reduction in the CS quantum yield via reversible protonation of an excited-state-quenching molecular switch moiety. As in the natural system, the populations of unquenched and quenched states and therefore the overall yields of CS were found to be dependent on acid concentration.« less

Two-leg ladder systems with dipole–dipole Fermion interactions

NASA Astrophysics Data System (ADS)

Mosadeq, Hamid; Asgari, Reza

2018-05-01

The ground-state phase diagram of a two-leg fermionic dipolar ladder with inter-site interactions is studied using density matrix renormalization group (DMRG) techniques. We use a state-of-the-art implementation of the DMRG algorithm and finite size scaling to simulate large system sizes with high accuracy. We also consider two different model systems and explore stable phases in half and quarter filling factors. We find that in the half filling, the charge and spin gaps emerge in a finite value of the dipole–dipole and on-site interactions. In the quarter filling case, s-wave superconducting state, charge density wave, homogenous insulating and phase separation phases occur depend on the interaction values. Moreover, in the dipole–dipole interaction, the D-Mott phase emerges when the hopping terms along the chain and rung are the same, whereas, this phase has been only proposed for the anisotropic Hubbard model. In the half filling case, on the other hand, there is either charge-density wave or charged Mott order phase depends on the orientation of the dipole moments of the particles with respect to the ladder geometry.

Charge-transfer state and large first hyperpolarizability constant in a highly electronically coupled zinc and gold porphyrin dyad.

PubMed

Fortage, Jérôme; Scarpaci, Annabelle; Viau, Lydie; Pellegrin, Yann; Blart, Errol; Falkenström, Magnus; Hammarström, Leif; Asselberghs, Inge; Kellens, Ruben; Libaers, Wim; Clays, Koen; Eng, Mattias P; Odobel, Fabrice

2009-09-14

We report the synthesis and the characterizations of a novel dyad composed of a zinc porphyrin (ZnP) linked to a gold porphyrin (AuP) through an ethynyl spacer. The UV/Vis absorption spectrum and the electrochemical properties clearly reveal that this dyad exhibits a strong electronic coupling in the ground state as evidenced by shifted redox potentials and the appearance of an intense charge-transfer band localized at lambda = 739 nm in dichloromethane. A spectroelectrochemical study of the dyad along with the parent homometallic system (i.e., ZnP-ZnP and AuP-AuP) was undertaken to determine the spectra of the reduced and oxidized porphyrin units. Femtosecond transient absorption spectroscopic analysis showed that the photoexcitation of the heterometallic dyad leads to an ultrafast formation of a charge-separated state ((+)ZnP-AuP(*)) that displays a particularly long lifetime (tau = 4 ns in toluene) for such a short separation distance. The molecular orbitals of the dyad were determined by DFT quantum-chemical calculations. This theoretical study confirms that the observed intense band at lambda = 739 nm corresponds to an interporphyrin charge-transfer transition from the HOMO orbital localized on the zinc porphyrin to LUMO orbitals localized on the gold porphyrin. Finally, a Hyper-Rayleigh scattering study shows that the dyad possesses a large first molecular hyperpolarizability coefficient (beta = 2100x10(-30) esu at lambda = 1064 nm), thus highlighting the valuable nonlinear optical properties of this new type of push-pull porphyrin system.

Charge Generation and Recombination in Organic Materials for Photovoltaics

NASA Astrophysics Data System (ADS)

Ramirez, Jessica Jacklyn

Understanding the nature of molecular exciton states is critical for the design of organic photovoltaic materials that push current device efficiencies into the next realm. This thesis describes several research projects that have sought to further our understanding of the generation and recombination of charge carriers, facilitated by such excitonic states, in organic systems. We begin with fundamental studies on the excited-state dynamics of several fullerene derivatives. We also venture away from the traditional fullerene-based electron acceptors and consider several derivatized perylene diimides as alternate electron acceptors. We then report on the observation of a broad, structureless, emission emanating from charge-generating films comprised of perfluoroalkyl fullerene derivatives dilutely dispersed in polyfluorene hosts. We have determined that this red-shifted PL signature is the result of radiative recombination from a charge-transfer state that is populated initially as a precursor to charge generation, and may be repopulated upon charge recombination. Our data offers an observable link between charge-generation and charge-transfer emission that is kinetically associated with carrier recombination, and we utilize this link to probe the influence of driving force and polymer microstructure in the fundamental processes of charge generation and decay in small molecule/polymer heterojunctions. Thereafter, we sought to develop our understanding of a novel photophysical mechanism (known as energy pooling) which would allow for the energy of multiple excitons to be 'pooled' towards a central molecular moiety, where the individual exciton energies may add together to create a single highly excited excitonic state. This upconversion-like process would facilitate more efficient photocurrent generation in devices utilizing this mode of charge separation. The primary modes of inquiry utilized in this work come from the spectroscopic techniques of absorbance, steady-state and time-resolved photoluminescence, transient absorption and time-resolved microwave conductivity. Some secondary methods employed include cyclic voltammetry, X-ray diffraction and computational tools from density functional theory. This utilization of both experimental and theoretical methodologies provides a powerful approach to furthering our understanding of both the fundamental photophysics of the systems studied, as well as the charge generation and recombination pathways occurring at organic donor-acceptor interfaces, helping to guide the design of more efficient organic photovoltaics.

14 CFR Appendix A to Part 187 - Methodology for Computation of Fees for Certification Services Performed Outside the United States

Code of Federal Regulations, 2010 CFR

2010-01-01

... persons outside the United States. (b) These rates are based on aviation safety inspector time rather than calculating a separate rate for managerial or clerical time because the inspector is the individual performing the actual service. Charging for inspector time, while building in all costs into the rate base...

14 CFR Appendix A to Part 187 - Methodology for Computation of Fees for Certification Services Performed Outside the United States

Code of Federal Regulations, 2014 CFR

2014-01-01

... persons outside the United States. (b) These rates are based on aviation safety inspector time rather than calculating a separate rate for managerial or clerical time because the inspector is the individual performing the actual service. Charging for inspector time, while building in all costs into the rate base...

14 CFR Appendix A to Part 187 - Methodology for Computation of Fees for Certification Services Performed Outside the United States

Code of Federal Regulations, 2012 CFR

2012-01-01

... persons outside the United States. (b) These rates are based on aviation safety inspector time rather than calculating a separate rate for managerial or clerical time because the inspector is the individual performing the actual service. Charging for inspector time, while building in all costs into the rate base...

14 CFR Appendix A to Part 187 - Methodology for Computation of Fees for Certification Services Performed Outside the United States

Code of Federal Regulations, 2011 CFR

2011-01-01

... persons outside the United States. (b) These rates are based on aviation safety inspector time rather than calculating a separate rate for managerial or clerical time because the inspector is the individual performing the actual service. Charging for inspector time, while building in all costs into the rate base...

Vesicle Adhesion and Fusion Studied by Small-Angle X-Ray Scattering.

PubMed

Komorowski, Karlo; Salditt, Annalena; Xu, Yihui; Yavuz, Halenur; Brennich, Martha; Jahn, Reinhard; Salditt, Tim

2018-04-24

We have studied the adhesion state (also denoted by docking state) of lipid vesicles as induced by the divalent ions Ca 2+ or Mg 2+ at well-controlled ion concentration, lipid composition, and charge density. The bilayer structure and the interbilayer distance in the docking state were analyzed by small-angle x-ray scattering. A strong adhesion state was observed for DOPC:DOPS vesicles, indicating like-charge attraction resulting from ion correlations. The observed interbilayer separations of ∼1.6 nm agree quantitatively with the predictions of electrostatics in the strong coupling regime. Although this phenomenon was observed when mixing anionic and zwitterionic (or neutral) lipids, pure anionic membranes (DOPS) with highest charge density σ resulted in a direct phase transition to a multilamellar state, which must be accompanied by rupture and fusion of vesicles. To extend the structural assay toward protein-controlled docking and fusion, we have characterized reconstituted N-ethylmaleimide-sensitive factor attachment protein receptors in controlled proteoliposome suspensions by small-angle x-ray scattering. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

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.

Photoinduced intercomponent excited-state decays in a molecular dyad made of a dinuclear rhenium(I) chromophore and a fullerene electron acceptor unit.

PubMed

Nastasi, Francesco; Puntoriero, Fausto; Natali, Mirco; Mba, Miriam; Maggini, Michele; Mussini, Patrizia; Panigati, Monica; Campagna, Sebastiano

2015-05-01

A novel molecular dyad, 1, made of a dinuclear {[Re2(μ-X)2(CO)6(μ-pyridazine)]} component covalently-linked to a fullerene unit by a carbocyclic molecular bridge has been prepared and its redox, spectroscopic, and photophysical properties - including pump-probe transient absorption spectroscopy in the visible and near-infrared region - have been investigated, along with those of its model species. Photoinduced, intercomponent electron transfer occurs in 1 from the thermally-equilibrated, triplet metal/ligand-to-ligand charge-transfer ((3)MLLCT) state of the dinuclear rhenium(I) subunit to the fullerene acceptor, with a time constant of about 100 ps. The so-formed triplet charge-separated state recombines in a few nanoseconds by a spin-selective process yielding, rather than the ground state, the locally-excited, triplet fullerene state, which finally decays to the ground state by intersystem crossing in about 290 ns.

Equivalent circuit model of Ge/Si separate absorption charge multiplication avalanche photodiode

NASA Astrophysics Data System (ADS)

Wang, Wei; Chen, Ting; Yan, Linshu; Bao, Xiaoyuan; Xu, Yuanyuan; Wang, Guang; Wang, Guanyu; Yuan, Jun; Li, Junfeng

2018-03-01

The equivalent circuit model of Ge/Si Separate Absorption Charge Multiplication Avalanche Photodiode (SACM-APD) is proposed. Starting from the carrier rate equations in different regions of device and considering the influences of non-uniform electric field, noise, parasitic effect and some other factors, the equivalent circuit model of SACM-APD device is established, in which the steady-state and transient current voltage characteristics can be described exactly. In addition, the proposed Ge/Si SACM APD equivalent circuit model is embedded in PSpice simulator. The important characteristics of Ge/Si SACM APD such as dark current, frequency response, shot noise are simulated, the simulation results show that the simulation with the proposed model are in good agreement with the experimental results.

Initial state q q g correlations as a background for the chiral magnetic effect in collision of small systems

DOE PAGES

Kovner, Alex; Lublinsky, Michael; Skokov, Vladimir

2017-11-13

Motivated by understanding the background to chiral magnetic effect in proton-nucleus collisions from first principles, we compute the three particle correlation in the projectile wave function. We extract the correlations between two quarks and one gluon in the framework of the color glass condensate. This is related to the same-charge correlation of the conventional observable for the chiral magnetic effect. We show that there are two different contributions to this correlation function. One contribution is rapidity-independent and as such can be identified with the pedestal; while the other displays rather strong rapidity dependence. The pedestal contribution and the rapidity-dependent contributionmore » at large rapidity separation between the two quarks result in the negative same charge correlations, while at small rapidity separation the second contribution changes sign. We argue that the computed initial state correlations might be partially responsible for the experimentally observed signal in proton-nucleus collisions.« less

Initial state q q g correlations as a background for the chiral magnetic effect in collision of small systems

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

Kovner, Alex; Lublinsky, Michael; Skokov, Vladimir

Motivated by understanding the background to chiral magnetic effect in proton-nucleus collisions from first principles, we compute the three particle correlation in the projectile wave function. We extract the correlations between two quarks and one gluon in the framework of the color glass condensate. This is related to the same-charge correlation of the conventional observable for the chiral magnetic effect. We show that there are two different contributions to this correlation function. One contribution is rapidity-independent and as such can be identified with the pedestal; while the other displays rather strong rapidity dependence. The pedestal contribution and the rapidity-dependent contributionmore » at large rapidity separation between the two quarks result in the negative same charge correlations, while at small rapidity separation the second contribution changes sign. We argue that the computed initial state correlations might be partially responsible for the experimentally observed signal in proton-nucleus collisions.« less

Initial state q q g correlations as a background for the chiral magnetic effect in collision of small systems

NASA Astrophysics Data System (ADS)

Kovner, Alex; Lublinsky, Michael; Skokov, Vladimir

2017-11-01

Motivated by understanding the background to chiral magnetic effect in proton-nucleus collisions from first principles, we compute the three particle correlation in the projectile wave function. We extract the correlations between two quarks and one gluon in the framework of the color glass condensate. This is related to the same-charge correlation of the conventional observable for the chiral magnetic effect. We show that there are two different contributions to this correlation function. One contribution is rapidity-independent and as such can be identified with the pedestal; while the other displays rather strong rapidity dependence. The pedestal contribution and the rapidity-dependent contribution at large rapidity separation between the two quarks result in the negative same charge correlations, while at small rapidity separation the second contribution changes sign. We argue that the computed initial state correlations might be partially responsible for the experimentally observed signal in proton-nucleus collisions.

Experimental and Theoretical Aspects of Excited State Electron Transfer and Related Phenomena: Conference Held in Honour of Zbigniew R. Grabowski in Pultusk, Poland on September 27-October 2, 1992

DTIC Science & Technology

1992-10-01

DBMBF2 ) undergoes photoreaction with olefins through a partial electron transfer that leads to cycloaddition or sensitized Diels - Alder reactions. We...8217 Fluorescence. 10:00 J.M. WARMAN: Photon-induced Intramolecular Charge Sepaiation Studied byTime-Resolved Microwave Conductivity. 10:30 Coffee 11:)) W...26 Photon-Induced Intramolecular Charge Separation Studied by Time-Resolved Microwave Conductivity John M. Warman IRI, Delft University of Technology

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

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.

2D coherent charge transport in highly ordered conducting polymers doped by solid state diffusion

NASA Astrophysics Data System (ADS)

Kang, Keehoon; Watanabe, Shun; Broch, Katharina; Sepe, Alessandro; Brown, Adam; Nasrallah, Iyad; Nikolka, Mark; Fei, Zhuping; Heeney, Martin; Matsumoto, Daisuke; Marumoto, Kazuhiro; Tanaka, Hisaaki; Kuroda, Shin-Ichi; Sirringhaus, Henning

2016-08-01

Doping is one of the most important methods to control charge carrier concentration in semiconductors. Ideally, the introduction of dopants should not perturb the ordered microstructure of the semiconducting host. In some systems, such as modulation-doped inorganic semiconductors or molecular charge transfer crystals, this can be achieved by spatially separating the dopants from the charge transport pathways. However, in conducting polymers, dopants tend to be randomly distributed within the conjugated polymer, and as a result the transport properties are strongly affected by the resulting structural and electronic disorder. Here, we show that in the highly ordered lamellar microstructure of a regioregular thiophene-based conjugated polymer, a small-molecule p-type dopant can be incorporated by solid state diffusion into the layers of solubilizing side chains without disrupting the conjugated layers. In contrast to more disordered systems, this allows us to observe coherent, free-electron-like charge transport properties, including a nearly ideal Hall effect in a wide temperature range, a positive magnetoconductance due to weak localization and the Pauli paramagnetic spin susceptibility.

Coherent states on horospheric three-dimensional Lobachevsky space

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

Kurochkin, Yu., E-mail: y.kurochkin@ifanbel.bas-net.by; Shoukavy, Dz., E-mail: shoukavy@ifanbel.bas-net.by; Rybak, I., E-mail: Ivan.Rybak@astro.up.pt

2016-08-15

In the paper it is shown that due to separation of variables in the Laplace-Beltrami operator (Hamiltonian of a free quantum particle) in horospheric and quasi-Cartesian coordinates of three dimensional Lobachevsky space, it is possible to introduce standard (“conventional” according to Perelomov [Generalized Coherent States and Their Applications (Springer-Verlag, 1986), p. 320]) coherent states. Some problems (oscillator on horosphere, charged particle in analogy of constant uniform magnetic field) where coherent states are suitable for treating were considered.

Nucleon scalar and tensor charges using lattice QCD simulations at the physical value of the pion mass

NASA Astrophysics Data System (ADS)

Alexandrou, C.; Constantinou, M.; Dimopoulos, P.; Frezzotti, R.; Hadjiyiannakou, K.; Jansen, K.; Kallidonis, C.; Kostrzewa, B.; Koutsou, G.; Mangin-Brinet, M.; Vaquero Avilès-Casco, A.; Wenger, U.

2017-06-01

We present results on the light, strange and charm nucleon scalar and tensor charges from lattice QCD, using simulations with Nf=2 flavors of twisted mass clover-improved fermions with a physical value of the pion mass. Both connected and disconnected contributions are included, enabling us to extract the isoscalar, strange and charm charges for the first time directly at the physical point. Furthermore, the renormalization is computed nonperturbatively for both isovector and isoscalar quantities. We investigate excited state effects by analyzing several sink-source time separations and by employing a set of methods to probe ground state dominance. Our final results for the scalar charges are gSu=5.20 (42 )(15 )(12 ), gSd=4.27 (26 )(15 )(12 ), gSs=0.33 (7 )(1 )(4 ), and gSc=0.062 (13 )(3 )(5 ) and for the tensor charges gTu=0.794 (16 )(2 )(13 ), gTd=-0.210 (10 )(2 )(13 ), gTs=0.00032 (24 )(0 ), and gTc=0.00062 (85 )(0 ) in the MS ¯ scheme at 2 GeV. The first error is statistical, the second is the systematic error due to the renormalization and the third the systematic arising from estimating the contamination due to the excited states, when our data are precise enough to probe the first excited state.

Physical stage of photosynthesis charge separation

NASA Astrophysics Data System (ADS)

Yakovlev, A. G.; Shuvalov, V. A.

2016-06-01

An analytical review is given concerning the biophysical aspects of light-driven primary charge separation in photosynthesis reaction centers (RCs) which are special pigment-protein complexes residing in a cell membrane. The primary (physical) stage of charge separation occurs in the pico- and femtosecond ranges and consists of transferring an electron along the active A-branch of pigments. The review presents vast factual material on both the general issues of primary photosynthesis and some more specific topics, including (1) the role of the inactive B-branch of pigments, (2) the effect of the protein environment on the charge separation, and (3) the participation of monomeric bacteriochlorophyll BA in primary electron acceptance. It is shown that the electron transfer and stabilization are strongly influenced by crystallographic water and tyrosine M210 molecules from the nearest environment of BA. A linkage between collective nuclear motions and electron transfer upon charge separation is demonstrated. The nature of the high quantum efficiency of primary charge separation reactions is discussed.

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.

Theoretical study on the cooperative exciton dissociation process based on dimensional and hot charge-transfer state effects in an organic photocell

NASA Astrophysics Data System (ADS)

Shimazaki, Tomomi; Nakajima, Takahito

2016-06-01

This paper discusses the exciton dissociation process at the donor-acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot charge-transfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron-hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behavior between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields.

Modeling the Electric Potential and Surface Charge Density near Charged Thunderclouds

ERIC Educational Resources Information Center

Neel, Matthew Stephen

2018-01-01

Thundercloud charge separation, or the process by which the bottom portion of a cloud gathers charge and the top portion of the cloud gathers the opposite charge, is still not thoroughly understood. Whatever the mechanism, though, a charge separation definitely exists and can lead to electrostatic discharge via cloud-to-cloud lightning and…

The electrification of stratiform anvils

NASA Astrophysics Data System (ADS)

Boccippio, Dennis J.

1997-10-01

Stratiform precipitation regions accompany convective activity on many spatial scales. The electrification of these regions is anomalous in a number of ways. Surface and above-cloud fields are often 'inverted' from normal thunderstorm conditions. Unusually large, bright, horizontal 'spider' lightning and high current and charge transfer positive cloud-to-ground (CC) lightning dominates in these regions. Mesospheric 'red sprite' emissions have to date been observed exclusively over stratiform cloud shields. We postulate that a dominant 'inverted dipole' charge structure may account for this anomalous electrification. This is based upon laboratory observations of charge separation which show that in low liquid water content (LWC) environments, or dry but ice- supersaturated environments, precipitation ice tends to charge positively (instead of negatively) upon collision with smaller crystals. Under typical stratiform cloud conditions, liquid water should be depleted and this charging regime favored. An inverted dipole would be the natural consequence of large-scale charge separation (net flux divergence of charged ice), given typical hydrometeor profiles. The inverted dipole hypothesis is tested using radar and electrical observations of four weakly organized, late- stage systems in Orlando, Albuquerque and the Western Pacific. Time-evolving, area-average vertical velocity profiles are inferred from single Doppler radar data. These profiles provide the forcing for a 1-D steady state micro-physical retrieval, which yields vertical hydrometeor profiles and ice/water saturation conditions. The retrieved microphysical parameters are then combined with laboratory charge transfer measurements to infer the instantaneous charging behavior of the systems. Despite limitations in the analysis technique, the retrievals yield useful results. Total charge transfer drops only modestly as the storm enters the late (stratiform) stage, suggesting a continued active generator is plausible. Generator currents show an enhanced lowermost inverted dipole charging structure, which we may infer will result in a comparable inverted dipole charge structure, consistent with surface, in-situ and remote observations. Fine-scale vertical variations in ice and liquid water content may yield multipolar generator current profiles, despite unipolar charge transfer regimes. This suggests that multipoles observed in balloon soundings may not necessarily conflict with the simple ice-ice collisional charge separation mechanism. Overall, the results are consistent with, but not proof of, the inverted dipole model. (Copies available exclusively from MIT Libraries, Rm. 14-0551, Cambridge, MA 02139-4307. Ph. 617-253-5668; Fax 617-253- 1690.)

Effective Electrostatic Interactions Between Two Overall Neutral Surfaces with Quenched Charge Heterogeneity Over Atomic Length Scale

NASA Astrophysics Data System (ADS)

Zhou, S.

2017-12-01

Using Monte Carlo results as a reference, a classical density functional theory ( CDFT) is shown to reliably predict the forces between two heterogeneously charged surfaces immersed in an electrolyte solution, whereas the Poisson-Boltzmann ( PB) theory is demonstrated to deteriorate obviously for the same system even if the system parameters considered fall within the validity range of the PB theory in the homogeneously charged surfaces. By applying the tested CDFT, we study the effective electrostatic potential of mean force ( EPMF) between two face-face planar and hard surfaces of zero net charge on which positive and negative charges are separated and considered to present as discontinuous spots on the inside edges of the two surfaces. Main conclusions are summarized as follows: (i) strength of the EPMF in the surface charge separation case is very sensitively and positively correlated with the surface charge separation level and valency of the salt ion. Particularly, the charge separation level and the salt ion valency have a synergistic effect, which makes high limit of the EPMF strength in the surface charge separation case significantly go beyond that of the ideal homogeneously charged surface counterpart at average surface charge density similar to the average surface positive or negative charge density in the charge separation case. (ii) The surface charge distribution patterns mainly influence sign of the EPMF: symmetrical and asymmetrical patterns induce repulsive and attractive (at small distances) EPMF, respectively; but with low valency salt ions and low charge separation level the opposite may be the case. With simultaneous presence of both higher valency cation and anion, the EPMF can be repulsive at intermediate distances for asymmetrical patterns. (iii) Salt ion size has a significant impact, which makes the EPMF tend to become more and more repulsive with the ion diameter regardless of the surface charge distribution patterns and the valency of the salt ion; whereas if the 1:1 type electrolyte and the symmetrical patterns are considered, then the opposite may be the case. All of these findings can be explained self-consistently from several perspectives: an excess adsorption of the salt ions (induced by the surface charge separation) serving to raise the osmotic pressure between the plates, configuration fine-tuning in the thinner ion adsorption layer driven by the energy decrease principle, direct Coulombic interactions operating between charged objects on the two face-to-face plates involved, and net charge strength in the ion adsorption layer responsible for the net electrostatic repulsion.

22 CFR 128.5 - Answer and demand for oral hearing.

Code of Federal Regulations, 2013 CFR

2013-04-01

... Section 128.5 Foreign Relations DEPARTMENT OF STATE INTERNATIONAL TRAFFIC IN ARMS REGULATIONS... be responsive to the charging letter. It must fully set forth the nature of the respondent's defense or defenses. In the answer, the respondent must admit or deny specifically each separate allegation...

22 CFR 128.5 - Answer and demand for oral hearing.

Code of Federal Regulations, 2011 CFR

2011-04-01

... Section 128.5 Foreign Relations DEPARTMENT OF STATE INTERNATIONAL TRAFFIC IN ARMS REGULATIONS... be responsive to the charging letter. It must fully set forth the nature of the respondent's defense or defenses. In the answer, the respondent must admit or deny specifically each separate allegation...

22 CFR 128.5 - Answer and demand for oral hearing.

Code of Federal Regulations, 2010 CFR

2010-04-01

... Section 128.5 Foreign Relations DEPARTMENT OF STATE INTERNATIONAL TRAFFIC IN ARMS REGULATIONS... be responsive to the charging letter. It must fully set forth the nature of the respondent's defense or defenses. In the answer, the respondent must admit or deny specifically each separate allegation...

22 CFR 128.5 - Answer and demand for oral hearing.

Code of Federal Regulations, 2012 CFR

2012-04-01

... Section 128.5 Foreign Relations DEPARTMENT OF STATE INTERNATIONAL TRAFFIC IN ARMS REGULATIONS... be responsive to the charging letter. It must fully set forth the nature of the respondent's defense or defenses. In the answer, the respondent must admit or deny specifically each separate allegation...

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

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

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

Femtosecond excited state studies of the two-center three-electron bond driven twisted internal charge transfer dynamics in 1,8-bis(dimethylamino)naphthalene.

PubMed

Balkowski, Grzegorz; Szemik-Hojniak, Anna; van Stokkum, Ivo H M; Zhang, Hong; Buma, Wybren J

2005-04-28

Femtosecond fluorescence upconversion and transient absorption experiments have been performed to monitor the photoinduced electronic, geometry, and solvent relaxation dynamics of 1,8-bis(dimethylamino)naphthalene dissolved in methylcyclohexane or n-hexane, n-dodecane, dichloromethane, and acetonitrile. The data have been analyzed by using a sequential global analysis method that gives rise to species associated difference spectra. The spectral features in these spectra and their dynamic behavior enable us to associate them with specific processes occurring in the molecule. The experiments show that the internal charge-transfer lpi* state is populated after internal conversion from the 1La state. In the lpi state the molecule is concluded to be subject to a large-amplitude motion, thereby confirming our previous predictions that internal charge transfer in this state is accompanied by the formation of a two-center three-electron bond between the two nitrogen atoms. Solvent relaxation and vibrational cooling in the lpi* state cannot be separated in polar solvents, but in apolar solvents a distinct vibrational cooling process in the lpi* state is discerned. The spectral and dynamic characteristics of the final species created in the experiments are shown to correspond well with what has been determined before for the relaxed emissive lpi state.

Approximate description of Stokes shifts in ICT fluorescence emission

NASA Astrophysics Data System (ADS)

Saielli, Giacomo; Braun, David; Polimeno, Antonino; Nordio, Pier Luigi

1996-07-01

The time-resolved emission spectrum of a dual fluorescent prototype system like DMABN is associated with an intramolecular adiabatic charge-transfer reaction and the simultaneous relaxation of the polarization coordinate describing the dynamic behaviour of the polar solvent. The dynamic Stokes shift of the frequency maximum of the long-wavelength emission band related to the charge-transfer (CT) state towards the red region is interpreted as a consequence of a kinetic pathway which deviates from steepest descent to the CT state, the rate-determining step being the solvent relaxation. The present stochastic treatment is based on the assumption that internal and solvent coordinates could be described separately, neglecting coupling elements in the case of slow solvent relaxation.

Energy relaxation of intense laser pulse-produced plasmas

NASA Astrophysics Data System (ADS)

Shihab, M.; Abou-Koura, G. H.; El-Siragy, N. M.

2016-05-01

We describe a collisional radiative model (CRE) of homogeneously expanded nickel plasmas in vacuum. The CRE model is coupled with two separate electron and ion temperature magneto-hydrodynamic equations. On the output, the model provides the temporal variation of the electron temperature, ion temperature, and average charge state. We demonstrate the effect of three-body recombination ({∝}N_e T^{-9/2}_e) on plasma parameters, as it changes the time dependence of electron temperature from t^{-2} to t^{-1} and exhibits a pronounced effect leading to a freezing feature in the average charge state. In addition, the effect of the three-body recombination on the warm up of ions and delaying the equilibration is addressed.

Strong coupling electrostatics for randomly charged surfaces: antifragility and effective interactions.

PubMed

Ghodrat, Malihe; Naji, Ali; Komaie-Moghaddam, Haniyeh; Podgornik, Rudolf

2015-05-07

We study the effective interaction mediated by strongly coupled Coulomb fluids between dielectric surfaces carrying quenched, random monopolar charges with equal mean and variance, both when the Coulomb fluid consists only of mobile multivalent counterions and when it consists of an asymmetric ionic mixture containing multivalent and monovalent (salt) ions in equilibrium with an aqueous bulk reservoir. We analyze the consequences that follow from the interplay between surface charge disorder, dielectric and salt image effects, and the strong electrostatic coupling that results from multivalent counterions on the distribution of these ions and the effective interaction pressure they mediate between the surfaces. In a dielectrically homogeneous system, we show that the multivalent counterions are attracted towards the surfaces with a singular, disorder-induced potential that diverges logarithmically on approach to the surfaces, creating a singular but integrable counterion density profile that exhibits an algebraic divergence at the surfaces with an exponent that depends on the surface charge (disorder) variance. This effect drives the system towards a state of lower thermal 'disorder', one that can be described by a renormalized temperature, exhibiting thus a remarkable antifragility. In the presence of an interfacial dielectric discontinuity, the singular behavior of counterion density at the surfaces is removed but multivalent counterions are still accumulated much more strongly close to randomly charged surfaces as compared with uniformly charged ones. The interaction pressure acting on the surfaces displays in general a highly non-monotonic behavior as a function of the inter-surface separation with a prominent regime of attraction at small to intermediate separations. This attraction is caused directly by the combined effects from charge disorder and strong coupling electrostatics of multivalent counterions, which dominate the surface-surface repulsion due to the (equal) mean charges on the two surfaces and the osmotic pressure of monovalent ions residing between them. These effects can be quite significant even with a small degree of surface charge disorder relative to the mean surface charge. The strong coupling, disorder-induced attraction is typically much stronger than the van der Waals interaction between the surfaces, especially within a range of several nanometers for the inter-surface separation, where such effects are predicted to be most pronounced.

Intermolecular interaction approach for TADF (Conference Presentation)

NASA Astrophysics Data System (ADS)

Wong, Ken-Tsung

2016-09-01

Materials with thermally activated delayed fluorescence (TADF) have recently emerged as new fluorescent emitters for highly efficient organic light-emitting diodes (OLEDs). Molecule with TADF behavior needs to have a small singlet-triplet energy difference (ΔES-T) that allows the up-conversion from nonradiative triplet state (T1) to radiative singlet state (S1) via reverse intersystem crossing (RISC) process. Generally, molecules with small ΔES-T can be obtained via carefully manipulate the degree of "intramolecular" charge transfer (ICT) between electron-donating and -accepting components, such that the electron exchange energy that contributes to ΔES-T, can be minimized. Alternatively, excited state with small ΔES-T can be feasibly realized via "intermolecular" charge transfer occurring at the interface between spatially separating donor (D) and acceptor (A) molecules. Because the exchange energy decreases as the HOMO-LUMO separation distance increases, theoretically, the intermolecular D/A charge transfer state (or exciplex) should have rather small ΔES-T, leading to efficient TADF. However, it is still a challenge to access highly efficient exciplex systems. This is mainly because exciplex formation is commonly accompanied with a large red shift of emission spectra and long radiative lifetime, which tend to diminish photoluminescence quantum yield (PLQY) as well as electroluminescence (EL) performance. Until now, exciplex-based OLEDs with external quantum efficiency (EQE) above 10% are still limited. By judicious selection of donor and acceptor, the formation of efficient exciplex can be feasibly achieved. In this conference, our recent efforts on highly efficient exciplexes using C3-symmetry triazine acceptors and various donors, and their device characteristics will be presented.

Spin-correlated doublet pairs as intermediate states in charge separation processes

NASA Astrophysics Data System (ADS)

Kraffert, Felix; Behrends, Jan

2017-10-01

Spin-correlated charge-carrier pairs play a crucial role as intermediate states in charge separation both in natural photosynthesis as well as in solar cells. Using transient electron paramagnetic resonance (trEPR) spectroscopy in combination with spectral simulations, we study spin-correlated polaron pairs in polymer:fullerene blends as organic solar cells materials. The semi-analytical simulations presented here are based on the well-established theoretical description of spin-correlated radical pairs in biological systems, however, explicitly considering the disordered nature of polymer:fullerene blends. The large degree of disorder leads to the fact that many different relative orientations between both polarons forming the spin-correlated pairs have to be taken into account. This has important implications for the spectra, which differ significantly from those of spin-correlated radical pairs with a fixed relative orientation. We systematically study the influence of exchange and dipolar couplings on the trEPR spectra and compare the simulation results to measured X- and Q-band trEPR spectra. Our results demonstrate that assuming dipolar couplings alone does not allow us to reproduce the experimental spectra. Due to the rather delocalised nature of polarons in conjugated organic semiconductors, a significant isotropic exchange coupling needs to be included to achieve good agreement between experiments and simulations.

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

PubMed

Fujisawa, Jun-ichi

2015-05-14

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

Factors that influence the efficiency of a fluidized-bed-type tribo-electrostatic separator for mixed granular plastics

NASA Astrophysics Data System (ADS)

Dascalescu, L.; Fati, O.; Bilici, M.; Rahou, F.; Dragan, C.; Samuila, A.; Iuga, A.

2011-06-01

Fluidized bed devices have already been used as tribochargers for various industrial electrostatic separation processes. In the present paper, the authors investigate the behaviour of polyamide - polycarbonate granular plastic mixtures in a parallelepiped bed, the height of which is roughly 2 times its length or width, so that the collisions between granules become the prevailing tribocharging mechanism. Two of the opposite walls of the tribocharging chamber consist of metallic plates connected to two DC high-voltage supplies of opposite polarities, so that the charged particles are attracted to the electrodes and separated while still in the fluidized state. The collecting hoppers are designed as Faraday cups connected to two electrometers, thus allowing the instantaneous measurement of the charge carried by the separated particles. Experimental design methodology was employed for the optimization of the tribo-aero-electrostatic separation process, the input variables being the high-voltage applied to the electrodes and the duration of the tribocharging. Higher voltages applied to the electrode system do not necessarily lead to larger quantities of collected products but improve the purity of the concentrates. The composition of the mixture influences the outcome of the process.

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.

Three-body dissociation of OCS3+: Separating sequential and concerted pathways

NASA Astrophysics Data System (ADS)

Kumar, Herendra; Bhatt, Pragya; Safvan, C. P.; Rajput, Jyoti

2018-02-01

Events from the sequential and concerted modes of the fragmentation of OCS3+ that result in coincident detection of fragments C+, O+, and S+ have been separated using a newly proposed representation. An ion beam of 1.8 MeV Xe9+ is used to make the triply charged molecular ion, with the fragments being detected by a recoil ion momentum spectrometer. By separating events belonging exclusively to the sequential mode of breakup, the electronic states of the intermediate molecular ion (CO2+ or CS2+) involved are determined, and from the kinetic energy release spectra, it is shown that the low lying excited states of the parent OCS3+ are responsible for this mechanism. An estimate of branching ratios of events coming from sequential versus concerted mode is presented.

Indirect double photoionization of water

NASA Astrophysics Data System (ADS)

Resccigno, T. N.; Sann, H.; Orel, A. E.; Dörner, R.

2011-05-01

The vertical double ionization thresholds of small molecules generally lie above the dissociation limits corresponding to formation of two singly charged fragments. This gives the possibility of populating singly charged molecular ions by photoionization in the Franck-Condon region at energies below the lowest dication state, but above the dissociation limit into two singly charged fragment ions. This process can produce a superexcited neutral fragment that autoionizes at large internuclear separation. We study this process in water, where absorption of a photon produces an inner-shell excited state of H2O+ that fragments to H++OH*. The angular distribution of secondary electrons produced by OH* when it autoionizes produces a characteristic asymmetric pattern that reveals the distance, and therefore the time, at which the decay takes place. LBNL, Berkeley, CA, J. W. Goethe Universität, Frankfurt, Germany. Work performed under auspices of US DOE and supported by OBES, Div. of Chemical Sciences.

Nucleon Charges from 2+1+1-flavor HISQ and 2+1-flavor clover lattices

DOE PAGES

Gupta, Rajan

2016-07-24

Precise estimates of the nucleon charges g A, g S and g T are needed in many phenomenological analyses of SM and BSM physics. In this talk, we present results from two sets of calculations using clover fermions on 9 ensembles of 2+1+1-flavor HISQ and 4 ensembles of 2+1-flavor clover lattices. In addition, we show that high statistics can be obtained cost-effectively using the truncated solver method with bias correction and the coherent source sequential propagator technique. By performing simulations at 4–5 values of the source-sink separation t sep, we demonstrate control over excited-state contamination using 2- and 3-state fits.more » Using the high-precision 2+1+1-flavor data, we perform a simultaneous fit in a, M π and M πL to obtain our final results for the charges.« less

Detection method for dissociation of multiple-charged ions

DOEpatents

Smith, Richard D.; Udseth, Harold R.; Rockwood, Alan L.

1991-01-01

Dissociations of multiple-charged ions are detected and analyzed by charge-separation tandem mass spectrometry. Analyte molecules are ionized to form multiple-charged parent ions. A particular charge parent ion state is selected in a first-stage mass spectrometer and its mass-to-charge ratio (M/Z) is detected to determine its mass and charge. The selected parent ions are then dissociated, each into a plurality of fragments including a set of daughter ions each having a mass of at least one molecular weight and a charge of at least one. Sets of daughter ions resulting from the dissociation of one parent ion (sibling ions) vary in number but typically include two to four ions, one or more multiply-charged. A second stage mass spectrometer detects mass-to-charge ratio (m/z) of the daughter ions and a temporal or temporo-spatial relationship among them. This relationship is used to correlate the daughter ions to determine which (m/z) ratios belong to a set of sibling ions. Values of mass and charge of each of the sibling ions are determined simultaneously from their respective (m/z) ratios such that the sibling ion charges are integers and sum to the parent ion charge.

Electronic structure and charge transfer excited states of endohedral fullerene containing electron donoracceptor complexes utilized in organic photovoltaics

NASA Astrophysics Data System (ADS)

Amerikheirabadi, Fatemeh

Organic Donor-Acceptor complexes form the main component of the organic photovoltaic devices (OPVs). The open circuit voltage of OPVs is directly related to the charge transfer excited state energies of these complexes. Currently a large number of different molecular complexes are being tested for their efficiency in photovoltaic devices. In this work, density functional theory as implemented in the NRLMOL code is used to investigate the electronic structure and related properties of these donor-acceptor complexes. The charge transfer excitation energies are calculated using the perturbative delta self-consistent field method recently developed in our group as the standard time dependent density functional approaches fail to accurately provide them. The model photovoltaics systems analyzed are as follows: Sc3N C 80--ZnTPP, Y3 N C80-- ZnTPP and Sc3 N C80-- ZnPc. In addition, a thorough analysis of the isolated donor and acceptor molecules is also provided. The studied acceptors are chosen from a class of fullerenes named trimetallic nitride endohedral fullerenes. These molecules have shown to possess advantages as acceptors such as long lifetimes of the charge-separated states.

A modified electronegativity equalization method for fast and accurate calculation of atomic charges in large biological molecules.

PubMed

Ouyang, Yongzhong; Ye, Fei; Liang, Yizeng

2009-08-07

To further extend the EEM approach to improve its accuracy, a new approach, in which the different connectivities and hybridized states are introduced to represent the different chemical environments, has been developed. The C, O and N atoms are distinguished between different hybridized states. Different states of hydrogen atoms are defined according to their different connectivities. Furthermore, the sp(2) carbons in the aromatic rings are also separated from the other sp(2) carbons. Geometries and NPA charges are calculated at the B3LYP/6-31G* level, and the effective electronegativity and hardness values could be calibrated with the help of a training set of 141 organic molecules using the Differential Evolution (DE) algorithm. The quality of the modified EEM charges is evaluated by comparison with the B3LYP/6-31G* charges calculated for a series of polypeptides, not contained in the training set. For further comparison, the atomic parameters of the original EEM without including chemical environments are recalibrated under the same conditions. It is found that the accuracy of the modified EEM method improves significantly as compared to that of the original EEM method.

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT

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

Cho, Sung; Rolczynski, Brian S.; Xu, Tao

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast,more » P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.« less

Solution Phase Exciton Diffusion Dynamics of a Charge-Transfer Copolymer PTB7 and a Homopolymer P3HT.

PubMed

Cho, Sung; Rolczynski, Brian S; Xu, Tao; Yu, Luping; Chen, Lin X

2015-06-18

Using ultrafast polarization-controlled transient absorption (TA) measurements, dynamics of the initial exciton states were investigated on the time scale of tens of femtoseconds to about 80 ps in two different types of conjugated polymers extensively used in active layers of organic photovoltaic devices. These polymers are poly(3-fluorothienothiophenebenzodithiophene) (PTB7) and poly-3-hexylthiophene (P3HT), which are charge-transfer polymers and homopolymers, respectively. In PTB7, the initial excitons with excess vibrational energy display two observable ultrafast time constants, corresponding to coherent exciton diffusion before the vibrational relaxation, and followed by incoherent exciton diffusion processes to a neighboring local state after the vibrational relaxation. In contrast, P3HT shows only one exciton diffusion or conformational motion time constant of 34 ps, even though its exciton decay kinetics are multiexponential. Based on the experimental results, an exciton dynamics mechanism is conceived taking into account the excitation energy and structural dependence in coherent and incoherent exciton diffusion processes, as well as other possible deactivation processes including the formation of the pseudo-charge-transfer and charge separate states, as well as interchain exciton hopping or coherent diffusion.

EBQ code: Transport of space-charge beams in axially symmetric devices

NASA Astrophysics Data System (ADS)

Paul, A. C.

1982-11-01

Such general-purpose space charge codes as EGUN, BATES, WODF, and TRANSPORT do not gracefully accommodate the simulation of relativistic space-charged beams propagating a long distance in axially symmetric devices where a high degree of cancellation has occurred between the self-magnetic and self-electric forces of the beam. The EBQ code was written specifically to follow high current beam particles where space charge is important in long distance flight in axially symmetric machines possessing external electric and magnetic field. EBQ simultaneously tracks all trajectories so as to allow procedures for charge deposition based on inter-ray separations. The orbits are treated in Cartesian geometry (position and momentum) with z as the independent variable. Poisson's equation is solved in cylindrical geometry on an orthogonal rectangular mesh. EBQ can also handle problems involving multiple ion species where the space charge from each must be included. Such problems arise in the design of ion sources where different charge and mass states are present.

Adverse Effects of Excess Residual PbI2 on Photovoltaic Performance, Charge Separation, and Trap-State Properties in Mesoporous Structured Perovskite Solar Cells.

PubMed

Wang, Hao-Yi; Hao, Ming-Yang; Han, Jun; Yu, Man; Qin, Yujun; Zhang, Pu; Guo, Zhi-Xin; Ai, Xi-Cheng; Zhang, Jian-Ping

2017-03-17

Organic-inorganic halide perovskite solar cells have rapidly come to prominence in the photovoltaic field. In this context, CH 3 NH 3 PbI 3 , as the most widely adopted active layer, has been attracting great attention. Generally, in a CH 3 NH 3 PbI 3 layer, unreacted PbI 2 inevitably coexists with the perovskite crystals, especially following a two-step fabrication process. There appears to be a consensus that an appropriate amount of unreacted PbI 2 is beneficial to the overall photovoltaic performance of a device, the only disadvantageous aspect of excess residual PbI 2 being viewed as its insulating nature. However, the further development of such perovskite-based devices requires a deeper understanding of the role of residual PbI 2 . In this work, PbI 2 -enriched and PbI 2 -controlled perovskite films, as two extreme cases, have been prepared by modulating the crystallinity of a pre-deposited PbI 2 film. The effects of excess residual PbI 2 have been elucidated on the basis of spectroscopic and optoelectronic studies. The initial charge separation, the trap-state density, and the trap-state distribution have all been found to be adversely affected in PbI 2 -enriched devices, to the detriment of photovoltaic performance. This leads to a biphasic recombination process and accelerates the charge carrier recombination dynamics. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A multi-pathway model for photosynthetic reaction center

NASA Astrophysics Data System (ADS)

Qin, M.; Shen, H. Z.; Yi, X. X.

2016-03-01

Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

Theoretical study on the cooperative exciton dissociation process based on dimensional and hot charge-transfer state effects in an organic photocell

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

Shimazaki, Tomomi; Nakajima, Takahito

2016-06-21

This paper discusses the exciton dissociation process at the donor–acceptor interface in organic photocells. In our previous study, we introduced a local temperature to handle the hot charge-transfer (CT) state and calculated the exciton dissociation probability based on the 1D organic semiconductor model [T. Shimazaki and T. Nakajima, Phys. Chem. Chem. Phys. 17, 12538 (2015)]. Although the hot CT state plays an essential role in exciton dissociations, the probabilities calculated are not high enough to efficiently separate bound electron–hole pairs. This paper focuses on the dimensional (entropy) effect together with the hot CT state effect and shows that cooperative behaviormore » between both effects can improve the exciton dissociation process. In addition, we discuss cooperative effects with site-disorders and external-electric-fields.« less

Characterization of charge separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source for mass spectrometry.

PubMed

Forbes, Thomas P; Dixon, R Brent; Muddiman, David C; Degertekin, F Levent; Fedorov, Andrei G

2009-09-01

An initial investigation into the effects of charge separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source is reported to gain understanding of ionization mechanisms and to improve analyte ionization efficiency and operation stability. In RF-only mode, AMUSE ejects, on average, an equal number of slightly positive and slightly negative charged droplets due to random charge fluctuations, providing inefficient analyte ionization. Charge separation at the nozzle orifice is achieved by the application of an external electric field. By bringing the counter electrode close to the nozzle array, strong electric fields can be applied at relatively low DC potentials. It has been demonstrated, through a number of electrode/electrical potential configurations, that increasing charge separation leads to improvement in signal abundance, signal-to-noise ratio, and signal stability.

Superconducting transmission line particle detector

DOEpatents

Gray, K.E.

1988-07-28

A microvertex particle detector for use in a high energy physic collider including a plurality of parallel superconducting thin film strips separated from a superconducting ground plane by an insulating layer to form a plurality of superconducting waveguides. The microvertex particle detector indicates passage of a charged subatomic particle by measuring a voltage pulse measured across a superconducting waveguide caused by the transition of the superconducting thin film strip from a superconducting to a non- superconducting state in response to the passage of a charged particle. A plurality of superconducting thin film strips in two orthogonal planes plus the slow electromagnetic wave propagating in a superconducting transmission line are used to resolve N/sup 2/ ambiguity of charged particle events. 6 figs.

Superconducting transmission line particle detector

DOEpatents

Gray, Kenneth E.

1989-01-01

A microvertex particle detector for use in a high energy physic collider including a plurality of parallel superconducting thin film strips separated from a superconducting ground plane by an insulating layer to form a plurality of superconducting waveguides. The microvertex particle detector indicates passage of a charged subatomic particle by measuring a voltage pulse measured across a superconducting waveguide caused by the transition of the superconducting thin film strip from a superconducting to a non-superconducting state in response to the passage of a charged particle. A plurality of superconducting thin film strips in two orthogonal planes plus the slow electromagnetic wave propogating in a superconducting transmission line are used to resolve N.sup.2 ambiguity of charged particle events.

Excess-Si related defect centers in buried SiO2 thin films

NASA Astrophysics Data System (ADS)

Warren, W. L.; Fleetwood, D. M.; Shaneyfelt, M. R.; Schwank, J. R.; Winokur, P. S.; Devine, R. A. B.

1993-06-01

Using electron paramagnetic resonance (EPR) and capacitance-voltage measurements we have investigated the role of excess-silicon related defect centers as charge traps in separation by the implantation of oxygen materials. Three types of EPR-active centers were investigated: oxygen vacancy Eγ' centers (O3≡Si• +Si≡O3), delocalized Eδ' centers, and D centers (Si3≡Si•). It was found that all of these paramagnetic centers are created by selective hole injection, and are reasonably ascribed as positively charged when paramagnetic. These results provide the first experimental evidence for (1) the charge state of the Eδ' center, and (2) that the D center is an electrically active point defect in these materials.

A charge-polarized porous metal-organic framework for gas chromatographic separation of alcohols from water.

PubMed

Sun, Jian-Ke; Ji, Min; Chen, Cheng; Wang, Wu-Gen; Wang, Peng; Chen, Rui-Ping; Zhang, Jie

2013-02-25

A bipyridinium ligand with a charge separated skeleton has been introduced into a metal-organic framework to yield a porous material with charge-polarized pore space, which exhibits selective adsorption for polar guest molecules and can be further used in gas chromatography for the separation of alcohol-water mixtures.

A Charge Separation Study to Enable the Design of a Complete Muon Cooling Channel

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

Yoshikawa, C.; Ankenbrandt, Charles M.; Johnson, Rolland P.

2013-12-01

The most promising designs for 6D muon cooling channels operate on a specific sign of electric charge. In particular, the Helical Cooling Channel (HCC) and Rectilinear RFOFO designs are the leading candidates to become the baseline 6D cooling channel in the Muon Accelerator Program (MAP). Time constraints prevented the design of a realistic charge separator, so a simplified study was performed to emulate the effects of charge separation on muons exiting the front end of a muon collider. The output of the study provides particle distributions that the competing designs will use as input into their cooling channels. We reportmore » here on the study of the charge separator that created the simulated particles.« less

Evolved phase separation toward balanced charge transport and high efficiency in polymer solar cells.

PubMed

Fan, Haijun; Zhang, Maojie; Guo, Xia; Li, Yongfang; Zhan, Xiaowei

2011-09-01

Understanding effect of morphology on charge carrier transport within polymer/fullerene bulk heterojunction is necessary to develop high-performance polymer solar cells. In this work, we synthesized a new benzodithiophene-based polymer with good self-organization behavior as well as favorable morphology evolution of its blend films with PC(71)BM under improved processing conditions. Charge carrier transport behavior of blend films was characterized by space charge limited current method. Evolved blend film morphology by controlling blend composition and additive content gradually reaches an optimized state, featured with nanoscale fibrilla polymer phase in moderate size and balanced mobility ratio close to 1:1 for hole and electron. This optimized morphology toward more balanced charge carrier transport accounts for the best power conversion efficiency of 3.2%, measured under simulated AM 1.5 solar irradiation 100 mW/cm(2), through enhancing short circuit current and reducing geminate recombination loss.

Results of the ETV-1 breadboard tests under steady-state and transient conditions. [conducted in the NASA-LeRC Road Load Simulator

NASA Technical Reports Server (NTRS)

Sargent, N. B.; Dustin, M. O.

1981-01-01

Steady state tests were run to characterize the system and component efficiencies over the complete speed-torque capabilities of the propulsion system in both motoring and regenerative modes of operation. The steady state data were obtained using a battery simulator to separate the effects on efficiency caused by changing battery state-of-charge and component temperature. Transient tests were performed to determine the energy profiles of the propulsion system operating over the SAE J227a driving schedules.

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.

Cofactors involved in light-driven charge separation in photosystem I identified by subpicosecond infrared spectroscopy.

PubMed

Di Donato, Mariangela; Stahl, Andreas D; van Stokkum, Ivo H M; van Grondelle, Rienk; Groot, Marie-Louise

2011-02-01

Photosystem I is one of the key players in the conversion of solar energy into chemical energy. While the chlorophyll dimer P(700) has long been identified as the primary electron donor, the components involved in the primary charge separation process in PSI remain undetermined. Here, we have studied the charge separation dynamics in Photosystem I trimers from Synechococcus elongatus by femtosecond vis-pump/mid-infrared-probe spectroscopy upon excitation at 700, 710, and 715 nm. Because of the high specificity of the infrared region for the redox state and small differences in the molecular structure of pigments, we were able to clearly identify specific marker bands indicating chlorophyll (Chl) oxidation. Magnitudes of chlorophyll cation signals are observed to increase faster than the time resolution of the experiment (~0.2 ps) upon both excitation conditions: 700 nm and selective red excitation. Two models, involving either ultrafast charge separation or charge transfer character of the red pigments in PSI, are discussed to explain this observation. A further increase in the magnitudes of cation signals on a subpicosecond time scale (0.8-1 ps) indicates the formation of the primary radical pair. Evolution in the cation region with time constants of 7 and 40 ps reveals the formation of the secondary radical pair, involving a secondary electron donor. Modeling of the data allows us to extract the spectra of the two radical pairs, which have IR signatures consistent with A+A₀- and P₇₀₀+A₁-. We conclude that the cofactor chlorophyll A acts as the primary donor in PSI. The existence of an equilibrium between the two radical pairs we interpret as concerted hole/electron transfer between the pairs of electron donors and acceptors, until after 40 ps, relaxation leads to a full population of the P₇₀₀+A₁. radical pair.

Role of charge separation mechanism and local disorder at hybrid solar cell interfaces

NASA Astrophysics Data System (ADS)

Ehrenreich, Philipp; Pfadler, Thomas; Paquin, Francis; Dion-Bertrand, Laura-Isabelle; Paré-Labrosse, Olivier; Silva, Carlos; Weickert, Jonas; Schmidt-Mende, Lukas

2015-01-01

Dye-sensitized metal oxide polymer hybrid solar cells deliver a promising basis in organic solar cell development due to many conceptual advantages. Since the power conversion efficiency is still in a noncompetitive state, it has to be understood how the photocurrent contribution can be maximized (i.e., which dye-polymer properties are most beneficial for efficient charge generation in hybrid solar cells). By the comparison of three model systems for hybrid solar cells with Ti O2 -dye-polymer interfaces, this paper was aimed at elucidating the role of the exact mechanism of charge generation. In the exciton dissociation (ED) case, an exciton that is generated in the polymer is split at the dye-polymer interface. Alternatively, this exciton can be transferred to the dye via an energy transfer (ET), upon which charge separation occurs between dye and Ti O2 . For comparison, the third case is included in which the high lowest unoccupied molecular orbital of the dye does not allow exciton separation or ET from the dye to the polymer, so that the dye only is responsible for charge generation. To separate effects owing to differences in energy levels of the involved materials from the impact of local order and disorder in the polymer close to the interface, this paper further comprises a detailed analysis of the polymer crystallinity based on the H-aggregate model. While the massive impact of the poly(3-hexylthiophene) crystallinity on device function has been outlined for bare metal oxide-polymer interfaces, it has not been considered for hybrid solar cells with dye-sensitized Ti O2 . The results presented here indicate that all dye molecules in general influence the polymer morphology, which has to be taken into account for future optimization of hybrid solar cells. Apart from that, it can be suggested that ED on the polymer needs an additional driving force to work efficiently; thus, energy transfer seems to be currently the most promising strategy to increase the polymer photocurrent contribution.

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

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

Two-terminal charge tunneling: Disentangling Majorana zero modes from partially separated Andreev bound states in semiconductor-superconductor heterostructures

NASA Astrophysics Data System (ADS)

Moore, Christopher; Stanescu, Tudor D.; Tewari, Sumanta

2018-04-01

We show that a pair of overlapping Majorana bound states (MBSs) forming a partially separated Andreev bound state (ps-ABS) represents a generic low-energy feature in spin-orbit-coupled semiconductor-superconductor (SM-SC) hybrid nanowire in the presence of a Zeeman field. The ps-ABS interpolates continuously between the "garden variety" ABS, which consists of two MBSs sitting on top of each other, and the topologically protected Majorana zero modes (MZMs), which are separated by a distance given by the length of the wire. The really problematic ps-ABSs consist of component MBSs separated by a distance of the order of the characteristic Majorana decay length ξ , and have nearly zero energy in a significant range of control parameters, such as the Zeeman field and chemical potential, within the topologically trivial phase. Despite being topologically trivial, such ps-ABSs can generate signatures identical to MZMs in local charge tunneling experiments. In particular, the height of the zero-bias conductance peak (ZBCP) generated by ps-ABSs has the quantized value 2 e2/h , and it can remain unchanged in an extended range of experimental parameters, such as Zeeman field and the tunnel barrier height. We illustrate the formation of such low-energy robust ps-ABSs in two experimentally relevant situations: a hybrid SM-SC system consisting of a proximitized nanowire coupled to a quantum dot and the SM-SC system in the presence of a spatially varying inhomogeneous potential. We then show that, unlike local measurements, a two-terminal experiment involving charge tunneling at both ends of the wire is capable of distinguishing between the generic ps-ABSs and the non-Abelian MZMs. While the MZMs localized at the opposite ends of the wire generate correlated differential conduction spectra, including correlations in energy splittings and critical Zeeman fields associated with the emergence of the ZBCPs, such correlations are absent if the ZBCPs are due to ps-ABSs emerging in the topologically trivial phase. Measuring such correlations is the clearest and most straightforward test of topological MZMs in SM-SC heterostructures that can be done in a currently accessible experimental setup.

Probing the solvation structure and dynamics in ionic liquids by time-resolved infrared spectroscopy of 4-(dimethylamino)benzonitrile.

PubMed

Ando, Rômulo A; Brown-Xu, Samantha E; Nguyen, Lisa N Q; Gustafson, Terry L

2017-09-20

In this work we demonstrate the use of the push-pull model system 4-(dimethylamino)benzonitrile (DMABN) as a convenient molecular probe to investigate the local solvation structure and dynamics by means of time-resolved infrared spectroscopy (TRIR). The photochemical features associated with this system provide several advantages due to the high charge separation between the ground and charge transfer states involving the characteristic nitrile bond, and an excited state lifetime that is long enough to observe the slow solvation dynamics in organic solvents and ionic liquids. The conversion from a locally excited state to an intramolecular charge transfer state (LE-ICT) in ionic liquids shows similar kinetic lifetimes in comparison to organic solvents. This similarity confirms that such conversion depends solely on the intramolecular reorganization of DMABN in the excited state, and not by the dynamics of solvation. In contrast, the relative shift of the ν(CN) vibration during the relaxation of the ICT state reveals two distinct lifetimes that are sensitive to the solvent environment. This study reveals a fast time component which is attributed to the dipolar relaxation of the solvent and a slower time component related to the rotation of the dimethylamino group of DMABN.

Characterization of Charge Separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) Ion Source for Mass Spectrometry

PubMed Central

Forbes, Thomas P.; Dixon, R. Brent; Muddiman, David C.; Degertekin, F. Levent; Fedorov, Andrei G.

2009-01-01

An initial investigation into the effects of charge separation in the Array of Micromachined UltraSonic Electrospray (AMUSE) ion source is reported in order to gain understanding of ionization mechanisms and to improve analyte ionization efficiency and operation stability. In RF-only mode, AMUSE ejects on average, an equal number of slightly positive and slightly negative charged droplets due to random charge fluctuations, providing inefficient analyte ionization. Charge separation at the nozzle orifice is achieved by the application of an external electric field. By bringing the counter electrode close to the nozzle array, strong electric fields can be applied at relatively low DC potentials. It has been demonstrated, through a number of electrode/electrical potential configurations that increasing charge separation leads to improvement in signal abundance, signal-to-noise ratio, and signal stability. PMID:19525123

Wide size range fast integrated mobility spectrometer

DOEpatents

Wang, Jian

2013-10-29

A mobility spectrometer to measure a nanometer particle size distribution is disclosed. The mobility spectrometer includes a conduit and a detector. The conduit is configured to receive and provide fluid communication of a fluid stream having a charged nanometer particle mixture. The conduit includes a separator section configured to generate an electrical field of two dimensions transverse to a dimension associated with the flow of the charged nanometer particle mixture through the separator section to spatially separate charged nanometer particles of the charged nanometer particle mixture in said two dimensions. The detector is disposed downstream of the conduit to detect concentration and position of the spatially-separated nanometer particles.

Charge separation and transport of the n=2 instability in C-2 FRC plasmas

NASA Astrophysics Data System (ADS)

Deng, Bihe; Sun, Xuan; Tuszewski, Michel

2012-10-01

Charge separation is critical in the positive feedback loop for gravitational type instabilities to grow [1], such as in the case of the n=2 mode in the C-2 field reversed configuration (FRC) experiment [2]. A fast time response Langmuir probe with minimum perturbation to the plasma is inserted into the edge of the C-2 plasma to measure the plasma floating potential. With the combined plasma wobble motion and spin motion, 2-D scans of the plasma floating potential are obtained, and evidence of charge separation associated with the n=2 instability is observed. The transport due to charge separation is estimated. Charge neutralization can provide an alternative method to stabilize the n=2 mode. An experiment is proposed to test this method with two probes inserted into the plasma from two azimuthally separated ports and an external shorting circuit, to constantly neutralize the charge separation, thus suppress the growth of the n=2 mode. [4pt] [1] R.J. Goldston and P.H. Rutherford, Introduction to Plasma Physics (Institute of Physics Publishing, Bristol, 2000).[0pt] [2]. M.W. Binderbauer et al, Phys. Rev. Lett. 105, 045003 (2010).

Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

DOE PAGES

Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda; ...

2016-12-06

Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that interfacing semiconductor QDs with transition-metal oxide NWs exhibiting intercalative midgap states yields a versatile platform wherein the thermodynamics and kinetics of charge transfer can be systematically modulated to improve the efficiency of charge separation across interfaces.« less

Programming interfacial energetic offsets and charge transfer in β-Pb 0.33V 2O 5/quantum-dot heterostructures: Tuning valence-band edges to overlap with midgap states

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

Pelcher, Kate E.; Milleville, Christopher C.; Wangoh, Linda

Here, semiconductor heterostructures for solar energy conversion interface light-harvesting semiconductor nanoparticles with wide-band-gap semiconductors that serve as charge acceptors. In such heterostructures, the kinetics of charge separation depend on the thermodynamic driving force, which is dictated by energetic offsets across the interface. A recently developed promising platform interfaces semiconductor quantum dots (QDs) with ternary vanadium oxides that have characteristic midgap states situated between the valence and conduction bands. In this work, we have prepared CdS/β-Pb 0.33V 2O 5 heterostructures by both linker-assisted assembly and surface precipitation and contrasted these materials with CdSe/β-Pb 0.33V 2O 5 heterostructures prepared by the samemore » methods. Increased valence-band (VB) edge onsets in X-ray photoelectron spectra for CdS/β-Pb 0.33V 2O 5 heterostructures relative to CdSe/β-Pb 0.33V 2O 5 heterostructures suggest a positive shift in the VB edge potential and, therefore, an increased driving force for the photoinduced transfer of holes to the midgap state of β-Pb 0.33V 2O 5. This approach facilitates a ca. 0.40 eV decrease in the thermodynamic barrier for hole injection from the VB edge of QDs suggesting an important design parameter. Transient absorption spectroscopy experiments provide direct evidence of hole transfer from photoexcited CdS QDs to the midgap states of β-Pb 0.33V 2O 5 NWs, along with electron transfer into the conduction band of the β-Pb 0.33V 2O 5 NWs. Hole transfer is substantially faster and occurs at <1-ps time scales, whereas completion of electron transfer requires 5—30 ps depending on the nature of the interface. The differentiated time scales of electron and hole transfer, which are furthermore tunable as a function of the mode of attachment of QDs to NWs, provide a vital design tool for designing architectures for solar energy conversion. More generally, the approach developed here suggests that interfacing semiconductor QDs with transition-metal oxide NWs exhibiting intercalative midgap states yields a versatile platform wherein the thermodynamics and kinetics of charge transfer can be systematically modulated to improve the efficiency of charge separation across interfaces.« less

The role of interfacial water layer in atmospherically relevant charge separation

NASA Astrophysics Data System (ADS)

Bhattacharyya, Indrani

Charge separation at interfaces is important in various atmospheric processes, such as thunderstorms, lightning, and sand storms. It also plays a key role in several industrial processes, including ink-jet printing and electrostatic separation. Surprisingly, little is known about the underlying physics of these charging phenomena. Since thin films of water are ubiquitous, they may play a role in these charge separation processes. This talk will focus on the experimental investigation of the role of a water adlayer in interfacial charging, with relevance to meteorologically important phenomena, such as atmospheric charging due to wave actions on oceans and sand storms. An ocean wave generates thousands of bubbles, which upon bursting produce numerous large jet droplets and small film droplets that are charged. In the 1960s, Blanchard showed that the jet droplets are positively charged. However, the charge on the film droplets was not known. We designed an experiment to exclusively measure the charge on film droplets generated by bubble bursting on pure water and aqueous salt solution surfaces. We measured their charge to be negative and proposed a model where a slight excess of hydroxide ions in the interfacial water layer is responsible for generating these negatively charged droplets. The findings from this research led to a better understanding of the ionic disposition at the air-water interface. Sand particles in a wind-blown sand layer, or 'saltation' layer, become charged due to collisions, so much so, that it can cause lightning. Silica, being hydrophilic, is coated with a water layer even under low-humidity conditions. To investigate the importance of this water adlayer in charging the silica surfaces, we performed experiments to measure the charge on silica surfaces due to contact and collision processes. In case of contact charging, the maximum charge separation occurred at an optimum relative humidity. On the contrary, in collisional charging process, no humidity effect was observed. We proposed an ion transfer mechanism in case of contact charging. However, an electron transfer mechanism explained the collisional charging process. The effects of temperature, surface roughness, and chemical nature of surface were also studied for both contact and collisional charging processes.

Combining extrapolation with ghost interaction correction in range-separated ensemble density functional theory for excited states

NASA Astrophysics Data System (ADS)

Alam, Md. Mehboob; Deur, Killian; Knecht, Stefan; Fromager, Emmanuel

2017-11-01

The extrapolation technique of Savin [J. Chem. Phys. 140, 18A509 (2014)], which was initially applied to range-separated ground-state-density-functional Hamiltonians, is adapted in this work to ghost-interaction-corrected (GIC) range-separated ensemble density-functional theory (eDFT) for excited states. While standard extrapolations rely on energies that decay as μ-2 in the large range-separation-parameter μ limit, we show analytically that (approximate) range-separated GIC ensemble energies converge more rapidly (as μ-3) towards their pure wavefunction theory values (μ → +∞ limit), thus requiring a different extrapolation correction. The purpose of such a correction is to further improve on the convergence and, consequently, to obtain more accurate excitation energies for a finite (and, in practice, relatively small) μ value. As a proof of concept, we apply the extrapolation method to He and small molecular systems (viz., H2, HeH+, and LiH), thus considering different types of excitations such as Rydberg, charge transfer, and double excitations. Potential energy profiles of the first three and four singlet Σ+ excitation energies in HeH+ and H2, respectively, are studied with a particular focus on avoided crossings for the latter. Finally, the extraction of individual state energies from the ensemble energy is discussed in the context of range-separated eDFT, as a perspective.

Effects of Magnetic Nanoparticles and External Magnetostatic Field on the Bulk Heterojunction Polymer Solar Cells

DOE PAGES

Wang, Kai; Yi, Chao; Liu, Chang; ...

2015-03-18

The price of energy to separate tightly bound electron-hole pair (or charge-transfer state) and extract freely movable charges from low-mobility materials represents fundamental losses for many low-cost photovoltaic devices. In bulk heterojunction (BHJ) polymer solar cells (PSCs), approximately 50% of the total efficiency lost among all energy loss pathways is due to the photogenerated charge carrier recombination within PSCs and low charge carrier mobility of disordered organic materials. To address these issues, we introduce magnetic nanoparticles (MNPs) and orientate these MNPS within BHJ composite by an external magnetostatic field. Over 50% enhanced efficiency was observed from BHJ PSCs incorporated withmore » MNPs and an external magnetostatic field alignment when compared to the control BHJ PSCs. The optimization of BHJ thin film morphology, suppression of charge carrier recombination, and enhancement in charge carrier collection result in a greatly increased short-circuit current density and fill factor, as a result, enhanced power conversion efficiency.« less

The Effect of Voltage Charging on the Transport Properties of Gold Nanotube Membranes.

PubMed

Experton, Juliette; Martin, Charles R

2018-05-01

Porous membranes are used in chemical separations and in many electrochemical processes and devices. Research on the transport properties of a unique class of porous membranes that contain monodisperse gold nanotubes traversing the entire membrane thickness is reviewed here. These gold nanotubes can act as conduits for ionic and molecular transports through the membrane. Because the tubes are electronically conductive, they can be electrochemically charged by applying a voltage to the membrane. How this "voltage charging" affects the transport properties of gold nanotube membranes is the subject of this Review. Experiments showing that voltage charging can be used to reversibly switch the membrane between ideally cation- and anion-transporting states are reviewed. Voltage charging can also be used to enhance the ionic conductivity of gold nanotube membranes. Finally, voltage charging to accomplish electroporation of living bacteria as they pass through gold nanotube membranes is reviewed. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photophysics of detection of explosive vapours via luminescence quenching of thin films: impact of inter-molecular interactions.

PubMed

Shoaee, Safa; Fan, Shengqiang; Burn, Paul L; Shaw, Paul E

2016-09-21

Fluorescence-based detection of explosive analytes requires an understanding of the nature of the excited state responsible for the luminescence response of a sensing material. Many measurements are carried out to elucidate the fundamental photophysical properties of an emissive material in solution. However, simple transfer of the understanding gained from the solution measurements to the solid-state can lead to errors. This is in part due to the absence of inter-molecular interactions of the chromophores in solution, which are present in the solid-state. To understand the role of inter-molecular interactions on the detection of explosive analytes we have chosen dendrimers from two different families, D1 and D2, which allow facile control of the inter-molecular interactions through the choice of dendrons and emissive chromophores. Using ultrafast transient absorption spectroscopy we find that the solution photoinduced absorption (PA) for both materials can be explained in terms of the generation of singlet excitons, which decay to the ground state, or intersystem cross (ISC) to form a triplet exciton. In neat films however, we observe different photophysical behaviours; first, ISC to the triplet state does not occur, and second, depending on the chromophore, charge transfer and charge separated states are formed. Furthermore, we find that when either dendrimer is interfaced with analyte vapour, the singlet state is strongly quenched, generating a charge transfer state that undergoes geminate recombination.

High intensity high charge state ion beam production with an evaporative cooling magnet ECRIS

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

Lu, W., E-mail: luwang@impcas.ac.cn; Qian, C.; Sun, L. T.

2016-02-15

LECR4 (Lanzhou ECR ion source No. 4) is a room temperature electron cyclotron resonance ion source, designed to produce high current, high charge state ion beams for the SSC-LINAC injector (a new injector for sector separated cyclotron) at the Institute of Modern Physics. LECR4 also serves as a PoP machine for the application of evaporative cooling technology in accelerator field. To achieve those goals, LECR4 ECR ion source has been optimized for the operation at 18 GHz. During 2014, LECR4 ion source was commissioned at 18 GHz microwave of 1.6 kW. To further study the influence of injection stage tomore » the production of medium and high charge state ion beams, in March 2015, the injection stage with pumping system was installed, and some optimum results were produced, such as 560 eμA of O{sup 7+}, 620 eμA of Ar{sup 11+}, 430 eμA of Ar{sup 12+}, 430 eμA of Xe{sup 20+}, and so on. The comparison will be discussed in the paper.« less

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

Excited-state charge separation in the photochemical mechanism of the light-driven enzyme protochlorophyllide oxidoreductase.

PubMed

Heyes, Derren J; Hardman, Samantha J O; Hedison, Tobias M; Hoeven, Robin; Greetham, Greg M; Towrie, Michael; Scrutton, Nigel S

2015-01-26

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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

State selected ion--molecule reactions by a TESICO technique. IV. Relative importance of the two spin-orbit states of Ar/sup +/ in the charge transfer reactions with N/sub 2/ and CO

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

Kato, T.; Tanaka, K.; Koyano, I.

1982-07-01

Charge transfer reactions Ar/sup +/ (/sup 2/P/sub J/)+N/sub 2/..-->..N/sup +//sub 2/+Ar (1) and Ar/sup +/(/sup 2/P/sub J/)+CO..-->..CO/sup +/+Ar (2) have been studied for the two spin-orbit states (J = 3/2 and 1/2) separately using the threshold electron-secondary ion coincidence (TESICO) technique. Relative cross sections for the two states sigma(3/2) and sigma(1/2) have been determined at three collision energies 0.2, 1.4, and 5.8 eV. It has been found that in Reaction (1), sigma(3/2) is larger than sigma (1/2) with ratio sigma(1/2)/sigma(3/2) ranging from 0.5 to 0.8 depending on the collision energy, whereas in Reaction (2), sigma(1/2) is larger than sigma(3/2) withmore » the ratio ranging from 1.2 to 1.6. The implications of these results are discussed with regard to the roles of energy resonance and Franck--Condon factors in charge transfer processes.« less

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-). Theoretical evidence for a competitive charge transfer mechanism.

PubMed

Hu, Zhenming; Boyd, Russell J; Nakatsuji, Hiroshi

2002-03-20

Molecular structures and excited states of CpM(CO)(2) (Cp = eta(5)-C(5)H(5); M = Rh, Ir) and [Cl(2)Rh(CO)(2)](-) complexes have been investigated using the B3LYP and the symmetry-adapted cluster (SAC)/SAC-configuration interaction (SAC-CI) theoretical methods. All the dicarbonyl complexes have singlet ground electronic states with large singlet-triplet separations. Thermal dissociations of CO from the parent dicarbonyls are energetically unfavorable. CO thermal dissociation is an activation process for [Cl(2)Rh(CO)(2)](-) while it is a repulsive potential for CpM(CO)(2). The natures of the main excited states of CpM(CO)(2) and [Cl(2)Rh(CO)(2)](-) are found to be quite different. For [Cl(2)Rh(CO)(2)](-), all the strong transitions are identified to be metal to ligand CO charge transfer (MLCT) excitations. A significant feature of the excited states of CpM(CO)(2) is that both MLCT excitation and a ligand Cp to metal and CO charge transfer excitation are strongly mixed in the higher energy states with the latter having the largest oscillator strength. A competitive charge transfer excited state has therefore been identified theoretically for CpRh(CO)(2) and CpIr(CO)(2). The wavelength dependence of the quantum efficiencies for the photoreactions of CpM(CO)(2) reported by Lees et al. can be explained by the existence of two different types of excited states. The origin of the low quantum efficiencies for the C-H/S-H bond activations of CpM(CO)(2) can be attributed to the smaller proportion of the MLCT excitation in the higher energy states.

True Anomalous Osmosis in Multi-Solute Model Membrane Systems

PubMed Central

Grim, Eugene; Sollner, Karl

1960-01-01

The transport of liquid across charged porous membranes separating two electrolytic solutions of different composition consists of both a normal and an anomalous osmotic component. Anomalous osmosis does not occur with electroneutral membranes. Thus, with membranes which can be charged and discharged reversibly, normal osmosis can be measured with the membrane in the electroneutral state, and normal together with anomalous osmosis with the membrane in a charged state, the difference between these two effects being the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, in multi-solute systems with 0.2 and 0.4 osmolar solutions of a variety of electrolytes and of glucose against solutions of other solutes of the same, one-half, and twice these osmolarities. In the simpler systems the magnitude of the true anomalous osmosis can be predicted semiquantitatively by reference to appropriate single-solute systems. In isoosmolar systems with two electrolytic solutions the anomalous osmotic flow rates may reach 300 µl./cm.2 hr. and more; systems with electrolytic solutions against solutions of glucose can produce twice this rate. These fluxes are of the same order of magnitude as the liquid transport rates across such living structures as the mucosa of dog gall bladder, ileum, and urinary bladder. PMID:13708691

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Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-19

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Carotenoids as electron or excited-state energy donors in artificial photosynthesis: an ultrafast investigation of a carotenoporphyrin and a carotenofullerene dyad.

PubMed

Pillai, Smitha; Ravensbergen, Janneke; Antoniuk-Pablant, Antaeres; Sherman, Benjamin D; van Grondelle, Rienk; Frese, Raoul N; Moore, Thomas A; Gust, Devens; Moore, Ana L; Kennis, John T M

2013-04-07

Photophysical investigations of molecular donor-acceptor systems have helped elucidate many details of natural photosynthesis and revealed design principles for artificial photosynthetic systems. To obtain insights into the factors that govern the partition between excited-state energy transfer (EET) and electron transfer (ET) processes among carotenoids and tetrapyrroles and fullerenes, we have designed artificial photosynthetic dyads that are thermodynamically poised to favor ET over EET processes. The dyads were studied using transient absorption spectroscopy with ∼100 femtosecond time resolution. For dyad , a carotenoporphyrin, excitation to the carotenoid S2 state induces ultrafast ET, competing with internal conversion (IC) to the carotenoid S1 state. In addition, the carotenoid S1 state gives rise to ET. In contrast with biological photosynthesis and many artificial photosynthetic systems, no EET at all was detected for this dyad upon carotenoid S2 excitation. Recombination of the charge separated state takes place in hundreds of picoseconds and yields a triplet state, which is interpreted as a triplet delocalized between the porphyrin and carotenoid moieties. In dyad , a carotenofullerene, excitation of the carotenoid in the S2 band results in internal conversion to the S1 state, ET and probably EET to fullerene on ultrafast timescales. From the carotenoid S1 state EET to fullerene occurs. Subsequently, the excited-state fullerene gives rise to ET from the carotenoid to the fullerene. Again, the charge separated state recombines in hundreds of picoseconds. The results illustrate that for a given rate of EET, the ratio of ET to EET can be controlled by adjusting the driving force for electron transfer.

Quenched dynamics and spin-charge separation in an interacting topological lattice

NASA Astrophysics Data System (ADS)

Barbiero, L.; Santos, L.; Goldman, N.

2018-05-01

We analyze the static and dynamical properties of a one-dimensional topological lattice, the fermionic Su-Schrieffer-Heeger model, in the presence of on-site interactions. Based on a study of charge and spin correlation functions, we elucidate the nature of the topological edge modes, which, depending on the sign of the interactions, either display particles of opposite spin on opposite edges, or a pair and a holon. This study of correlation functions also highlights the strong entanglement that exists between the opposite edges of the system. This last feature has remarkable consequences upon subjecting the system to a quench, where an instantaneous edge-to-edge signal appears in the correlation functions characterizing the edge modes. Besides, other correlation functions are shown to propagate in the bulk according to the light cone imposed by the Lieb-Robinson bound. Our study reveals how one-dimensional lattices exhibiting entangled topological edge modes allow for a nontrivial correlation spreading, while providing an accessible platform to detect spin-charge separation using state-of-the-art experimental techniques.

Deconstructing three-dimensional (3D) structure of absorptive glass mat (AGM) separator to tailor pore dimensions and amplify electrolyte uptake

NASA Astrophysics Data System (ADS)

Rawal, Amit; Rao, P. V. Kameswara; Kumar, Vijay

2018-04-01

Absorptive glass mat (AGM) separator is a vital technical component in valve regulated lead acid (VRLA) batteries that can be tailored for a desired application. To selectively design and tailor the AGM separator, the intricate three-dimensional (3D) structure needs to be unraveled. Herein, a toolkit of 3D analytical models of pore size distribution and electrolyte uptake expressed via wicking characteristics of AGM separators under unconfined and confined states is presented. 3D data of fiber orientation distributions obtained previously through X-ray micro-computed tomography (microCT) analysis are used as key set of input parameters. The predictive ability of pore size distribution model is assessed through the commonly used experimental set-up that usually apply high level of compressive stresses. Further, the existing analytical model of wicking characteristics of AGM separators has been extended to account for 3D characteristics, and subsequently, compared with the experimental results. A good agreement between the theory and experiments pave the way to simulate the realistic charge-discharge modes of the battery by applying cyclic loading condition. A threshold criterion describing the invariant behavior of pore size and wicking characteristics in terms of maximum permissible limit of key structural parameters during charge-discharge mode of the battery has also been proposed.

Insights into collaborative separation process of photogenerated charges and superior performance of solar cells

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

Liu, Xiangyang, E-mail: lxy081276@126.com; Wang, Shun; Zheng, Haiwu

2016-07-25

ZnO nanowires/Cu{sub 4}Bi{sub 4}S{sub 9} (ZnO/CBS) and ZnO nanowires/CBS-graphene nanoplates (ZnO/CBS-GNs), as well as two types of solar cells were prepared. The photovoltaic responses of CBS-GNs and ZnO/CBS-GNs can be improved with incorporation of GNs. The transient surface photovoltage (TPV) can provide detailed information on the separation and transport of photogenerated carriers. The multichannel separation process from the TPVs indicates that the macro-photoelectric signals can be attributed to the photogenerated charges separated at the interface of CBS/GNs, rather than CBS/ZnO. The multi-interfacial recombination is the major carrier loss, and the hole selective p-V{sub 2}O{sub 5} can efficiently accelerate the chargemore » extraction to the external circuit. The ZnO/CBS-GNs cell exhibits the superior performance, and the highest efficiency is 10.9%. With the adequate interfaces of CBS/GNs, GNs conductive network, energy level matching, etc., the excitons can easily diffuse to the interface of CBS/GNs, and the separated electrons and holes can be collected quickly, inducing the high photoelectric properties. Here, a facile strategy for solid state solar cells with superior performance presents a potential application.« less

Photosynthetic antenna-reaction center mimicry with a covalently linked monostyryl boron-dipyrromethene-aza-boron-dipyrromethene-C60 triad.

PubMed

Shi, Wen-Jing; El-Khouly, Mohamed E; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K P

2013-08-19

An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP-ADP and ADP-C60 , and the triad BDP-ADP-C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Is the ground state of Yang-Mills theory Coulombic?

NASA Astrophysics Data System (ADS)

Heinzl, T.; Ilderton, A.; Langfeld, K.; Lavelle, M.; Lutz, W.; McMullan, D.

2008-08-01

We study trial states modelling the heavy quark-antiquark ground state in SU(2) Yang-Mills theory. A state describing the flux tube between quarks as a thin string of glue is found to be a poor description of the continuum ground state; the infinitesimal thickness of the string leads to UV artifacts which suppress the overlap with the ground state. Contrastingly, a state which surrounds the quarks with non-Abelian Coulomb fields is found to have a good overlap with the ground state for all charge separations. In fact, the overlap increases as the lattice regulator is removed. This opens up the possibility that the Coulomb state is the true ground state in the continuum limit.

Highly-Efficient Charge Separation and Polaron Delocalization in Polymer-Fullerene Bulk-Heterojunctions: A Comparative Multi-Frequency EPR & DFT Study

PubMed Central

Niklas, Jens; Mardis, Kristy L.; Banks, Brian P.; Grooms, Gregory M.; Sperlich, Andreas; Dyakonov, Vladimir; Beaupré, Serge; Leclerc, Mario; Xu, Tao; Yu, Luping; Poluektov, Oleg G.

2016-01-01

The ongoing depletion of fossil fuels has led to an intensive search for additional renewable energy sources. Solar-based technologies could provide sufficient energy to satisfy the global economic demands in the near future. Photovoltaic (PV) cells are the most promising man-made devices for direct solar energy utilization. Understanding the charge separation and charge transport in PV materials at a molecular level is crucial for improving the efficiency of the solar cells. Here, we use light-induced EPR spectroscopy combined with DFT calculations to study the electronic structure of charge separated states in blends of polymers (P3HT, PCDTBT, and PTB7) and fullerene derivatives (C60-PCBM and C70-PCBM). Solar cells made with the same composites as active layers show power conversion efficiencies of 3.3% (P3HT), 6.1% (PCDTBT), and 7.3% (PTB7), respectively. Under illumination of these composites, two paramagnetic species are formed due to photo-induced electron transfer between the conjugated polymer and the fullerene. They are the positive, P+, and negative, P-, polarons on the polymer backbone and fullerene cage, respectively, and correspond to radical cations and radical anions. Using the high spectral resolution of high-frequency EPR (130 GHz), the EPR spectra of these species were resolved and principal components of the g-tensors were assigned. Light-induced pulsed ENDOR spectroscopy allowed the determination of 1H hyperfine coupling constants of photogenerated positive and negative polarons. The experimental results obtained for the different polymer-fullerene composites have been compared with DFT calculations, revealing that in all three systems the positive polaron is distributed over distances of 40 - 60 Å on the polymer chain. This corresponds to about 15 thiophene units for P3HT, approximately three units PCDTBT, and about three to four units for PTB7. No spin density delocalization between neighboring fullerene molecules was detected by EPR. Strong delocalization of the positive polaron on the polymer donor is an important reason for the efficient charge separation in bulk heterojunction systems as it minimizes the wasteful process of charge recombination. The combination of advanced EPR spectroscopy and DFT is a powerful approach for investigation of light-induced charge dynamics in organic photovoltaic materials. PMID:23670645

Native red electrophoresis--a new method suitable for separation of native proteins.

PubMed

Dráb, Tomáš; Kračmerová, Jana; Tichá, Ivana; Hanzlíková, Eva; Tichá, Marie; Ryšlavá, Helena; Doubnerová, Veronika; Maňásková-Postlerová, Pavla; Liberda, Jiří

2011-12-01

A new type of native electrophoresis was developed to separate and characterize proteins. In this modification of the native blue electrophoresis, the dye Ponceau Red S is used instead of Coomassie Brilliant Blue to impose uniform negative charge on proteins to enable their electrophoretic separation according to their relative molecular masses. As Ponceau Red S binds less tightly to proteins, in comparison with Coomassie Blue, it can be easily removed after the electrophoretic separation and a further investigation of protein properties is made possible (e.g. an enzyme detection or electroblotting). The tested proteins also kept their native properties (enzyme activity or aggregation state). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separating large microscale particles by exploiting charge differences with dielectrophoresis.

PubMed

Polniak, Danielle V; Goodrich, Eric; Hill, Nicole; Lapizco-Encinas, Blanca H

2018-04-13

Dielectrophoresis (DEP), the migration of particles due to polarization effects under the influence of a nonuniform electric field, was employed for characterizing the behavior and achieving the separation of larger (diameter >5 μm) microparticles by exploiting differences in electrical charge. Usually, electrophoresis (EP) is the method of choice for separating particles based on differences in electrical charge; however, larger particles, which have low electrophoretic mobilities, cannot be easily separated with EP-based techniques. This study presents an alternative for the characterization, assessment, and separation of larger microparticles, where charge differences are exploited with DEP instead of EP. Polystyrene microparticles with sizes varying from 5 to 10 μm were characterized employing microdevices for insulator-based dielectrophoresis (iDEP). Particles within an iDEP microchannel were exposed simultaneously to DEP, EP, and electroosmotic (EO) forces. The electrokinetic behavior of four distinct types of microparticles was carefully characterized by means of velocimetry and dielectrophoretic capture assessments. As a final step, a dielectropherogram separation of two distinct types of 10 μm particles was devised by first characterizing the particles and then performing the separation. The two types of 10 μm particles were eluted from the iDEP device as two separate peaks of enriched particles in less than 80 s. It was demonstrated that particles with the same size, shape, surface functionalization, and made from the same bulk material can be separated with iDEP by exploiting slight differences in the magnitude of particle charge. The results from this study open the possibility for iDEP to be used as a technique for the assessment and separation of biological cells that have very similar characteristics (shape, size, similar make-up), but slight variance in surface electrical charge. Copyright © 2018 Elsevier B.V. All rights reserved.

Superconducting transmission line particle detector

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

Gray, K.E.

This paper describes a microvertex particle detector for use in a high energy physic collider including a plurality of parallel superconducting thin film strips separated from a superconducting ground plane by an insulating layer to form a plurality of superconducting waveguides. The microvertex particle detector indicates passage of a charged subatomic particle by measuring a voltage pulse measured across a superconducting waveguide caused by the transition of the superconducting thin film strip from a superconducting to a non-superconducting state in response to the passage of a charged particle. A plurality of superconducting thin film strips in two orthogonal planes plusmore » the slow electromagnetic wave propogating in a superconducting transmission line are used to resolve N{sup 2} ambiguity of charged particle events.« less

Superconducting transmission line particle detector

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

Gray, K.E.

A microvertex particle detector for use in a high energy physic collider including a plurality of parallel superconducting thin film strips separated from a superconducting ground plane by an insulating layer to form a plurality of superconducting waveguides. The microvertex particle detector indicates passage of a charged subatomic particle by measuring a voltage pulse measured across a superconducting waveguide caused by the transition of the superconducting thin film strip from a superconducting to a non- superconducting state in response to the passage of a charged particle. A plurality of superconducting thin film strips in two orthogonal planes plus the slowmore » electromagnetic wave propagating in a superconducting transmission line are used to resolve N/sup 2/ ambiguity of charged particle events. 6 figs.« less

Nonadiabatic excited-state molecular dynamics modeling of photoinduced dynamics in conjugated molecules.

PubMed

Nelson, Tammie; Fernandez-Alberti, Sebastian; Chernyak, Vladimir; Roitberg, Adrian E; Tretiak, Sergei

2011-05-12

Nonadiabatic dynamics generally defines the entire evolution of electronic excitations in optically active molecular materials. It is commonly associated with a number of fundamental and complex processes such as intraband relaxation, energy transfer, and light harvesting influenced by the spatial evolution of excitations and transformation of photoexcitation energy into electrical energy via charge separation (e.g., charge injection at interfaces). To treat ultrafast excited-state dynamics and exciton/charge transport we have developed a nonadiabatic excited-state molecular dynamics (NA-ESMD) framework incorporating quantum transitions. Our calculations rely on the use of the Collective Electronic Oscillator (CEO) package accounting for many-body effects and actual potential energy surfaces of the excited states combined with Tully's fewest switches algorithm for surface hopping for probing nonadiabatic processes. This method is applied to model the photoinduced dynamics of distyrylbenzene (a small oligomer of polyphenylene vinylene, PPV). Our analysis shows intricate details of photoinduced vibronic relaxation and identifies specific slow and fast nuclear motions that are strongly coupled to the electronic degrees of freedom, namely, torsion and bond length alternation, respectively. Nonadiabatic relaxation of the highly excited mA(g) state is predicted to occur on a femtosecond time scale at room temperature and on a picosecond time scale at low temperature.

Discrete space charge affected field emission: Flat and hemisphere emitters

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

Jensen, Kevin L., E-mail: kevin.jensen@nrl.navy.mil; Shiffler, Donald A.; Tang, Wilkin

Models of space-charge affected thermal-field emission from protrusions, able to incorporate the effects of both surface roughness and elongated field emitter structures in beam optics codes, are desirable but difficult. The models proposed here treat the meso-scale diode region separate from the micro-scale regions characteristic of the emission sites. The consequences of discrete emission events are given for both one-dimensional (sheets of charge) and three dimensional (rings of charge) models: in the former, results converge to steady state conditions found by theory (e.g., Rokhlenko et al. [J. Appl. Phys. 107, 014904 (2010)]) but show oscillatory structure as they do. Surfacemore » roughness or geometric features are handled using a ring of charge model, from which the image charges are found and used to modify the apex field and emitted current. The roughness model is shown to have additional constraints related to the discrete nature of electron charge. The ability of a unit cell model to treat field emitter structures and incorporate surface roughness effects inside a beam optics code is assessed.« less

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.

The Impact of the Affordable Care Act on Funding for Newborn Screening Services.

PubMed

Costich, Julia F; Durst, Andrea L

2016-01-01

The Affordable Care Act requires most health plans to cover the federal Recommended Uniform Screening Panel of newborn screening (NBS) tests with no cost sharing. However, state NBS programs vary widely in both the number of mandated tests and their funding mechanisms, including a combination of state laboratory fees, third-party billing, and other federal and state funding. We assessed the potential impact of the Affordable Care Act coverage mandate on states' NBS funding. We performed an extensive review of the refereed literature, federal and state agency reports, relevant organizations' websites, and applicable state laws and regulations; interviewed 28 state and federal officials from August to December 2014; and then assessed the interview findings manually. Although a majority of states had well-established systems for including laboratory-based NBS tests in bundled charges for newborn care, billing practices for critical congenital heart disease and newborn hearing tests were less uniform. Most commonly, birthing facilities either prepaid the costs of laboratory-based tests when acquiring the filter paper kits, or the facilities paid for the tests when the kits were submitted. Some states had separate arrangements for billing Medicaid, and smaller facilities sometimes contracted with hearing test vendors that billed families separately. Although the Affordable Care Act coverage mandate may offset some state NBS funding for the screenings themselves, federal support is still required to assure access to the full range of NBS program services. Limiting reimbursement to the costs of screening tests alone would undermine the common practice of using screening charges to fund follow-up services counseling, and medical food or formula, particularly for low-income families.

Histidine in Continuum Electrostatics Protonation State Calculations

PubMed Central

Couch, Vernon; Stuchebruckhov, Alexei

2014-01-01

A modification to the standard continuum electrostatics approach to calculate protein pKas which allows for the decoupling of histidine tautomers within a two state model is presented. Histidine with four intrinsically coupled protonation states cannot be easily incorporated into a two state formalism because the interaction between the two protonatable sites of the imidazole ring is not purely electrostatic. The presented treatment, based on a single approximation of the interrelation between histidine’s charge states, allows for a natural separation of the two protonatable sites associated with the imidazole ring as well as the inclusion of all protonation states within the calculation. PMID:22072521

Ultrafast dynamics in multifunctional Ru(II)-loaded polymers for solar energy conversion.

PubMed

Morseth, Zachary A; Wang, Li; Puodziukynaite, Egle; Leem, Gyu; Gilligan, Alexander T; Meyer, Thomas J; Schanze, Kirk S; Reynolds, John R; Papanikolas, John M

2015-03-17

The use of sunlight to make chemical fuels (i.e., solar fuels) is an attractive approach in the quest to develop sustainable energy sources. Using nature as a guide, assemblies for artificial photosynthesis will need to perform multiple functions. They will need to be able to harvest light across a broad region of the solar spectrum, transport excited-state energy to charge-separation sites, and then transport and store redox equivalents for use in the catalytic reactions that produce chemical fuels. This multifunctional behavior will require the assimilation of multiple components into a single macromolecular system. A wide variety of different architectures including porphyrin arrays, peptides, dendrimers, and polymers have been explored, with each design posing unique challenges. Polymer assemblies are attractive due to their relative ease of production and facile synthetic modification. However, their disordered nature gives rise to stochastic dynamics not present in more ordered assemblies. The rational design of assemblies requires a detailed understanding of the energy and electron transfer events that follow light absorption, which can occur on time scales ranging from femtoseconds to hundreds of microseconds, necessitating the use of sophisticated techniques. We have used a combination of time-resolved absorption and emission spectroscopies with observation times that span 9 orders of magnitude to follow the excited-state evolution within polymer-based molecular assemblies. We complement experimental observations with molecular dynamics simulations to develop a microscopic view of these dynamics. This Account provides an overview of our work on polymers decorated with pendant Ru(II) chromophores, both in solution and on surfaces. We have examined site-to-site energy transport among the Ru(II) complexes, and in systems incorporating π-conjugated polymers, we have observed ultrafast formation of a long-lived charge-separated state. When attached to TiO2, these assemblies exhibit multifunctional behavior in which photon absorption is followed by energy transport to the surface and electron injection to produce an oxidized metal complex. The oxidizing equivalent is then transferred to the conjugated polymer, giving rise to a long-lived charge-separated state.

Collision-Induced Dissociation of Electrosprayed Protein Complexes: An All-Atom Molecular Dynamics Model with Mobile Protons.

PubMed

Popa, Vlad; Trecroce, Danielle A; McAllister, Robert G; Konermann, Lars

2016-06-16

Electrospray ionization mass spectrometry (ESI-MS) has become an indispensable technique for examining noncovalent protein complexes. Collision-induced dissociation (CID) of these multiply protonated gaseous ions usually culminates in ejection of a single subunit with a disproportionately large amount of charge. Experiments suggest that this process involves subunit unfolding prior to separation from the residual complex, as well as H(+) migration onto the unravelling chain. Molecular dynamics (MD) simulations are a promising avenue for gaining detailed insights into these CID events. Unfortunately, typical MD algorithms do not allow for mobile protons. Here we address this limitation by implementing a strategy that combines atomistic force fields (such as OPLS/AA and CHARMM36) with a proton hopping algorithm, focusing on the tetrameric complexes transthyretin and streptavidin. Protons are redistributed over all acidic and basic sites in 20 ps intervals, subject to an energy function that reflects electrostatic interactions and proton affinities. Our simulations predict that nativelike conformers at the onset of collisional heating contain multiple salt bridges. Collisional heating initially causes subtle structural changes that lead to a gradual decline of these zwitterionic patterns. Many of the MD runs show gradual unfolding of a single subunit in conjunction with H(+) migration, culminating in subunit separation from the complex. However, there are also instances where two or more chains start to unfold simultaneously, giving rise to charge competition. The scission point where the "winning" subunit separates from the complex can be attained for different degrees of unfolding, giving rise to product ions in various charge states. The simulated product ion distributions are in close agreement with experimental CID data. Proton enrichment in the departing subunit is driven by charge-charge repulsion, but the combination of salt bridge depletion, charge migration, and proton affinity causes surprising compensation effects among the various energy terms. It appears that this work provides the most detailed account to date of the mechanism whereby noncovalent protein complexes disassemble during CID.

Real-space decoupling transformation for quantum many-body systems.

PubMed

Evenbly, G; Vidal, G

2014-06-06

We propose a real-space renormalization group method to explicitly decouple into independent components a many-body system that, as in the phenomenon of spin-charge separation, exhibits separation of degrees of freedom at low energies. Our approach produces a branching holographic description of such systems that opens the path to the efficient simulation of the most entangled phases of quantum matter, such as those whose ground state violates a boundary law for entanglement entropy. As in the coarse-graining transformation of Vidal [Phys. Rev. Lett. 99, 220405 (2007).

Effect of NaI/I 2 mediators on properties of PEO/LiAlO 2 based all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Yin, Yijing; Zhou, Juanjuan; Mansour, Azzam N.; Zhou, Xiangyang

NaI/I 2 mediators and activated carbon were added into poly(ethylene oxide) (PEO)/lithium aluminate (LiAlO 2) electrolyte to fabricate composite electrodes. All solid-state supercapacitors were fabricated using the as prepared composite electrodes and a Nafion 117 membrane as a separator. Cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge/discharge measurements were conducted to evaluate the electrochemical properties of the supercapacitors. With the addition of NaI/I 2 mediators, the specific capacitance increased by 27 folds up to 150 F g -1. The specific capacitance increased with increases in the concentration of mediators in the electrodes. The addition of mediators also reduced the electrode resistance and rendered a higher electron transfer rate between mediator and mediator. The stability of the all-solid-state supercapacitor was tested over 2000 charge/discharge cycles.

Critical Role of the Exchange Interaction for the Electronic Structure and Charge-Density-Wave Formation in TiSe2

NASA Astrophysics Data System (ADS)

Hellgren, Maria; Baima, Jacopo; Bianco, Raffaello; Calandra, Matteo; Mauri, Francesco; Wirtz, Ludger

2017-10-01

We show that the inclusion of screened exchange via hybrid functionals provides a unified description of the electronic and vibrational properties of TiSe2 . In contrast to local approximations in density functional theory, the explicit inclusion of exact, nonlocal exchange captures the effects of the electron-electron interaction needed to both separate the Ti -d states from the Se -p states and stabilize the charge-density-wave (CDW) (or low-T ) phase through the formation of a p -d hybridized state. We further show that this leads to an enhanced electron-phonon coupling that can drive the transition even if a small gap opens in the high-T phase. Finally, we demonstrate that the hybrid functionals can generate a CDW phase where the electronic bands, the geometry, and the phonon frequencies are in agreement with experiments.

Control of mobility in molecular organic semiconductors by dendrimer generation

NASA Astrophysics Data System (ADS)

Lupton, J. M.; Samuel, I. D.; Beavington, R.; Frampton, M. J.; Burn, P. L.; Bässler, H.

2001-04-01

Conjugated dendrimers are of interest as novel materials for light-emitting diodes. They consist of a luminescent chromophore at the core with highly branched conjugated dendron sidegroups. In these materials, light emission occurs from the core and is independent of generation. The dendron branching controls the separation between the chromophores. We present here a family of conjugated dendrimers and investigate the effect of dendron branching on light emission and charge transport. We apply a number of transport measurement techniques to thin films of a conjugated dendrimer in a light-emitting diode configuration to determine the effect of chromophore spacing on charge transport. We find that the mobility is reduced by two orders of magnitude as the size of the molecule doubles with increased branching or dendrimer generation. The degree of branching allows a unique control of mobility by molecular structure. An increase in chromophore separation also results in a reduction of intermolecular interactions, which reduces the red emission tail in film photoluminescence. We find that the steady-state charge transport is well described by a simple device model incorporating the effect of generation, and use the materials to shed light on the interpretation of transient electroluminescence data. We demonstrate the significance of the ability to tune the mobility in bilayer devices, where a more balanced charge transport can be achieved.

26 CFR 1.163-2 - Installment purchases where interest charge is not separately stated.

Code of Federal Regulations, 2010 CFR

2010-04-01

.... (a) In general. (1) Whenever there is a contract with a seller for the purchase of personal property... payments to be treated as interest shall be equal to 6 percent of the average unpaid balance under the contract during the taxable year. For purposes of this computation, the average unpaid balance under the...

Two possible improvements for mass spectrometry analysis of intact biomolecules.

PubMed

Raznikov, Valeriy V; Zelenov, Vladislav V; Aparina, Elena V; Pikhtelev, Alexander R; Sulimenkov, Ilia V; Raznikova, Marina O

2017-08-01

The goals of our study were to investigate abilities of two approaches to eliminate possible errors in electrospray mass spectrometry measurements of biomolecules. Passing of a relatively dense supersonic gas jet through ionization region followed by its hitting the spray of the analyzed solution in low vacuum may be effective to keep an initial biomolecule structure in solution. Provided that retention of charge carriers for some sites in the biomolecule cannot be changed noticeably in electrospray ion source, decomposition and separation of charge-state distributions of electrosprayed ions may give additional information about native structure of biomolecules in solution.

Search for doubly charged Higgs bosons with lepton-flavor-violating decays involving tau leptons.

PubMed

Aaltonen, T; Adelman, J; Akimoto, T; Albrow, M G; Alvarez González, B; Amerio, S; Amidei, D; Anastassov, A; Annovi, A; Antos, J; Aoki, M; Apollinari, G; Apresyan, A; Arisawa, T; Artikov, A; Ashmanskas, W; Attal, A; Aurisano, A; Azfar, F; Azzi-Bacchetta, P; Azzurri, P; Bacchetta, N; Badgett, W; Barbaro-Galtieri, A; Barnes, V E; Barnett, B A; Baroiant, S; Bartsch, V; Bauer, G; Beauchemin, P-H; Bedeschi, F; Bednar, P; Behari, S; Bellettini, G; Bellinger, J; Belloni, A; Benjamin, D; Beretvas, A; Beringer, J; Berry, T; Bhatti, A; Binkley, M; Bisello, D; Bizjak, I; Blair, R E; Blocker, C; Blumenfeld, B; Bocci, A; Bodek, A; Boisvert, V; Bolla, G; Bolshov, A; Bortoletto, D; Boudreau, J; Boveia, A; Brau, B; Bridgeman, A; Brigliadori, L; Bromberg, C; Brubaker, E; Budagov, J; Budd, H S; Budd, S; Burkett, K; Busetto, G; Bussey, P; Buzatu, A; Byrum, K L; Cabrera, S; Campanelli, M; Campbell, M; Canelli, F; Canepa, A; Carlsmith, D; Carosi, R; Carrillo, S; Carron, S; Casal, B; Casarsa, M; Castro, A; Catastini, P; Cauz, D; Cavalli-Sforza, M; Cerri, A; Cerrito, L; Chang, S H; Chen, Y C; Chertok, M; Chiarelli, G; Chlachidze, G; Chlebana, F; Cho, K; Chokheli, D; Chou, J P; Choudalakis, G; Chuang, S H; Chung, K; Chung, W H; Chung, Y S; Ciobanu, C I; Ciocci, M A; Clark, A; Clark, D; Compostella, G; Convery, M E; Conway, J; Cooper, B; Copic, K; Cordelli, M; Cortiana, G; Crescioli, F; Cuenca Almenar, C; Cuevas, J; Culbertson, R; Cully, J C; Dagenhart, D; Datta, M; Davies, T; de Barbaro, P; De Cecco, S; Deisher, A; De Lentdecker, G; De Lorenzo, G; Dell'Orso, M; Demortier, L; Deng, J; Deninno, M; De Pedis, D; Derwent, P F; Di Giovanni, G P; Dionisi, C; Di Ruzza, B; Dittmann, J R; D'Onofrio, M; Donati, S; Dong, P; Donini, J; Dorigo, T; Dube, S; Efron, J; Erbacher, R; Errede, D; Errede, S; Eusebi, R; Fang, H C; Farrington, S; Fedorko, W T; Feild, R G; Feindt, M; Fernandez, J P; Ferrazza, C; Field, R; Flanagan, G; Forrest, R; Forrester, S; Franklin, M; Freeman, J C; Furic, I; Gallinaro, M; Galyardt, J; Garberson, F; Garcia, J E; Garfinkel, A F; Genser, K; Gerberich, H; Gerdes, D; Giagu, S; Giakoumopolou, V; Giannetti, P; Gibson, K; Gimmell, J L; Ginsburg, C M; Giokaris, N; Giordani, M; Giromini, P; Giunta, M; Glagolev, V; Glenzinski, D; Gold, M; Goldschmidt, N; Golossanov, A; Gomez, G; Gomez-Ceballos, G; Goncharov, M; González, O; Gorelov, I; Goshaw, A T; Goulianos, K; Gresele, A; Grinstein, S; Grosso-Pilcher, C; Grundler, U; Guimaraes da Costa, J; Gunay-Unalan, Z; Haber, C; Hahn, K; Hahn, S R; Halkiadakis, E; Hamilton, A; Han, B-Y; Han, J Y; Handler, R; Happacher, F; Hara, K; Hare, D; Hare, M; Harper, S; Harr, R F; Harris, R M; Hartz, M; Hatakeyama, K; Hauser, J; Hays, C; Heck, M; Heijboer, A; Heinemann, B; Heinrich, J; Henderson, C; Herndon, M; Heuser, J; Hewamanage, S; Hidas, D; Hill, C S; Hirschbuehl, D; Hocker, A; Hou, S; Houlden, M; Hsu, S-C; Huffman, B T; Hughes, R E; Husemann, U; Huston, J; Incandela, J; Introzzi, G; Iori, M; Ivanov, A; Iyutin, B; James, E; Jayatilaka, B; Jeans, D; Jeon, E J; Jindariani, S; Johnson, W; Jones, M; Joo, K K; Jun, S Y; Jung, J E; Junk, T R; Kamon, T; Kar, D; Karchin, P E; Kato, Y; Kephart, R; Kerzel, U; Khotilovich, V; Kilminster, B; Kim, D H; Kim, H S; Kim, J E; Kim, M J; Kim, S B; Kim, S H; Kim, Y K; Kimura, N; Kirsch, L; Klimenko, S; Klute, M; Knuteson, B; Ko, B R; Koay, S A; Kondo, K; Kong, D J; Konigsberg, J; Korytov, A; Kotwal, A V; Kraus, J; Kreps, M; Kroll, J; Krumnack, N; Kruse, M; Krutelyov, V; Kubo, T; Kuhlmann, S E; Kuhr, T; Kulkarni, N P; Kusakabe, Y; Kwang, S; Laasanen, A T; Lai, S; Lami, S; Lammel, S; Lancaster, M; Lander, R L; Lannon, K; Lath, A; Latino, G; Lazzizzera, I; LeCompte, T; Lee, J; Lee, J; Lee, Y J; Lee, S W; Lefèvre, R; Leonardo, N; Leone, S; Levy, S; Lewis, J D; Lin, C; Lin, C S; Linacre, J; Lindgren, M; Lipeles, E; Lister, A; Litvintsev, D O; Liu, T; Lockyer, N S; Loginov, A; Loreti, M; Lovas, L; Lu, R-S; Lucchesi, D; Lueck, J; Luci, C; Lujan, P; Lukens, P; Lungu, G; Lyons, L; Lys, J; Lysak, R; Lytken, E; Mack, P; MacQueen, D; Madrak, R; Maeshima, K; Makhoul, K; Maki, T; Maksimovic, P; Malde, S; Malik, S; Manca, G; Manousakis, A; Margaroli, F; Marino, C; Marino, C P; Martin, A; Martin, M; Martin, V; Martínez, M; Martínez-Ballarín, R; Maruyama, T; Mastrandrea, P; Masubuchi, T; Mattson, M E; Mazzanti, P; McFarland, K S; McIntyre, P; McNulty, R; Mehta, A; Mehtala, P; Menzemer, S; Menzione, A; Merkel, P; Mesropian, C; Messina, A; Miao, T; Miladinovic, N; Miles, J; Miller, R; Mills, C; Milnik, M; Mitra, A; Mitselmakher, G; Miyake, H; Moed, S; Moggi, N; Moon, C S; Moore, R; Morello, M; Movilla Fernandez, P; Mülmenstädt, J; Mukherjee, A; Muller, Th; Mumford, R; Murat, P; Mussini, M; Nachtman, J; Nagai, Y; Nagano, A; Naganoma, J; Nakamura, K; Nakano, I; Napier, A; Necula, V; Neu, C; Neubauer, M S; Nielsen, J; Nodulman, L; Norman, M; Norniella, O; Nurse, E; Oh, S H; Oh, Y D; Oksuzian, I; Okusawa, T; Oldeman, R; Orava, R; Osterberg, K; Pagan Griso, S; Pagliarone, C; Palencia, E; Papadimitriou, V; Papaikonomou, A; Paramonov, A A; Parks, B; Pashapour, S; Patrick, J; Pauletta, G; Paulini, M; Paus, C; Pellett, D E; Penzo, A; Phillips, T J; Piacentino, G; Piedra, J; Pinera, L; Pitts, K; Plager, C; Pondrom, L; Portell, X; Poukhov, O; Pounder, N; Prakoshyn, F; Pronko, A; Proudfoot, J; Ptohos, F; Punzi, G; Pursley, J; Rademacker, J; Rahaman, A; Ramakrishnan, V; Ranjan, N; Redondo, I; Reisert, B; Rekovic, V; Renton, P; Rescigno, M; Richter, S; Rimondi, F; Ristori, L; Robson, A; Rodrigo, T; Rogers, E; Rolli, S; Roser, R; Rossi, M; Rossin, R; Roy, P; Ruiz, A; Russ, J; Rusu, V; Saarikko, H; Safonov, A; Sakumoto, W K; Salamanna, G; Saltó, O; Santi, L; Sarkar, S; Sartori, L; Sato, K; Savoy-Navarro, A; Scheidle, T; Schlabach, P; Schmidt, E E; Schmidt, M A; Schmidt, M P; Schmitt, M; Schwarz, T; Scodellaro, L; Scott, A L; Scribano, A; Scuri, F; Sedov, A; Seidel, S; Seiya, Y; Semenov, A; Sexton-Kennedy, L; Sfyrla, A; Shalhout, S Z; Shapiro, M D; Shears, T; Shepard, P F; Sherman, D; Shimojima, M; Shochet, M; Shon, Y; Shreyber, I; Sidoti, A; Sinervo, P; Sisakyan, A; Slaughter, A J; Slaunwhite, J; Sliwa, K; Smith, J R; Snider, F D; Snihur, R; Soderberg, M; Soha, A; Somalwar, S; Sorin, V; Spalding, J; Spinella, F; Spreitzer, T; Squillacioti, P; Stanitzki, M; St Denis, R; Stelzer, B; Stelzer-Chilton, O; Stentz, D; Strologas, J; Stuart, D; Suh, J S; Sukhanov, A; Sun, H; Suslov, I; Suzuki, T; Taffard, A; Takashima, R; Takeuchi, Y; Tanaka, R; Tecchio, M; Teng, P K; Terashi, K; Thom, J; Thompson, A S; Thompson, G A; Thomson, E; Tipton, P; Tiwari, V; Tkaczyk, S; Toback, D; Tokar, S; Tollefson, K; Tomura, T; Tonelli, D; Torre, S; Torretta, D; Tourneur, S; Trischuk, W; Tu, Y; Turini, N; Ukegawa, F; Uozumi, S; Vallecorsa, S; van Remortel, N; Varganov, A; Vataga, E; Vázquez, F; Velev, G; Vellidis, C; Veszpremi, V; Vidal, M; Vidal, R; Vila, I; Vilar, R; Vine, T; Vogel, M; Volobouev, I; Volpi, G; Würthwein, F; Wagner, P; Wagner, R G; Wagner, R L; Wagner-Kuhr, J; Wagner, W; Wakisaka, T; Wallny, R; Wang, S M; Warburton, A; Waters, D; Weinberger, M; Wester, W C; Whitehouse, B; Whiteson, D; Wicklund, A B; Wicklund, E; Williams, G; Williams, H H; Wilson, P; Winer, B L; Wittich, P; Wolbers, S; Wolfe, C; Wright, T; Wu, X; Wynne, S M; Yagil, A; Yamamoto, K; Yamaoka, J; Yamashita, T; Yang, C; Yang, U K; Yang, Y C; Yao, W M; Yeh, G P; Yoh, J; Yorita, K; Yoshida, T; Yu, G B; Yu, I; Yu, S S; Yun, J C; Zanello, L; Zanetti, A; Zaw, I; Zhang, X; Zheng, Y; Zucchelli, S

2008-09-19

We search for pair production of doubly charged Higgs particles (H+/- +/-) followed by decays into electron-tau (etau) and muon-tau (mutau) pairs using data (350 pb(-1) collected from [over]pp collisions at sqrt[s]=1.96 TeV by the CDF II experiment. We search separately for cases where three or four final-state leptons are detected, and combine results for exclusive decays to left-handed etau (mutau) pairs. We set an H+/- +/- lower mass limit of 114(112) GeV/c(2) at the 95% confidence level.

A solution-processed binary cathode interfacial layer facilitates electron extraction for inverted polymer solar cells.

PubMed

Zhang, Xinyuan; Li, Zhiqi; Liu, Chunyu; Guo, Jiaxin; Shen, Liang; Guo, Wenbin

2018-03-15

The charge transfer and separation are significantly affected by the electron properties of the interface between the electron-donor layer and the carrier-transporting layer in polymer solar cells (PSCs). In this study, we investigate the electron extraction mechanism of PSCs with a low temperature solution-processed ZnO/PEI as electron transport layer. The incorporation of PEI layer can decrease the work function of ZnO and reduce interfacial barrier, which facilitates electron extraction and suppresses bimolecular recombination, leading to a significant performance enhancement. Furthermore, PEI layer can induce phase separation and passivite inorganic surface trap states as well as shift the interfacial energy offset between metal oxide and organic materials. This work offers a simple and effective way to improve the charge transporting property of organic photovoltaic devices. Copyright © 2017 Elsevier Inc. All rights reserved.

Scattering of charged particles on two spatially separated time-periodic optical fields

NASA Astrophysics Data System (ADS)

Szabó, Lóránt Zs.; Benedict, Mihály G.; Földi, Péter

2017-12-01

We consider a monoenergetic beam of moving charged particles interacting with two separated oscillating electric fields. Time-periodic linear potential is assumed to model the light-particle interaction using a nonrelativistic, quantum mechanical description based on Gordon-Volkov states. Applying Floquet theory, we calculate transmission probabilities as a function of the laser field parameters. The transmission resonances in this Ramsey-like setup are interpreted as if they originated from a corresponding static double-potential barrier with heights equal to the ponderomotive potential resulting from the oscillating field. Due to the opening of new "Floquet channels," the resonances are repeated at input energies when the corresponding frequency is shifted by an integer multiple of the exciting frequency. These narrow resonances can be used as precise energy filters. The fine structure of the transmission spectra is determined by the phase difference between the two oscillating light fields, allowing for the optical control of the transmission.

Harvesting solar energy by means of charge-separating nanocrystals and their solids.

PubMed

Diederich, Geoffrey; O'Connor, Timothy; Moroz, Pavel; Kinder, Erich; Kohn, Elena; Perera, Dimuthu; Lorek, Ryan; Lambright, Scott; Imboden, Martene; Zamkov, Mikhail

2012-08-23

Conjoining different semiconductor materials in a single nano-composite provides synthetic means for the development of novel optoelectronic materials offering a superior control over the spatial distribution of charge carriers across material interfaces. As this study demonstrates, a combination of donor-acceptor nanocrystal (NC) domains in a single nanoparticle can lead to the realization of efficient photocatalytic materials, while a layered assembly of donor- and acceptor-like nanocrystals films gives rise to photovoltaic materials. Initially the paper focuses on the synthesis of composite inorganic nanocrystals, comprising linearly stacked ZnSe, CdS, and Pt domains, which jointly promote photoinduced charge separation. These structures are used in aqueous solutions for the photocatalysis of water under solar radiation, resulting in the production of H2 gas. To enhance the photoinduced separation of charges, a nanorod morphology with a linear gradient originating from an intrinsic electric field is used. The inter-domain energetics are then optimized to drive photogenerated electrons toward the Pt catalytic site while expelling the holes to the surface of ZnSe domains for sacrificial regeneration (via methanol). Here we show that the only efficient way to produce hydrogen is to use electron-donating ligands to passivate the surface states by tuning the energy level alignment at the semiconductor-ligand interface. Stable and efficient reduction of water is allowed by these ligands due to the fact that they fill vacancies in the valence band of the semiconductor domain, preventing energetic holes from degrading it. Specifically, we show that the energy of the hole is transferred to the ligand moiety, leaving the semiconductor domain functional. This enables us to return the entire nanocrystal-ligand system to a functional state, when the ligands are degraded, by simply adding fresh ligands to the system. To promote a photovoltaic charge separation, we use a composite two-layer solid of PbS and TiO2 films. In this configuration, photoinduced electrons are injected into TiO2 and are subsequently picked up by an FTO electrode, while holes are channeled to a Au electrode via PbS layer. To develop the latter we introduce a Semiconductor Matrix Encapsulated Nanocrystal Arrays (SMENA) strategy, which allows bonding PbS NCs into the surrounding matrix of CdS semiconductor. As a result, fabricated solids exhibit excellent thermal stability, attributed to the heteroepitaxial structure of nanocrystal-matrix interfaces, and show compelling light-harvesting performance in prototype solar cells.

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.

Acquisition of a High Performance Computer Cluster for Materials Research and Education

DTIC Science & Technology

2015-04-17

separation in all-organic and hybrid organic- inorganic solar cells. The outcome of the project 1. REPORT DATE (DD-MM-YYYY) 4. TITLE AND SUBTITLE 13...diffusion and interfacial charge separation in all-organic and hybrid organic- inorganic solar cells. The outcome of the project is the development...simulations to predict charge carrier mobilities, exciton diffusion and interfacial charge separation in all- organic and hybrid organic- inorganic solar

Charge separation at nanoscale interfaces: energy-level alignment including two-quasiparticle interactions.

PubMed

Li, Huashan; Lin, Zhibin; Lusk, Mark T; Wu, Zhigang

2014-10-21

The universal and fundamental criteria for charge separation at interfaces involving nanoscale materials are investigated. In addition to the single-quasiparticle excitation, all the two-quasiparticle effects including exciton binding, Coulomb stabilization, and exciton transfer are considered, which play critical roles on nanoscale interfaces for optoelectronic applications. We propose a scheme allowing adding these two-quasiparticle interactions on top of the single-quasiparticle energy level alignment for determining and illuminating charge separation at nanoscale interfaces. Employing the many-body perturbation theory based on Green's functions, we quantitatively demonstrate that neglecting or simplifying these crucial two-quasiparticle interactions using less accurate methods is likely to predict qualitatively incorrect charge separation behaviors at nanoscale interfaces where quantum confinement dominates.

Directional charge separation in isolated organic semiconductor crystalline nanowires

DOE PAGES

Labastide, J. A.; Thompson, H. B.; Marques, S. R.; ...

2016-02-25

One of the fundamental design paradigms in organic photovoltaic device engineering is based on the idea that charge separation is an extrinsically driven process requiring an interface for exciton fission. This idea has driven an enormous materials science engineering effort focused on construction of domain sizes commensurate with a nominal exciton diffusion length of order 10 nm. Here, we show that polarized optical excitation of isolated pristine crystalline nanowires of a small molecule n-type organic semiconductor, 7,8,15,16-tetraazaterrylene, generates a significant population of charge-separated polaron pairs along the π-stacking direction. Charge separation was signalled by pronounced power-law photoluminescence decay polarized alongmore » the same axis. In the transverse direction, we observed exponential decay associated with excitons localized on individual monomers. We propose that this effect derives from an intrinsic directional charge-transfer interaction that can ultimately be programmed by molecular packing geometry.« less

Means and method of detection in chemical separation procedures

DOEpatents

Yeung, Edward S.; Koutny, Lance B.; Hogan, Barry L.; Cheung, Chan K.; Ma, Yinfa

1993-03-09

A means and method for indirect detection of constituent components of a mixture separated in a chemical separation process. Fluorescing ions are distributed across the area in which separation of the mixture will occur to provide a generally uniform background fluorescence intensity. For example, the mixture is comprised of one or more charged analytes which displace fluorescing ions where its constituent components separate to. Fluorescing ions of the same charge as the charged analyte components cause a displacement. The displacement results in the location of the separated components having a reduced fluorescence intensity to the remainder of the background. Detection of the lower fluorescence intensity areas can be visually, by photographic means and methods, or by automated laser scanning.

Means and method of detection in chemical separation procedures

DOEpatents

Yeung, E.S.; Koutny, L.B.; Hogan, B.L.; Cheung, C.K.; Yinfa Ma.

1993-03-09

A means and method are described for indirect detection of constituent components of a mixture separated in a chemical separation process. Fluorescing ions are distributed across the area in which separation of the mixture will occur to provide a generally uniform background fluorescence intensity. For example, the mixture is comprised of one or more charged analytes which displace fluorescing ions where its constituent components separate to. Fluorescing ions of the same charge as the charged analyte components cause a displacement. The displacement results in the location of the separated components having a reduced fluorescence intensity to the remainder of the background. Detection of the lower fluorescence intensity areas can be visually, by photographic means and methods, or by automated laser scanning.

Electrophoretic sample insertion. [device for uniformly distributing samples in flow path

NASA Technical Reports Server (NTRS)

Mccreight, L. R. (Inventor)

1974-01-01

Two conductive screens located in the flow path of an electrophoresis sample separation apparatus are charged electrically. The sample is introduced between the screens, and the charge is sufficient to disperse and hold the samples across the screens. When the charge is terminated, the samples are uniformly distributed in the flow path. Additionally, a first separation by charged properties has been accomplished.

Mixing-Chamber Preamplifier for Spin Qubit Readout

NASA Astrophysics Data System (ADS)

Curry, Matthew; Mounce, Andrew; England, Troy; Manginell, Ronald; Wendt, Joel; Pluym, Tammy; Carr, Stephen; Carroll, Malcolm

Spin qubit states are often read out with a nearby charge sensor. To improve signal-to-noise ratio (SNR) and bandwidth, we amplify a charge sensor with a low-current-bias, silicon-germanium heterojunction-bipolar-transistor (HBT). The HBT is located at the mixing chamber of a dilution refrigerator, which minimizes parasitic capacitance and amplifies signal before fridge noise is introduced. Using the HBT-charge-sensor circuit, we tune a few-electron quantum dot (QD) into resonance with a donor-like object and observe singlet-triplet (ST) behavior. ST separation in this MOS donor-implanted-QD molecular system is measured using magnetospectroscopy to be approximately 100 μeV. The low current bias of the HBT minimizes both heating of the charge-sensed QD as well as maintains an overall low power at the mixing chamber. HBT bias impact on QD electron temperature is examined and we find that the HBT preamplifier can operate at around 100 nW with a current gain of around 500 without influencing the electron temperature, which is around 150 mK. We will also examine single-shot readout of a charge state using the HBT preamplifier. Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a Lockheed-Martin Company, for the U. S. Department of Energy under Contract No. DE-AC04-94AL85000.

Freezing, fragmentation, and charge separation in sonic sprayed water droplets

NASA Astrophysics Data System (ADS)

Zilch, Lloyd W.; Maze, Joshua T.; Smith, John W.; Jarrold, Martin F.

2009-06-01

Water droplets are generated by sonic spray, transferred into vacuum through a capillary interface, and then passed through two image charge detectors separated by a drift region. The image charge detectors measure the charge and velocity of each droplet. For around 1% of the droplets, the charge changes significantly between the detectors. In some cases it increases, in others it decreases, and for some droplets the charge changes polarity. We attribute the charge changing behavior to fragmentation caused by freezing. Simulations indicate that the time required for a droplet to cool and freeze in vacuum depends on its size, and that droplets with radii of 1-2 [mu]m have the right size to freeze between the two detectors. These sizes correspond to the smaller end of the distribution present in the experiment. When the charge on a droplet increases or changes polarity, fragmentation must be accompanied by charge separation where fragments carry away opposite charges. In some cases, two fission fragments were observed in the second charge detector. We show examples where the droplet breaks apart to give fragments of the same charge and opposite charges. The fragmentation and charge changing behavior found here is consistent with what has been found in the freezing of larger suspended and supported droplets.

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

PubMed

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

2011-03-17

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

Energy decomposition analysis for exciplexes using absolutely localized molecular orbitals

NASA Astrophysics Data System (ADS)

Ge, Qinghui; Mao, Yuezhi; Head-Gordon, Martin

2018-02-01

An energy decomposition analysis (EDA) scheme is developed for understanding the intermolecular interaction involving molecules in their excited states. The EDA utilizes absolutely localized molecular orbitals to define intermediate states and is compatible with excited state methods based on linear response theory such as configuration interaction singles and time-dependent density functional theory. The shift in excitation energy when an excited molecule interacts with the environment is decomposed into frozen, polarization, and charge transfer contributions, and the frozen term can be further separated into Pauli repulsion and electrostatics. These terms can be added to their counterparts obtained from the ground state EDA to form a decomposition of the total interaction energy. The EDA scheme is applied to study a variety of systems, including some model systems to demonstrate the correct behavior of all the proposed energy components as well as more realistic systems such as hydrogen-bonding complexes (e.g., formamide-water, pyridine/pyrimidine-water) and halide (F-, Cl-)-water clusters that involve charge-transfer-to-solvent excitations.

Synthesis and Exciton Dynamics of Donor-Orthogonal Acceptor Conjugated Polymers: Reducing the Singlet-Triplet Energy Gap.

PubMed

Freeman, David M E; Musser, Andrew J; Frost, Jarvist M; Stern, Hannah L; Forster, Alexander K; Fallon, Kealan J; Rapidis, Alexandros G; Cacialli, Franco; McCulloch, Iain; Clarke, Tracey M; Friend, Richard H; Bronstein, Hugo

2017-08-16

The presence of energetically low-lying triplet states is a hallmark of organic semiconductors. Even though they present a wealth of interesting photophysical properties, these optically dark states significantly limit optoelectronic device performance. Recent advances in emissive charge-transfer molecules have pioneered routes to reduce the energy gap between triplets and "bright" singlets, allowing thermal population exchange between them and eliminating a significant loss channel in devices. In conjugated polymers, this gap has proved resistant to modification. Here, we introduce a general approach to reduce the singlet-triplet energy gap in fully conjugated polymers, using a donor-orthogonal acceptor motif to spatially separate electron and hole wave functions. This new generation of conjugated polymers allows for a greatly reduced exchange energy, enhancing triplet formation and enabling thermally activated delayed fluorescence. We find that the mechanisms of both processes are driven by excited-state mixing between π-π*and charge-transfer states, affording new insight into reverse intersystem crossing.

Device and method for separating minerals, carbon and cement additives from fly ash

DOEpatents

Link, Thomas A.; Schoffstall, Micael R.; Soong, Yee

2004-01-27

A process for separating organic and inorganic particles from a dry mixture by sizing the particles into isolated fractions, contacting the sized particles to a charged substrate and subjecting the charged particles to an electric field to separate the particles.

Tribo-charging properties of waste plastic granules in process of tribo-electrostatic separation

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

Li, Jia, E-mail: weee@sjtu.edu.cn; Wu, Guiqing; Xu, Zhenming

Highlights: • The cyclone charging was more effective and stable than vibrating charging. • The small particle size was better changed than large ones and was more suitable recycled by TES. • The drying pretreatment is good for improving the short-term charging effect. - Abstract: Plastic products can be found everywhere in people’s daily life. With the consistent growth of plastic consumption, more and more plastic waste is generated. Considering the stable chemical and physics characteristics of plastic, regular waste management methods are not suitable for recycling economic strategy of each government, which has become a serious environmental problem. Recyclingmore » plastic waste is considered to be the best way to treat it, because it cannot only deduce the waste but also save the energy to produce new virgin plastic. Tribo-electrostatic separation is strongly recommended for plastic separation as it can preserve the original properties of plastic and has little additional pollution. In this study, plastic granules are generated by crushing plastic waste in waste electric and electronic equipment. The tribo-charging properties of plastic waste were studied by vibrating tribo-charging and cyclone tribo-charging. The triboelectric series obtained by vibrating was: (−)-PE–PS–PC–PVC–ABS–PP-(+), while the triboelectric series obtained by cyclone was (−)-PE–PS–PC–PVC–ABS–PP-(+). Further, the cyclone charging was more effective and stable than vibrating charging. The impact factors experiments showed that small particle size was better changed than large ones and were more suitable recycled by tribo-electrostatic separation. High relative humidity was identified as impede charging effect. The results of this study will help defining the operating parameters of subsequent separator.« less

High-Field Asymmetric-Waveform Ion Mobility Spectrometry and Electron Detachment Dissociation of Isobaric Mixtures of Glycosaminoglycans

NASA Astrophysics Data System (ADS)

Kailemia, Muchena J.; Park, Melvin; Kaplan, Desmond A.; Venot, Andre; Boons, Geert-Jan; Li, Lingyun; Linhardt, Robert J.; Amster, I. Jonathan

2014-02-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is shown to be capable of resolving isomeric and isobaric glycosaminoglycan negative ions and to have great utility for the analysis of this class of molecules when combined with Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and tandem mass spectrometry. Electron detachment dissociation (EDD) and other ion activation methods for tandem mass spectrometry can be used to determine the sites of labile sulfate modifications and for assigning the stereochemistry of hexuronic acid residues of glycosaminoglycans (GAGs). However, mixtures with overlapping mass-to-charge values present a challenge, as their precursor species cannot be resolved by a mass analyzer prior to ion activation. FAIMS is shown to resolve two types of mass-to-charge overlaps. A mixture of chondroitin sulfate A (CSA) oligomers with 4-10 saccharides units produces ions of a single mass-to-charge by electrospray ionization, as the charge state increases in direct proportion to the degree of polymerization for these sulfated carbohydrates. FAIMS is shown to resolve the overlapping charge. A more challenging type of mass-to-charge overlap occurs for mixtures of diastereomers. FAIMS is shown to separate two sets of epimeric GAG tetramers. For the epimer pairs, the complexity of the separation is reduced when the reducing end is alkylated, suggesting that anomers are also resolved by FAIMS. The resolved components were activated by EDD and the fragment ions were analyzed by FTICR-MS. The resulting tandem mass spectra were able to distinguish the two epimers from each other.

Self-assembled via axial coordination magnesium porphyrin-imidazole appended fullerene dyad: spectroscopic, electrochemical, computational, and photochemical studies.

PubMed

D'Souza, Francis; El-Khouly, Mohamed E; Gadde, Suresh; McCarty, Amy L; Karr, Paul A; Zandler, Melvin E; Araki, Yasuyaki; Ito, Osamu

2005-05-26

Spectroscopic, redox, and electron transfer reactions of a self-assembled donor-acceptor dyad formed by axial coordination of magnesium meso-tetraphenylporphyrin (MgTPP) and fulleropyrrolidine appended with an imidazole coordinating ligand (C(60)Im) were investigated. Spectroscopic studies revealed the formation of a 1:1 C(60)Im:MgTPP supramolecular complex, and the anticipated 1:2 complex could not be observed because of the needed large amounts of the axial coordinating ligand. The formation constant, K(1), for the 1:1 complex was found to be (1.5 +/- 0.3) x 10(4) M(-1), suggesting fairly stable complex formation. The geometric and electronic structures of the dyads were probed by ab initio B3LYP/3-21G() methods. The majority of the highest occupied frontier molecular orbital (HOMO) was found to be located on the MgTPP entity, while the lowest unoccupied molecular orbital (LUMO) was on the fullerene entity, suggesting that the charge-separated state of the supramolecular complex is C(60)Im(*-):MgTPP(*+). Redox titrations involving MgTPP and C(60)Im allowed accurate determination of the oxidation and reduction potentials of the donor and acceptor entities in the supramolecular complex. These studies revealed more difficult oxidation, by about 100 mV, for MgTPP in the pentacoordinated C(60)Im:MgTPP compared to pristine MgTPP in o-dichlorobenzene. A total of six one-electron redox processes corresponding to the oxidation and reduction of the zinc porphyrin ring and the reduction of fullerene entities was observed within the accessible potential window of the solvent. The excited state events were monitored by both steady state and time-resolved emission as well as transient absorption techniques. In o-dichlorobenzene, upon coordination of C(60)Im to MgTPP, the main quenching pathway involved electron transfer from the singlet excited MgTPP to the C(60)Im moiety. The rate of forward electron transfer, k(CS), calculated from the picosecond time-resolved emission studies was found to be 1.1 x 10(10) s(-1) with a quantum yield, Phi(CS), of 0.99, indicating fast and efficient charge separation. The rate of charge recombination, k(CR), evaluated from nanosecond transient absorption studies, was found to be 8.3 x 10(7) s(-1). A comparison between k(CS) and k(CR) suggested an excellent opportunity to utilize the charge-separated state for further electron-mediating processes.

Charge Carrier Dynamics and pH Effect on Optical Properties of Anionic and Cationic Porphyrin-Graphene Oxide Composites

NASA Astrophysics Data System (ADS)

Bajjou, O.; Bakour, A.; Khenfouch, M.; Baitoul, M.; Mothudi, B.; Maaza, M.; Faulques, E.

2018-02-01

Composites of graphene oxide (GO) functionalized with Sn(V) tetrakis (4-pyridyl)porphyrin (SnTPyP2+) and meso-tetrakis(4-phenylsulfonic acid)porphyrin (H4TPPS4 2- ) were prepared at different pH values.Successful synthesis of water-soluble stable suspension of GO-SnTPyP2+ and GO-H4TPPS4 2-was confirmed using various spectroscopic techniques, including scanning electronic microscopy (SEM), Raman spectroscopy, and ultraviolet-visible (UV-Vis) absorption. Variation of the pH was found to strongly influence the optical properties of the GO-SnTPyP2+ and GO-H4TPPS4 2-composites, as demonstrated by the UV-Vis absorption results. Steady-state photoluminescence (PL) and time-resolved PL (TRPL) results for both composites showed PL quenching and decrease in the exciton mean lifetime, suggesting strong excited-state interactions between the different components. Moreover, charge carrier dynamics study revealed that insertion of GO into both porphyrin derivatives led to faster mean lifetime for excitons with a slight advantage in the case of the cationic porphyrin-GO composite, making it a better choice for charge separation applications thanks to the higher efficiency of charge/energy transfer interactions.

Correlated scattering states of N-body Coulomb systems

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

Berakdar, J.

1997-03-01

For N charged particles of equal masses moving in the field of a heavy residual charge, an approximate analytical solution of the many-body time-independent Schr{umlt o}dinger equation is derived at a total energy above the complete fragmentation threshold. All continuum particles are treated on equal footing. The proposed correlated wave function represents, to leading order, an exact solution of the many-body Schr{umlt o}dinger equation in the asymptotic region defined by large interparticle separations. Thus, in this asymptotic region the N-body Coulomb modifications to the plane-wave motion of free particles are rigorously estimated. It is shown that the Kato cusp conditionsmore » are satisfied by the derived wave function at all two-body coalescence points. An expression of the normalization of this wave function is also given. To render possible the calculations of scattering amplitudes for transitions leading to a four-body scattering state, an effective-charge method is suggested in which the correlations between the continuum particles are completely subsumed into effective interactions with the residual charge. Analytical expressions for these effective interactions are derived and discussed for physical situations. {copyright} {ital 1997} {ital The American Physical Society}« less

THE CONTRIBUTIONS OF NORMAL AND ANOMALOUS OSMOSIS TO THE OSMOTIC EFFECTS ARISING ACROSS CHARGED MEMBRANES WITH SOLUTIONS OF ELECTROLYTES

PubMed Central

Grim, Eugene; Sollner, Karl

1957-01-01

The osmotic effect arising across a porous membrane separating the solution of an electrolyte from water (or a more dilute solution) is ordinarily due to both normal osmosis, as it occurs also with non-electrolytes, and to "anomalous" osmosis. It is shown that the normal osmotic component cannot be measured quantitatively by the conventional comparison with a non-electrolytic reference solute. Anomalous osmosis does not occur with electroneutral membranes. Accordingly, with membranes which can be charged and discharged reversibly (without changes in geometrical structure), such as many proteinized membranes, the osmotic effects caused by an electrolyte can be measured both when only normal osmosis arises (with the membrane in the electroneutral state) and when normal as well as anomalous osmosis occurs (with the membrane in a charged state). The difference between these two effects is the true anomalous osmosis. Data are presented on the osmotic effects across an oxyhemoglobin membrane in the uncharged state at pH 6.75 and in two charged states, positive at pH 4.0 and negative at pH 10.0, with solutions of a variety of electrolytes using a concentration ratio of 2:1 over a wide range of concentrations. The rates of the movement of liquid across the membrane against an inconsequentially small hydrostatic head are recorded instead of, as conventional, the physiologically less significant pressure rises after a standard time. PMID:13439166

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

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

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

Long-Lived Charge Separation at Heterojunctions between Semiconducting Single-Walled Carbon Nanotubes and Perylene Diimide Electron Acceptors

DOE PAGES

Kang, Hyun Suk; Sisto, Thomas J.; Peurifoy, Samuel; ...

2018-04-13

Nonfullerene electron acceptors have facilitated a recent surge in the efficiencies of organic solar cells, although fundamental studies of the nature of exciton dissociation at interfaces with nonfullerene electron acceptors are still relatively sparse. Semiconducting single-walled carbon nanotubes (s-SWCNTs), unique one-dimensional electron donors with molecule-like absorption and highly mobile charges, provide a model system for studying interfacial exciton dissociation. Here, we investigate excited-state photodynamics at the heterojunction between (6,5) s-SWCNTs and two perylene diimide (PDI)-based electron acceptors. Each of the PDI-based acceptors, hPDI2-pyr-hPDI2 and Trip-hPDI2, is deposited onto (6,5) s-SWCNT films to form a heterojunction bilayer. Transient absorption measurements demonstratemore » that photoinduced hole/electron transfer occurs at the photoexcited bilayer interfaces, producing long-lived separated charges with lifetimes exceeding 1.0 us. Both exciton dissociation and charge recombination occur more slowly for the hPDI2-pyr-hPDI2 bilayer than for the Trip-hPDI2 bilayer. To explain such differences, we discuss the potential roles of the thermodynamic charge transfer driving force available at each interface and the different molecular structure and intermolecular interactions of PDI-based acceptors. As a result, detailed photophysical analysis of these model systems can develop the fundamental understanding of exciton dissociation between organic electron donors and nonfullerene acceptors, which has not been systematically studied.« less

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

High precision computing with charge domain devices and a pseudo-spectral method therefor

NASA Technical Reports Server (NTRS)

Barhen, Jacob (Inventor); Toomarian, Nikzad (Inventor); Fijany, Amir (Inventor); Zak, Michail (Inventor)

1997-01-01

The present invention enhances the bit resolution of a CCD/CID MVM processor by storing each bit of each matrix element as a separate CCD charge packet. The bits of each input vector are separately multiplied by each bit of each matrix element in massive parallelism and the resulting products are combined appropriately to synthesize the correct product. In another aspect of the invention, such arrays are employed in a pseudo-spectral method of the invention, in which partial differential equations are solved by expressing each derivative analytically as matrices, and the state function is updated at each computation cycle by multiplying it by the matrices. The matrices are treated as synaptic arrays of a neural network and the state function vector elements are treated as neurons. In a further aspect of the invention, moving target detection is performed by driving the soliton equation with a vector of detector outputs. The neural architecture consists of two synaptic arrays corresponding to the two differential terms of the soliton-equation and an adder connected to the output thereof and to the output of the detector array to drive the soliton equation.

Motion-based, high-yielding, and fast separation of different charged organics in water.

PubMed

Xuan, Mingjun; Lin, Xiankun; Shao, Jingxin; Dai, Luru; He, Qiang

2015-01-12

We report a self-propelled Janus silica micromotor as a motion-based analytical method for achieving fast target separation of polyelectrolyte microcapsules, enriching different charged organics with low molecular weights in water. The self-propelled Janus silica micromotor catalytically decomposes a hydrogen peroxide fuel and moves along the direction of the catalyst face at a speed of 126.3 μm s(-1) . Biotin-functionalized Janus micromotors can specifically capture and rapidly transport streptavidin-modified polyelectrolyte multilayer capsules, which could effectively enrich and separate different charged organics in water. The interior of the polyelectrolyte multilayer microcapsules were filled with a strong charged polyelectrolyte, and thus a Donnan equilibrium is favorable between the inner solution within the capsules and the bulk solution to entrap oppositely charged organics in water. The integration of these self-propelled Janus silica micromotors and polyelectrolyte multilayer capsules into a lab-on-chip device that enables the separation and analysis of charged organics could be attractive for a diverse range of applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Promoting Charge Separation and Injection by Optimizing the Interfaces of GaN:ZnO Photoanode for Efficient Solar Water Oxidation.

PubMed

Wang, Zhiliang; Zong, Xu; Gao, Yuying; Han, Jingfeng; Xu, Zhiqiang; Li, Zheng; Ding, Chunmei; Wang, Shengyang; Li, Can

2017-09-13

Photoelectrochemical water splitting provides an attractive way to store solar energy in molecular hydrogen as a kind of sustainable fuel. To achieve high solar conversion efficiency, the most stringent criteria are effective charge separation and injection in electrodes. Herein, efficient photoelectrochemical water oxidation is realized by optimizing charge separation and surface charge transfer of GaN:ZnO photoanode. The charge separation can be greatly improved through modified moisture-assisted nitridation and HCl acid treatment, by which the interfaces in GaN:ZnO solid solution particles are optimized and recombination centers existing at the interfaces are depressed in GaN:ZnO photoanode. Moreover, a multimetal phosphide of NiCoFeP was employed as water oxidation cocatalyst to improve the charge injection at the photoanode/electrolyte interface. Consequently, it significantly decreases the overpotential and brings the photocurrent to a benchmark of 3.9 mA cm -2 at 1.23 V vs RHE and a solar conversion efficiency over 1% was obtained.

Isovector charges of the nucleon from 2 + 1 -flavor QCD with clover fermions

DOE PAGES

Yoon, Boram; Jang, Yong -Chull; Gupta, Rajan; ...

2017-04-13

We present high-statistics estimates of the isovector charges of the nucleon from four 2+1-flavor ensembles generated using Wilson-clover fermions with stout smearing and tree-level tadpole improved Symanzik gauge action at lattice spacingsmore » $a=0.114$ and $0.080$ fm and with $$M_\\pi \\approx 315$$ and 200 MeV. The truncated solver method with bias correction and the coherent source sequential propagator construction are used to cost-effectively achieve $O(10^5)$ measurements on each ensemble. Using these data, the analysis of two-point correlation functions is extended to include four states in the fits and of three-point functions to three states. Control over excited-state contamination in the calculation of the nucleon mass, the mass gaps between excited states, and in the matrix elements is demonstrated by the consistency of estimates using this multistate analysis of the spectral decomposition of the correlation functions and from simulations of the three-point functions at multiple values of the source-sink separation. Lastly, the results for all three charges, $$g_A$$, $$g_S$$ and $$g_T$$, are in good agreement with calculations done using the clover-on-HISQ lattice formulation with similar values of the lattice parameters.« less

Electron in higher-dimensional weakly charged rotating black hole spacetimes

NASA Astrophysics Data System (ADS)

Cariglia, Marco; Frolov, Valeri P.; Krtouš, Pavel; Kubizňák, David

2013-03-01

We demonstrate separability of the Dirac equation in weakly charged rotating black hole spacetimes in all dimensions. The electromagnetic field of the black hole is described by a test field approximation, with the vector potential proportional to the primary Killing vector field. It is shown that the demonstrated separability can be intrinsically characterized by the existence of a complete set of mutually commuting first-order symmetry operators generated from the principal Killing-Yano tensor. The presented results generalize the results on integrability of charged particle motion and separability of charged scalar field studied in V. P. Frolov and P. Krtous [Phys. Rev. D 83, 024016 (2011)].

Oligothiophene/graphene supramolecular ensembles managing light induced processes: preparation, characterization, and femtosecond transient absorption studies leading to charge-separation

NASA Astrophysics Data System (ADS)

Stergiou, A.; Gobeze, H. B.; Petsalakis, I. D.; Zhao, S.; Shinohara, H.; D'Souza, F.; Tagmatarchis, N.

2015-09-01

Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles.Advances in organic synthetic chemistry combined with the exceptional electronic properties of carbon allotropes, particularly graphene, is the basis used to design and fabricate novel electron donor-acceptor ensembles with desired properties for technological applications. Thiophene-based materials, which are mainly thiophene-containing polymers, are known for their notable electronic properties. In this frame moving from polymer to oligomer forms, new fundamental information would help for a better understanding of their electrochemical and photophysical properties. Furthermore, a successful combination of their electronic properties with those of graphene is a challenging goal. In this study, two oligothiophene compounds, which consist of three and nine thiophene-rings and are abbreviated 3T and 9T, respectively, were synthesized and noncovalently associated with liquid phase exfoliated few-layered graphene sheets (abbreviated eG), thus forming donor-acceptor 3T/eG and 9T/eG nanoensembes. Markedly, intra-ensemble electronic interactions between the two components in the ground and excited states were evaluated with the aid of UV-Vis and photoluminescence spectroscopy. Furthermore, redox assays revealed the one-electron oxidation of 3T accompanied by one-electron reduction due to eG in 3T/eG, whereas there were two reversible one-electron oxidations of 9T accompanied by one-electron reduction of eG9T/eG. The electrochemical band gap for the 3T/eG and 9T/eG ensembles were calculated and verified, in which the negative free-energy change for the charge-separated state of 3T/eG and 9T/eGvia the singlet excited state of 3T and 9T, respectively, were thermodynamically favorable. Finally, the results of transient pump-probe spectroscopy studies at the femtosecond time scale were supportive of charge transfer type interactions in the 3T/eG and 9T/eG ensembles. The estimated rates for intra-ensemble charge separation were found to be 9.52 × 109 s-1 and 2.2 × 1011 s-1, respectively, for 3T/eG and 9T/eG in THF, which reveal moderate to ultrafast photoinduced events in the oligothiophene/graphene supramolecular ensembles. Electronic supplementary information (ESI) available: NMR, MS, ATR-IR, UV-Vis spectra, CV graphs, femto- and nano-second transient absorption spectra of oligothiophenes and their ensembles with exfoliated graphene. See DOI: 10.1039/c5nr04875c

Method and apparatus for measuring the state of charge in a battery based on volume of battery components

DOEpatents

Rouhani, S. Zia

1996-10-22

The state of charge of electrochemical batteries of different kinds is determined by measuring the incremental change in the total volume of the reactive masses in the battery. The invention is based on the principle that all electrochemical batteries, either primary or secondary (rechargeable), produce electricity through a chemical reaction with at least one electrode, and the chemical reactions produce certain changes in the composition and density of the electrode. The reactive masses of the electrodes, the electrolyte, and any separator or spacers are usually contained inside a battery casing of a certain volume. As the battery is used, or recharged, the specific volume of at least one of the electrode masses will change and, since the masses of the materials do not change considerably, the total volume occupied by at least one of the electrodes will change. These volume changes may be measured in many different ways and related to the state of charge in the battery. In one embodiment, the volume change can be measured by monitoring the small changes in one of the principal dimensions of the battery casing as it expands or shrinks to accommodate the combined volumes of its components.

Structural insight of the charge-ordering phenomena in manganites

NASA Astrophysics Data System (ADS)

Garcia, Joaquin

2005-03-01

Recent experiments using x-ray absorption spectroscopy (XAS) and x-ray resonant scattering (XRS) techniques show that the conventional description of the so-called charge ordering phases of manganites in terms of Mn^3+/Mn^4+ ionic ordering is far from reality. I present here the XRS study of the low temperature phase of Nd0.5Sr0.5MnO3 manganite. Strong resonances are observed in the energy dependent spectra of (300), (030) and (05/20) reflections. Their azimuthal and polarization dependencies are well explained by the anisotropy of the local geometrical structure. Two different Mn sites were found. One of them is surrounded by a tetragonal distorted oxygen octahedron, whereas the other site has a nearly regular octahedral environment. The charge separation between the intermediate valence states is less than 0.2 e-. The analysis performed resolves some of the apparent contradictions with previous XRS and XAS experiments in manganites. These results joined to those recently obtained on the Verwey transition in magnetite indicate that the electronic states in transition-metal oxides need to be described in terms of band states instead of localized ones. Colaborators: G. Sub'ias, J. Blasco, M. G. Proietti, M. S'anchez and J. Herrero-Martin

Efficient Yttrium(III) Chloride-Treated TiO2 Electron Transfer Layers for Performance-Improved and Hysteresis-Less Perovskite Solar Cells.

PubMed

Li, Minghua; Huan, Yahuan; Yan, Xiaoqin; Kang, Zhuo; Guo, Yan; Li, Yong; Liao, Xinqin; Zhang, Ruxiao; Zhang, Yue

2018-01-10

Hybrid organic-inorganic metal halide perovskite solar cells have attracted widespread attention, owing to their high performance, and have undergone rapid development. In perovskite solar cells, the charge transfer layer plays an important role for separating and transferring photogenerated carriers. In this work, an efficient YCl 3 -treated TiO 2 electron transfer layer (ETL) is used to fabricate perovskite solar cells with enhanced photovoltaic performance and less hysteresis. The YCl 3 -treated TiO 2 layers bring about an upward shift of the conduction band minimum (E CBM ), which results in a better energy level alignment for photogenerated electron transfer and extraction from the perovskite into the TiO 2 layer. After optimization, perovskite solar cells based on the YCl 3 -treated TiO 2 layers achieve a maximum power conversion efficiency of about 19.99 % (19.29 % at forward scan) and a steady-state power output of about 19.6 %. Steady-state and time-resolved photoluminescence measurements and impedance spectroscopy are carried out to investigate the charge transfer and recombination dynamics between the perovskite and the TiO 2 electron transfer layer interface. The improved perovskite/TiO 2 ETL interface with YCl 3 treatment is found to separate and extract photogenerated charge rapidly and suppress recombination effectively, which leads to the improved performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substituent effects on photosensitized splitting of thymine cyclobutane dimer by an attached indole.

PubMed

Tang, Wenjian; Zhou, Hongmei; Wang, Jing; Pan, Chunxiao; Shi, Jingbo; Song, Qinhua

2012-12-21

In chromophore-containing cyclobutane pyrimidine dimer (CPD) model systems, solvent effects on the splitting efficiency may depend on the length of the linker, the molecular conformation, and the oxidation potential of the donor. To further explore the relationship between chromophore structure and splitting efficiency, we prepared a series of substituted indole-T< >T model compounds 2 a-2 g and measured their splitting quantum yields in various solvents. Two reverse solvent effects were observed: an increase in splitting efficiency in solvents of lower polarity for models 2 a-2 d with an electron-donating group (EDG), and vice versa for models 2 e-2 g with an electron-withdrawing group (EWG). According to the Hammett equation, the negative value of the slope of the Hammett plot indicates that the indole moiety during the T< >T-splitting reaction loses negative charge, and the larger negative value implies that the repair reaction is more sensitive to substituent effects in low-polarity solvents. The EDGs of the models 2 a-2 d can delocalize the charge-separated state, and low-polarity solvents make it more stable, which leads to higher splitting efficiency in low-polarity solvents. Conversely, the EWGs of models 2 e-2 g favor destabilization of the charge-separated state, and high-polarity solvents decrease the destabilization and hence lead to more efficient splitting in high-polarity solvents. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ewald Electrostatics for Mixtures of Point and Continuous Line Charges.

PubMed

Antila, Hanne S; Tassel, Paul R Van; Sammalkorpi, Maria

2015-10-15

Many charged macro- or supramolecular systems, such as DNA, are approximately rod-shaped and, to the lowest order, may be treated as continuous line charges. However, the standard method used to calculate electrostatics in molecular simulation, the Ewald summation, is designed to treat systems of point charges. We extend the Ewald concept to a hybrid system containing both point charges and continuous line charges. We find the calculated force between a point charge and (i) a continuous line charge and (ii) a discrete line charge consisting of uniformly spaced point charges to be numerically equivalent when the separation greatly exceeds the discretization length. At shorter separations, discretization induces deviations in the force and energy, and point charge-point charge correlation effects. Because significant computational savings are also possible, the continuous line charge Ewald method presented here offers the possibility of accurate and efficient electrostatic calculations.

Charge state breeding experiences and plans at TRIUMF

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

Ames, F., E-mail: ames@triumf.ca; Marchetto, M.; Mjøs, A.

At the Isotope Separation and ACceleration (ISAC) facility at TRIUMF, an electron cyclotron resonance ion source (ECRIS) has been set up for the charge state breeding of radioactive ions. In order to reduce background from stable ions generated in the ECRIS, several measures, including changing materials for the plasma chamber and the surrounding components, have been implemented. Further reduction has been achieved by using the post-accelerator chain as a mass filter. Since the implementation of those measures in 2013, physics experiments with accelerated radioactive isotopes of Rb, Sr, K, and Mg have been performed. In most cases, a charge breedingmore » efficiency of several percent has been achieved. With the planned expansion of the isotope production capabilities at TRIUMF within the Advanced Rare IsotopE Laboratory project, two new target stations, one using photo-fission induced by a high-power electron beam at 50 MeV and the other one using 480 MeV protons as at ISAC, will be put into operation within the next 5 yr. Additionally, a new electron beam ion source (EBIS) based charge state breeding system will be installed. Background from such a source is expected to be much lower. The drawback is that for the efficient operation of such a system, pulsed beam operation is required, which makes the installation of an additional ion buncher in front of the EBIS necessary.« less

Design principle for efficient charge separation at the donor-acceptor interface for high performance organic solar cell device

NASA Astrophysics Data System (ADS)

Nie, Wanyi; Gupta, Gautam; Crone, Brian; Wang, Hsing-Lin; Mohite, Aditya; MPA-11 Material synthesis and integrated device Team; MPA-chemistry Team

2014-03-01

The performance of donor (D) /acceptor (A) structure based organic electronic devices, such as solar cell, light emitting devices etc., relays on the charge transfer process at the interface dramatically. In organic solar cell, the photo-induced electron-hole pair is tightly bonded and will form a charge transfer (CT) state at the D/A interface after dissociation. There is a large chance for them to recombine through CT state and thus is a major loss that limit the overall performance. Here, we report three different strategies that allow us to completely suppress the exciplex (or charge transfer state) recombination between any D/A system. We observe that the photocurrent increases by 300% and the power conversion efficiency increases by 4-5 times simply by inserting a spacer layer in the form of an a) insulator b) Oliogomer or using a c) heavy atom at the donor-acceptor interface in a P3HT/C60 bilayer device. By using those different functional mono layers, we successfully suppressed the exciplex recombination in evidence of increased photocurrent and open circuit voltage. Moreover, these strategies are applicable universally to any donor-acceptor interface. And we demonstrated such strategies in a bulk-heterojunction device which improved the power conversion efficiency from 3.5% up to 4.6%.

Design of a CW high charge state heavy ion RFQ for SSC-LINAC

NASA Astrophysics Data System (ADS)

Liu, G.; Lu, Y. R.; He, Y.; Wang, Z.; Xiao, C.; Gao, S. L.; Yang, Y. Q.; Zhu, K.; Yan, X. Q.; Chen, J. E.; Yuan, Y. J.; Zhao, H. W.

2013-02-01

The new linac injector SSC-LINAC has been proposed to replace the existing Separator Sector Cyclotron (SSC). This effort is to improve the beam efficiency of the Heavy Ion Research Facility of Lanzhou (HIRFL). As a key component of the linac, a continuous-wave (CW) mode high charge state heavy ion radio-frequency quadrupole (RFQ) accelerator has been designed. It accelerates ions with the ratio of mass to charge up to 7 from 3.728 keV/u to 143 keV/u. The requirements of CW mode operation and the transportation of intense beam have been considered as the greatest challenges. The design is based on 238U34+ beams, whose current is 0.5 pmA (0.5 particle mili-ampere, which is the measured 17 emA electric current divided by charge state of heavy ions). It achieves the transmission efficiency of 94% with 2508.46 mm long vanes in simulation. To improve the transmission efficiency and quality of the beams, the phase advance has been taken into account to analyze the reasons of beam loss and emittance growth. Parametric resonance and beam mismatch have been carefully avoided by adjusting the structure parameters. The parameter-sensitivity of the design is checked by transportation simulations of various input beams. To verify the applicability of machining, the effects of different vane manufacturing methods on beam dynamics are presented in this paper.

Dissecting the dynamic conformations of the metamorphic protein lymphotactin.

PubMed

Harvey, Sophie R; Porrini, Massimiliano; Konijnenberg, Albert; Clarke, David J; Tyler, Robert C; Langridge-Smith, Patrick R R; MacPhee, Cait E; Volkman, Brian F; Barran, Perdita E

2014-10-30

A mass spectrometer provides an ideal laboratory to probe the structure and stability of isolated protein ions. Interrogation of each discrete mass/charge-separated species enables the determination of the intrinsic stability of a protein fold, gaining snapshots of unfolding pathways. In solution, the metamorphic protein lymphotactin (Ltn) exists in equilibrium between two distinct conformations, a monomeric (Ltn10) and a dimeric (Ltn40) fold. Here, we use electron capture dissociation (ECD) and drift tube ion mobility-mass spectrometry (DT IM-MS) to analyze both forms and use molecular dynamics (MD) to consider how the solution fold alters in a solvent-free environment. DT IM-MS reveals significant conformational flexibility for the monomer, while the dimer appears more conformationally restricted. These findings are supported by MD calculations, which reveal how salt bridges stabilize the conformers in vacuo. Following ECD experiments, a distinctive fragmentation pattern is obtained for both the monomer and dimer. Monomer fragmentation becomes more pronounced with increasing charge state especially in the disordered regions and C-terminal α-helix in the solution fold. Lower levels of fragmentation are seen in the β-sheet regions and in regions that contain salt bridges, identified by MD simulations. The lowest charge state of the dimer for which we obtain ECD data ([D+9H](9+)) exhibits extensive fragmentation with no relationship to the solution fold and has a smaller collision cross section (CCS) than charge states 10-13+, suggesting a "collapsed" encounter complex. Other charge states of the dimer, as for the monomer, are resistant to fragmentation in regions of β-sheets in the solution fold. This study provides evidence for preservation and loss of global fold and secondary structural elements, providing a tantalizing glimpse into the power of the emerging field of native top-down mass spectrometry.

Macroscopic electric charge separation during hypervelocity impacts: Potential implications for planetary paleomagnetism

NASA Technical Reports Server (NTRS)

Crawford, D. A.; Schultz, P. H.

1993-01-01

The production of transient magnetic fields by hypervelocity meteoroid impact has been proposed to possibly explain the presence of paleomagnetic fields in certain lunar samples as well as across broader areas of the lunar surface. In an effort to understand the lunar magnetic record, continued experiments at the NASA Ames Vertical Gun Range allow characterizing magnetic fields produced by the 5 km/s impacts of 0.32-0.64 cm projectiles over a broad range of impact angles and projectile/target compositions. From such studies, another phenomenon has emerged, macroscopic electric charge separation, that may have importance for the magnetic state of solid-body surfaces. This phenomenon was observed during explosive cratering experiments, but the magnetic consequences of macroscopic electric charge separation (as opposed to plasma production) during explosion and impact cratering have not, to our knowledge, been explored before now. It is straightforward to show that magnetic field production due to this process may scale as a weakly increasing function of impactor kinetic energy, although more work is needed to precisely assess the scaling dependence. The original intent of our experiments was to assess the character of purely electrostatic signals for comparison with inferred electrostatic noise signals acquired by shielded magnetic sensors buried within particulate dolomite targets. The results demonstrated that electrostatic noise does affect the magnetic sensors but only at relatively short distances (less than 4 cm) from the impact point (our magnetic studies are generally performed at distances greater than approximately 5.5 cm). However, to assess models for magnetic field generation during impact, measurements are needed of the magnetic field as close to the impact point as possible; hence, work with an improved magnetic sensor design is in progress. In this paper, we focus on electric charge separation during hypervelocity impacts as a potential transient magnetic field production mechanism in its own right.

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 vibrational movement are coupled in a donor-bridge-acceptor complex based on a Pt(II) trans-acetylide design motif. Time-resolved IR (TRIR) spectroscopy reveals that the rate of electron transfer (ET) is highly dependent on the amount of excess energy localized on the bridge following electronic excitation. Using an adaptation of T-2DIR, we are able to selectively perturb bridge-localized vibrational modes during charge separation, resulting in the donor-acceptor charge separation pathway being completely switched off, with all excess energy redirected toward the formation of a long-lived intraligand triplet state. A series of control experiments reveal that this effect is mode specific: it is only when the high-frequency bridging C≡C stretching mode is pumped that radical changes in photoproduct yields are observed. These experiments therefore suggest that one may perturb electronic movement by stimulating structural motion along the reaction coordinate using IR light. These studies add to a growing body of evidence suggesting that controlling the pathways and efficiency of charge transfer may be achieved through synthetic and perturbative approaches aiming to modulate vibronic coupling. Achieving such control would represent a breakthrough for charge transfer-based applications such as solar energy conversion and molecular electronics.

The physics of charge separation preceding lightning strokes in thunderclouds

NASA Technical Reports Server (NTRS)

Kyrala, Ali

1987-01-01

The physics of charge separation preceding lightning strokes in thunderclouds is presented by three types of arguments: An explanation is given for the aggregation of electrical charges of like sign overcoming Coulomb repulsion by attraction due to exchange interaction. The latter is well known in quantum mechanics from the theories of the nuclear bond and the covalent bond. A classical electrostatic model of charge balls of segregated positive and negative charges in the thundercloud is presented. These charge balls can only be maintained in temporarily stable locations by a containing vortex. Because they will be of different sizes and masses, they will stabilize at different altitudes when drag forces are included with the given electrostatic force. The question of how the charges become concentrated again after lightning discharges is approached by means of the collisional Boltzmann transport equation to explain quasi-periodic recharging. It is shown that solutions cannot be separable in both position and time if they are to represent aggregation.

Directional Charge Separation in Isolated Organic Semiconductor Crystalline Nanowires

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

Barnes, Michael; Labastide, Joelle; Bond-Thompson, Hilary

2017-03-01

In the conventional view of organic photovoltaics (OPV), localized electronic excitations (excitons) formed in the active layer are transported by random 3D diffusion to an interface where charge separation and extraction take place. Because radiative de-excitation is usually strongly allowed in organic semiconductors, efficient charge separation requires high exciton mobility, with much of the diffusive motion ‘wasted’ in directions that don’t result in an interface encounter. Our research efforts are focused on ways to enforce a preferred directionality in energy and/or charge transport using ordered crystalline nanowires in which the intermolecular interactions that facilitate transport along, for example, the pi-stackingmore » axis, can be made several orders of magnitude stronger than those in a transverse direction. The results presented in our recent work (Nature Communications) is a first step towards realizing the goal of directional control of both energy transport and charge separation, where excitons shared between adjacent molecules dissociate exclusively along the pi-stacking direction.« less

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

NASA Astrophysics Data System (ADS)

Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

2016-11-01

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow.

Charge-specific size-dependent separation of water-soluble organic molecules by fluorinated nanoporous networks

PubMed Central

Byun, Jeehye; Patel, Hasmukh A.; Thirion, Damien; Yavuz, Cafer T.

2016-01-01

Molecular architecture in nanoscale spaces can lead to selective chemical interactions and separation of species with similar sizes and functionality. Substrate specific sorbent chemistry is well known through highly crystalline ordered structures such as zeolites, metal organic frameworks and widely available nanoporous carbons. Size and charge-dependent separation of aqueous molecular contaminants, on the contrary, have not been adequately developed. Here we report a charge-specific size-dependent separation of water-soluble molecules through an ultra-microporous polymeric network that features fluorines as the predominant surface functional groups. Treatment of similarly sized organic molecules with and without charges shows that fluorine interacts with charges favourably. Control experiments using similarly constructed frameworks with or without fluorines verify the fluorine-cation interactions. Lack of a σ-hole for fluorine atoms is suggested to be responsible for this distinct property, and future applications of this discovery, such as desalination and mixed matrix membranes, may be expected to follow. PMID:27830697

The impact of long-range electron-hole interaction on the charge separation yield of molecular photocells

NASA Astrophysics Data System (ADS)

Nemati Aram, Tahereh; Ernzerhof, Matthias; Asgari, Asghar; Mayou, Didier

2017-01-01

We discuss the effects of charge carrier interaction and recombination on the operation of molecular photocells. Molecular photocells are devices where the energy conversion process takes place in a single molecular donor-acceptor complex attached to electrodes. Our investigation is based on the quantum scattering theory, in particular on the Lippmann-Schwinger equation; this minimizes the complexity of the problem while providing useful and non-trivial insight into the mechanism governing photocell operation. In this study, both exciton pair creation and dissociation are treated in the energy domain, and therefore there is access to detailed spectral information, which can be used as a framework to interpret the charge separation yield. We demonstrate that the charge carrier separation is a complex process that is affected by different parameters, such as the strength of the electron-hole interaction and the non-radiative recombination rate. Our analysis helps to optimize the charge separation process and the energy transfer in organic solar cells and in molecular photocells.

First-principles prediction of new photocatalyst materials with visible-light absorption and improved charge separation: surface modification of rutile TiO₂ with nanoclusters of MgO and Ga₂O₃.

PubMed

Nolan, Michael

2012-11-01

Titanium dioxide is an important and widely studied photocatalytic material, but to achieve photocatalytic activity under visible-light absorption, it needs to have a narrower band gap and reduced charge carrier recombination. First-principles simulations are presented in this paper to show that heterostructures of rutil TiO₂ modified with nanoclusters of MgO and Ga₂O₃ will be new photocatalytically active materials in the UV (MgO-TiO₂) and visible (Ga₂O₃-TiO₂) regions of the solar spectrum. In particular, our investigations of a model of the excited state of the heterostructures demonstrate that upon light excitation electrons and holes can be separated onto the TiO₂ surface and the metal oxide nanocluster, which will reduce charge recombination and improve photocatalytic activity. For MgO-modified TiO₂, no significant band gap change is predicted, but for Ga₂O₃-modified TiO₂ we predict a band gap change of up to 0.6 eV, which is sufficient to induce visible light absorption. Comparisons with unmodified TiO₂ and other TiO₂-based photocatalyst structures are presented.

Supercharging Reagent for Enhanced Liquid Chromatographic Separation and Charging of Sialylated and High-Molecular-Weight Glycopeptides for NanoHPLC-ESI-MS/MS Analysis.

PubMed

Lin, Chia-Wei; Haeuptle, Micha A; Aebi, Markus

2016-09-06

Recent developments in proteomic techniques have led to the development of mass spectrometry (MS)-based methods to characterize site-specific glycosylation of proteins. However, appropriate analytical tools to characterize acidic and high-molecular-weight (hMW) glycopeptides are still lacking. In this study, we demonstrate that the addition of supercharging reagent, m-nitrobenzyl alcohol (m-NBA), into mobile phases greatly facilitates the analysis of acidic and hMW glycopeptides. Using commercial glycoproteins, we demonstrated that in the presence of m-NBA the charge state of sialylated glycopeptides increased and the chromatographic separation of neutral and acidic glycopeptides revealed a remarkable improvement. Next, we applied this system to the characterization of a glycoconjugate vaccine candidate consisting of a genetically detoxified exotoxin A of Pseudomonas aeruginosa covalently linked to Shigella flexneri type 2a O-antigen (Sf2E) produced by engineered Escherichia coli. The addition of m-NBA, allowed us to identify peptides with glycan chains of unprecedented size, up to 20 repeat units (98 monosaccharides). Our results indicated that incorporation of m-NBA into reversed-phase liquid chromatography (LC) solvents improves sensitivity, charging, and chromatographic resolution for acidic and hMW glycopeptides.

Out-of-equilibrium spin transport in mesoscopic superconductors.

PubMed

Quay, C H L; Aprili, M

2018-08-06

The excitations in conventional superconductors, Bogoliubov quasi-particles, are spin-[Formula: see text] fermions but their charge is energy-dependent and, in fact, zero at the gap edge. Therefore, in superconductors (unlike normal metals) spin and charge degrees of freedom may be separated. In this article, we review spin injection into conventional superconductors and focus on recent experiments on mesoscopic superconductors. We show how quasi-particle spin transport and out-of-equilibrium spin-dependent superconductivity can be triggered using the Zeeman splitting of the quasi-particle density of states in thin-film superconductors with small spin-mixing scattering. Finally, we address the spin dynamics and the feedback of quasi-particle spin imbalances on the amplitude of the superconducting energy gap.This article is part of the theme issue 'Andreev bound states'. © 2018 The Author(s).

Variations in Patterns of Utilization and Charges for the Care of Headache in North Carolina, 2000-2009: A Statewide Claims' Data Analysis.

PubMed

Hurwitz, Eric L; Vassilaki, Maria; Li, Dongmei; Schneider, Michael J; Stevans, Joel M; Phillips, Reed B; Phelan, Shawn P; Lewis, Eugene A; Armstrong, Richard C

2016-05-01

The purpose of the study was to compare patterns of utilization and charges generated by medical doctors (MDs), doctors of chiropractic (DCs), and physical therapists (PTs) for the treatment of headache in North Carolina. Retrospective analysis of claims data from the North Carolina State Health Plan for Teachers and State Employees from 2000 to 2009. Data were extracted from Blue Cross Blue Shield of North Carolina for the North Carolina State Health Plan using International Classification of Diseases, Ninth Revision, diagnostic codes for headache. The claims were separated by individual provider type, combination of provider types, and referral patterns. The majority of patients and claims were in the MD-only or MD plus referral patterns. Chiropractic patterns represented less than 10% of patients. Care patterns with single-provider types and no referrals incurred the least charges on average for headache. When care did not include referral providers or services, MD with DC care was generally less expensive than MD care with PT. However, when combined with referral care, MD care with PT was generally less expensive. Compared with MD-only care, risk-adjusted charges (available 2006-2009) for patients in the middle risk quintile were significantly less for DC-only care. Utilization and expenditures for headache treatment increased from 2000 to 2009 across all provider groups. MD care represented the majority of total allowed charges in this study. MD care and DC care, alone or in combination, were overall the least expensive patterns of headache care. Risk-adjusted charges were significantly less for DC-only care. Copyright © 2016 National University of Health Sciences. Published by Elsevier Inc. All rights reserved.

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.

Electron beam induced strong organic/inorganic grafting for thermally stable lithium-ion battery separators

NASA Astrophysics Data System (ADS)

Choi, Yunah; Kim, Jin Il; Moon, Jungjin; Jeong, Jongyeob; Park, Jong Hyeok

2018-06-01

A tailored interface between organic and inorganic materials is of great importance to maximize the synergistic effects from hybridization. Polyethylene separators over-coated with inorganic thin films are the state-of-the art technology for preparing various secondary batteries with high safety. Unfortunately, the organic/inorganic hybrid separators have the drawback of a non-ideal interface, thus causing poor thermal/dimensional stability. Here, we report a straightforward method to resolve the drawback of the non-ideal interface between vapor deposited SiO2 and polyethylene separators, to produce a highly stable lithium-ion battery separator through strong chemical linking generated by direct electron beam irradiation. The simple treatment with an electron beam with an optimized dose generates thermally stable polymer separators, which may enhance battery safety under high-temperature conditions. Additionally, the newly formed Si-O-C or Si-CH3 chemical bonding enhances electrolyte-separator compatibility and thus may provide a better environment for ionic transport between the cathode and anode, thereby leading to better charge/discharge behaviors.

Monodispersed Zinc Oxide Nanoparticle-Dye Dyads and Triads

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

Gladfelter, Wayne L.; Blank, David A.; Mann, Kent R.

The overall energy conversion efficiency of photovoltaic cells depends on the combined efficiencies of light absorption, charge separation and charge transport. Dye-sensitized solar cells are photovoltaic devices in which a molecular dye absorbs light and uses this energy to initiate charge separation. The most efficient dye-sensitized solar cells (DSSCs) use nanocrystal titanium dioxide films to which are attached ruthenium complexes. Numerous studies have provided valuable insight into the dynamics of these and analogous photosystems, but the lack of site homogeneity in binding dye molecules to metal oxide films and nanocrystals (NCs) is a significant impediment to extracting fundamental details aboutmore » the electron transfer across the interface. Although zinc oxide is emerging as a potential semiconducting component in DSSCs, there is less known about the factors controlling charge separation across the dye/ZnO interface. Zinc oxide crystallizes in the wurtzite lattice and has a band gap of 3.37 eV. One of the features that makes ZnO especially attractive is the remarkable ability to control the morphology of the films. Using solution deposition processes, one can prepare NCs, nanorods and nanowires having a variety of shapes and dimensions. This project solved problems associated with film heterogeneity through the use of dispersible sensitizer/ZnO NC ensembles. The overarching goal of this research was to study the relationship between structure, energetics and dynamics in a set of synthetically controlled donor-acceptor dyads and triads. These studies provided access to unprecedented understanding of the light absorption and charge transfer steps that lie at the heart of DSSCs, thus enabling significant future advances in cell efficiencies. The approach began with the construction of well-defined dye-NC dyads that were sufficiently dispersible to allow the use of state of the art pulsed laser spectroscopic and kinetic methods to understand the charge transfer events at a fundamental level. This was combined with the synthesis of a broad range of sensitizers that provide systematic variation of the energetics, excited state dynamics, structure and interfacial bonding. The key is that the monodisperse nature and high dispersibility of the ZnO NCs made these experiments reproducible; in essence, the measurements were on discrete molecular species rather than on the complicated mixtures that resulted from the typical fabrication of functional photovoltaic cells. The monodispersed nature of the NCs also allowed the use of quantum confinement to investigate the role of donor/acceptor energetic alignment in chemically identical systems. The results added significantly to our basic understanding of energy and charge transfer events at molecule-semiconductor interfaces and will help the R&D community realize zinc oxide's full potential in solar cell applications.« less

Tribo-charging properties of waste plastic granules in process of tribo-electrostatic separation.

PubMed

Li, Jia; Wu, Guiqing; Xu, Zhenming

2015-01-01

Plastic products can be found everywhere in people's daily life. With the consistent growth of plastic consumption, more and more plastic waste is generated. Considering the stable chemical and physics characteristics of plastic, regular waste management methods are not suitable for recycling economic strategy of each government, which has become a serious environmental problem. Recycling plastic waste is considered to be the best way to treat it, because it cannot only deduce the waste but also save the energy to produce new virgin plastic. Tribo-electrostatic separation is strongly recommended for plastic separation as it can preserve the original properties of plastic and has little additional pollution. In this study, plastic granules are generated by crushing plastic waste in waste electric and electronic equipment. The tribo-charging properties of plastic waste were studied by vibrating tribo-charging and cyclone tribo-charging. The triboelectric series obtained by vibrating was: (-)-PE-PS-PC-PVC-ABS-PP-(+), while the triboelectric series obtained by cyclone was (-)-PE-PS-PC-PVC-ABS-PP-(+). Further, the cyclone charging was more effective and stable than vibrating charging. The impact factors experiments showed that small particle size was better changed than large ones and were more suitable recycled by tribo-electrostatic separation. High relative humidity was identified as impede charging effect. The results of this study will help defining the operating parameters of subsequent separator. Copyright © 2014 Elsevier Ltd. All rights reserved.

High yield of secondary B-side electron transfer in mutant Rhodobacter capsulatus reaction centers

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

Kressel, Lucas; Faries, Kaitlyn M.; Wander, Marc J.

2014-08-01

From the crystal structures of reaction centers (RCs) from purple photosynthetic bacteria, two pathways for electron transfer (ET) are apparent but only one pathway (the A side) operates in the native protein-cofactor complex. Partial activation of the B-side pathway has unveiled the true inefficiencies of ET processes on that side in comparison to analogous reactions on the A side. Of significance are the relative rate constants for forward ET and the competing charge recombination reactions. On the B side, these rate constants are nearly equal for the secondary charge-separation step (ET from bacteriopheophytin to quinone), relegating the yield of thismore » process to < 50%. Herein we report efforts to optimize this step. In surveying all possible residues at position 131 in the M subunit, we discovered that when glutamic acid replaces the native valine the efficiency of the secondary ET is nearly two-fold higher than in the wild-type RC. The positive effect of M131 Glu is likely due to formation of a hydrogen bond with the ring V keto group of the B-side bacteriopheophytin leading to stabilization of the charge-separated state involving this cofactor. In conclusion, this change slows charge recombination by roughly a factor of two and affords the improved yield of the desired forward ET to the B-side quinone terminal acceptor.« less

Charge and spin in low-dimensional cuprates

NASA Astrophysics Data System (ADS)

Maekawa, Sadamichi; Tohyama, Takami

2001-03-01

One of the central issues in the study of high-temperature superconducting cuprates which are composed of two-dimensional (2D) CuO2 planes is whether the 2D systems with strong electron correlation behave as a Fermi liquid or a non-Fermi-liquid-like one-dimensional (1D) system with electron correlation. In this article, we start with the detailed examination of the electronic structure in cuprates and study theoretically the spin and charge dynamics in 1D and 2D cuprates. The theoretical background of spin-charge separation in the 1D model systems including the Hubbard and t-J models is presented. The first direct observation of collective modes of spin and charge excitations in a 1D cuprate, which are called spinons and holons respectively, in angle-resolved photoemission spectroscopy (ARPES) experiments is reviewed in the light of the theoretical results based on the numerically exact-diagonalization method. The charge and spin dynamics in 1D insulating cuprates is also discussed in connection with the spin-charge separation. The arguments are extended to the 2D cuprates, and the unique aspects of the electronic properties of high-temperature superconductors are discussed. Special emphasis is placed on the d-wave-like excitations in insulating 2D cuprates observed in ARPES experiments. We explain how the excitations are caused by the spin-charge separation. The charge stripes observed in the underdoped cuprates are examined in connection with spin-charge separation in real space.

Computational modeling of electrostatic charge and fields produced by hypervelocity impact

DOE PAGES

Crawford, David A.

2015-05-19

Following prior experimental evidence of electrostatic charge separation, electric and magnetic fields produced by hypervelocity impact, we have developed a model of electrostatic charge separation based on plasma sheath theory and implemented it into the CTH shock physics code. Preliminary assessment of the model shows good qualitative and quantitative agreement between the model and prior experiments at least in the hypervelocity regime for the porous carbonate material tested. The model agrees with the scaling analysis of experimental data performed in the prior work, suggesting that electric charge separation and the resulting electric and magnetic fields can be a substantial effectmore » at larger scales, higher impact velocities, or both.« less

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.

Complete Monitoring of Coherent and Incoherent Spin Flip Domains in the Recombination of Charge-Separated States of Donor-Iridium Complex-Acceptor Triads.

PubMed

Klein, Johannes H; Schmidt, David; Steiner, Ulrich E; Lambert, Christoph

2015-09-02

The spin chemistry of photoinduced charge-separated (CS) states of three triads comprising one or two triarylamine donors, a cyclometalated iridium complex sensitizer and a naphthalene diimide (NDI) acceptor, was investigated by transient absorption spectroscopy in the ns-μs time regime. Strong magnetic-field effects (MFE) were observed for two triads with a phenylene bridge between iridium complex sensitizer and NDI acceptor. For these triads, the lifetimes of the CS states increased from 0.6 μs at zero field to 40 μs at about 2 T. Substituting the phenylene by a biphenyl bridge causes the lifetime of the CS state at zero field to increase by more than 2 orders of magnitude (τ = 79 μs) and the MFE to disappear almost completely. The kinetic MFE was analyzed in the framework of a generalized Hayashi-Nagakura scheme describing coherent (S, T0 ↔ T±) as well as incoherent (S, T0 ⇌ T±) processes by a single rate constant k±. The magnetic-field dependence of k± of the triads with phenylene bridge spans 2 orders of magnitude and exhibits a biphasic behavior characterized by a superposition of two Lorentzians. This biphasic MFE is observed for the first time and is clearly attributable to the coherent (B < 10 mT) and incoherent (10 mT < B < 2 T) domains of spin motion induced by isotropic and anisotropic hyperfine coupling. The parameters of both domains are well understood in terms of the structural properties of the two triads, including the effect of electron hopping in the triad with two donor moieties. The kinetic model also accounts for the reduction of the MFE on reducing the rate constant of charge recombination in the triad with the biphenyl bridge.

Design for simultaneous acceleration of stable and unstable beams in a superconducting heavy-ion linear accelerator for RISP

NASA Astrophysics Data System (ADS)

Kim, Jongwon; Son, Hyock-Jun; Park, Young-Ho

2017-11-01

The post-accelerator of isotope separation on-line (ISOL) system for rare isotope science project (RISP) is a superconducting linear accelerator (SC-linac) with a DC equivalent voltage of around 160 MV. An isotope beam extracted from the ISOL is in a charge state of 1+ and its charge state is increased to n+ by charge breeding with an electron beam ion source (EBIS). The charge breeding takes tens of ms and the pulse width of extracted beam from the EBIS is tens of μs, which operates at up to 30 Hz. Consequently a large portion of radio frequency (rf) time of the post SC-linac is unused. The post-linac is equipped also with an electron cyclotron resonance (ECR) ion source for stable ion acceleration. Thanks to the large phase acceptance of SC-linac, it is possible to accelerate simultaneously both stable and radioisotope ions with a similar charge to mass ratio by sharing rf time. This operation scheme is implemented for RISP with the addition of an electric chopper and magnetic kickers. The facility will be capable of providing the users of the ISOL and in-flight fragmentation (IF) systems with different beams simultaneously, which would help nuclear science users in obtaining a beam time as high-precision measurements often need long hours.

Ultrafast photoinduced charge separation in metal-semiconductor nanohybrids.

PubMed

Mongin, Denis; Shaviv, Ehud; Maioli, Paolo; Crut, Aurélien; Banin, Uri; Del Fatti, Natalia; Vallée, Fabrice

2012-08-28

Hybrid nano-objects formed by two or more disparate materials are among the most promising and versatile nanosystems. A key parameter in their properties is interaction between their components. In this context we have investigated ultrafast charge separation in semiconductor-metal nanohybrids using a model system of gold-tipped CdS nanorods in a matchstick architecture. Experiments are performed using an optical time-resolved pump-probe technique, exciting either the semiconductor or the metal component of the particles, and probing the light-induced change of their optical response. Electron-hole pairs photoexcited in the semiconductor part of the nanohybrids are shown to undergo rapid charge separation with the electron transferred to the metal part on a sub-20 fs time scale. This ultrafast gold charging leads to a transient red-shift and broadening of the metal surface plasmon resonance, in agreement with results for free clusters but in contrast to observation for static charging of gold nanoparticles in liquid environments. Quantitative comparison with a theoretical model is in excellent agreement with the experimental results, confirming photoexcitation of one electron-hole pair per nanohybrid followed by ultrafast charge separation. The results also point to the utilization of such metal-semiconductor nanohybrids in light-harvesting applications and in photocatalysis.

Change of carrier density at the pseudogap critical point of a cuprate superconductor.

PubMed

Badoux, S; Tabis, W; Laliberté, F; Grissonnanche, G; Vignolle, B; Vignolles, D; Béard, J; Bonn, D A; Hardy, W N; Liang, R; Doiron-Leyraud, N; Taillefer, Louis; Proust, Cyril

2016-03-10

The pseudogap is a partial gap in the electronic density of states that opens in the normal (non-superconducting) state of cuprate superconductors and whose origin is a long-standing puzzle. Its connection to the Mott insulator phase at low doping (hole concentration, p) remains ambiguous and its relation to the charge order that reconstructs the Fermi surface at intermediate doping is still unclear. Here we use measurements of the Hall coefficient in magnetic fields up to 88 tesla to show that Fermi-surface reconstruction by charge order in the cuprate YBa2Cu3Oy ends sharply at a critical doping p = 0.16 that is distinctly lower than the pseudogap critical point p* = 0.19 (ref. 11). This shows that the pseudogap and charge order are separate phenomena. We find that the change in carrier density n from n = 1 + p in the conventional metal at high doping (ref. 12) to n = p at low doping (ref. 13) starts at the pseudogap critical point. This shows that the pseudogap and the antiferromagnetic Mott insulator are linked.

Twenty-First Century Research Needs in Electrostatic Processes Applied to Industry and Medicine

NASA Technical Reports Server (NTRS)

Mazumder, M. K.; Sims, R. A.; Biris, A. S.; Srirama, P. K.; Saini, D.; Yurteri, C. U.; Trigwell, S.; De, S.; Sharma, R.

2005-01-01

From the early century Nobel Prize winning (1923) experiments with charged oil droplets, resulting in the discovery of the elementary electronic charge by Robert Millikan, to the early 21st century Nobel Prize (2002) awarded to John Fenn for his invention of electrospray ionization mass spectroscopy and its applications to proteomics, electrostatic processes have been successfully applied to many areas of industry and medicine. Generation, transport, deposition, separation, analysis, and control of charged particles involved in the four states of matter: solid, liquid, gas, and plasma are of interest in many industrial and biomedical processes. In this paper, we briefly discuss some of the applications and research needs involving charged particles in industrial and medical applications including: (1) Generation and deposition of unipolarly charged dry powder without the presence of ions or excessive ozone, (2) Control of tribocharging process for consistent and reliable charging, (3) Thin film (less than 25 micrometers) powder coating and Powder coating on insulative surfaces, (4) Fluidization and dispersion of fine powders, (5) Mitigation of Mars dust, (6) Effect of particle charge on the lung deposition of inhaled medical aerosols, (7) Nanoparticle deposition, and (8) Plasma/Corona discharge processes. A brief discussion on the measurements of charged particles and suggestions for research needs are also included.

Laser desorption vs. electrospray of polyyne-threaded rotaxanes: Preventing covalent cross-linking and promoting noncovalent aggregation

NASA Astrophysics Data System (ADS)

Neugebauer, Thomas S.; Franz, Michael; Frankenberger, Stephanie; Tykwinski, Rik R.; Drewello, Thomas

2018-02-01

Laser-induced cross-linking of polyynes is successfully hindered when the polyyne is encapsulated as part of a rotaxane and therefore protected by a surrounding macrocycle. When the rotaxane is electrosprayed, however, noncovalent aggregate ions are efficiently formed. Aggregates of considerable size (including more than 50 rotaxane molecules with masses beyond 100k Da) and charge states (up to 13 charges and beyond) have been observed. Either protons or sodium cations act as the charge carriers. These aggregates are not formed when the individual components of the rotaxane, i.e., the macrocycle or the polyyne, are separately electrosprayed. This underlines the structural importance of the rotaxane for the aggregate formation. Straightforward force field calculations indicate that the polyyne thread hinders the folding of the macrocycles, which facilitates the bonding interaction between the two components.

Entanglement scrambling in 2d conformal field theory

DOE PAGES

Asplund, Curtis T.; Bernamonti, Alice; Galli, Federico; ...

2015-09-17

Here, we investigate how entanglement spreads in time-dependent states of a 1+1 dimensional conformal field theory (CFT). The results depend qualitatively on the value of the central charge. In rational CFTs, which have central charge below a critical value, entanglement entropy behaves as if correlations were carried by free quasiparticles. This leads to long-term memory effects, such as spikes in the mutual information of widely separated regions at late times. When the central charge is above the critical value, the quasiparticle picture fails. Assuming no extended symmetry algebra, any theory with c > 1 has diminished memory effects compared tomore » the rational models. In holographic CFTs, with c >> 1, these memory effects are eliminated altogether at strong coupling, but reappear after the scrambling time t ≳ β log c at weak coupling.« less

Negatively charged excitons and photoluminescence in asymmetric quantum wells

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

Szlufarska, Izabela; Wojs, Arkadiusz; Quinn, John J.

2001-02-15

We study photoluminescence (PL) of charged excitons (X{sup -}) in narrow asymmetric quantum wells in high magnetic fields B. The binding of all X{sup -} states strongly depends on the separation {delta} of electron and hole layers. The most sensitive is the ''bright'' singlet, whose binding energy decreases quickly with increasing {delta} even at relatively small B. As a result, the value of B at which the singlet-triplet crossing occurs in the X{sup -} spectrum also depends on {delta}, and decreases from 35 T in a symmetric 10 nm GaAs well to 16 T for {delta}=0.5 nm. Since the criticalmore » values of {delta} at which different X{sup -} states unbind are surprisingly small compared to the well width, the observation of strongly bound X{sup -} states in an experimental PL spectrum implies virtually no layer displacement in the sample. This casts doubt on the interpretation of PL spectra of heterojunctions in terms of X{sup -} recombination.« less

Charge carriers' trapping states in pentacene films studied by modulated photocurrent

NASA Astrophysics Data System (ADS)

Gorgolis, S.; Giannopoulou, A.; Kounavis, P.

2013-03-01

The modulated photocurrent (MPC) technique is employed to study the charge carriers' trapping states of pentacene films. The characteristics of the experimental MPC spectra were found to be compatible with trapping-detrapping process of holes in gap states in which their occupancy can be modified by the bias illumination. A demarcation energy level separating empty from partially occupied traps was deduced from the MPC spectra, which can be used to monitor bias-light induced changes in the quasi Fermi level. An exponential trap distribution from structural disorder and a deep metastable gaussian trap distribution from adsorbed environmental impurities were extracted by means of the MPC spectroscopy. An attempt to escape frequency of the order of 1010s-1 was deduced for the gap sates. The derived trap distributions agree with those found before by means of other techniques. The present results indicate that the MPC technique can be used as a valuable tool for pentacene films characterization since it can be also applied to field effect samples.

Simulations of stretching a flexible polyelectrolyte with varying charge separation

DOE PAGES

Stevens, Mark J.; Saleh, Omar A.

2016-07-22

We calculated the force-extension curves for a flexible polyelectrolyte chain with varying charge separations by performing Monte Carlo simulations of a 5000 bead chain using a screened Coulomb interaction. At all charge separations, the force-extension curves exhibit a Pincus-like scaling regime at intermediate forces and a logarithmic regime at large forces. As the charge separation increases, the Pincus regime shifts to a larger range of forces and the logarithmic regime starts are larger forces. We also found that force-extension curve for the corresponding neutral chain has a logarithmic regime. Decreasing the diameter of bead in the neutral chain simulations removedmore » the logarithmic regime, and the force-extension curve tends to the freely jointed chain limit. In conclusion, this result shows that only excluded volume is required for the high force logarithmic regime to occur.« less

Graphitic Nitrogen Triggers Red Fluorescence in Carbon Dots.

PubMed

Holá, Kateřina; Sudolská, Mária; Kalytchuk, Sergii; Nachtigallová, Dana; Rogach, Andrey L; Otyepka, Michal; Zbořil, Radek

2017-12-26

Carbon dots (CDs) are a stable and highly biocompatible fluorescent material offering great application potential in cell labeling, optical imaging, LED diodes, and optoelectronic technologies. Because their emission wavelengths provide the best tissue penetration, red-emitting CDs are of particular interest for applications in biomedical technologies. Current synthetic strategies enabling red-shifted emission include increasing the CD particle size (sp 2 domain) by a proper synthetic strategy and tuning the surface chemistry of CDs with suitable functional groups (e.g., carboxyl). Here we present an elegant route for preparing full-color CDs with well-controllable fluorescence at blue, green, yellow, or red wavelengths. The two-step procedure involves the synthesis of a full-color-emitting mixture of CDs from citric acid and urea in formamide followed by separation of the individual fluorescent fractions by column chromatography based on differences in CD charge. Red-emitting CDs, which had the most negative charge, were separated as the last fraction. The trend in the separation, surface charge, and red-shift of photoluminescence was caused by increasing amount of graphitic nitrogen in the CD structure, as was clearly proved by XPS, FT-IR, Raman spectroscopy, and DFT calculations. Importantly, graphitic nitrogen generates midgap states within the HOMO-LUMO gap of the undoped systems, resulting in significantly red-shifted light absorption that in turn gives rise to fluorescence at the low-energy end of the visible spectrum. The presented findings identify graphitic nitrogen as another crucial factor that can red-shift the CD photoluminescence.

Charge Splitting In Situ Recorder (CSIR) for Real-Time Examination of Plasma Charging Effect in FinFET BEOL Processes

NASA Astrophysics Data System (ADS)

Tsai, Yi-Pei; Hsieh, Ting-Huan; Lin, Chrong Jung; King, Ya-Chin

2017-09-01

A novel device for monitoring plasma-induced damage in the back-end-of-line (BEOL) process with charge splitting capability is first-time proposed and demonstrated. This novel charge splitting in situ recorder (CSIR) can independently trace the amount and polarity of plasma charging effects during the manufacturing process of advanced fin field-effect transistor (FinFET) circuits. Not only does it reveal the real-time and in situ plasma charging levels on the antennas, but it also separates positive and negative charging effect and provides two independent readings. As CMOS technologies push for finer metal lines in the future, the new charge separation scheme provides a powerful tool for BEOL process optimization and further device reliability improvements.

Charge exchange molecular ion source

DOEpatents

Vella, Michael C.

2003-06-03

Ions, particularly molecular ions with multiple dopant nucleons per ion, are produced by charge exchange. An ion source contains a minimum of two regions separated by a physical barrier and utilizes charge exchange to enhance production of a desired ion species. The essential elements are a plasma chamber for production of ions of a first species, a physical separator, and a charge transfer chamber where ions of the first species from the plasma chamber undergo charge exchange or transfer with the reactant atom or molecules to produce ions of a second species. Molecular ions may be produced which are useful for ion implantation.

Modulating protein behaviors on responsive surface by external electric fields: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Xie, Yun; Pan, Yufang; Zhang, Rong; Liang, Ying; Li, Zhanchao

2015-01-01

Molecular dynamics simulations were employed to investigate the modulation of protein behaviors on the electrically responsive zwitterionic phosphorylcholine self-assembled monolayers (PC-SAMs). Results show that PC-SAMs could sensitively respond to the applied electric fields and exhibit three states with different charge distributions, namely both the negatively charged phosphate groups and the positively charged choline groups are exposed to the solution in the absence of electric fields (state 1), phosphate groups exposed in the presence of positive electric fields (state 2), and choline groups exposed in the presence of negative electric fields (state 3). Under state 1, the adsorption of Cyt c on the PC-SAM is reversible and the orientations of Cyt c are randomly distributed. Under state 2, the adsorption of Cyt c is enhanced due to the electrostatic attractions between the exposed phosphate groups and the positively charged protein; when adsorbed on the PC-SAMs, Cyt c tends to adopt the orientation with the heme plane perpendicular to the surface plane, and the percentage of this orientation increases as the field strength rises up. Under state 3, the adsorption of Cyt c is retarded because of the electrostatic repulsions between the exposed choline groups and the protein; however, if the gaps between PC chains are large enough, Cyt c could insert into the PC-SAM and access the phosphate groups after overcoming a slight energy barrier. Under three states, the basic backbone structures of Cyt c are well kept within the simulation time since the conformation of Cyt c is mainly affected by the surface-generated electric fields, whose strengths are modulated by the external electric fields and are not strong enough to deform protein. The results indicate the possibility of regulating protein behaviors, including promoting or retarding protein adsorption and regulating protein orientations, on responsive surfaces by applying electric fields on the surfaces without worrying protein deformation, which may be helpful in the applications of protein separation and controlled drug delivery.

Fragment charge difference method for estimating donor-acceptor electronic coupling: Application to DNA π-stacks

NASA Astrophysics Data System (ADS)

Voityuk, Alexander A.; Rösch, Notker

2002-09-01

The purpose of this communication is two-fold. We introduce the fragment charge difference (FCD) method to estimate the electron transfer matrix element HDA between a donor D and an acceptor A, and we apply this method to several aspects of hole transfer electronic couplings in π-stacks of DNA, including systems with several donor-acceptor sites. Within the two-state model, our scheme can be simplified to recover a convenient estimate of the electron transfer matrix element HDA=(1-Δq2)1/2(E2-E1)/2 based on the vertical excitation energy E2-E1 and the charge difference Δq between donor and acceptor. For systems with strong charge separation, Δq≳0.95, one should resort to the FCD method. As favorable feature, we demonstrate the stability of the FCD approach for systems which require an approach beyond the two-state model. On the basis of ab initio calculations of various DNA related systems, we compared three approaches for estimating the electronic coupling: the minimum splitting method, the generalized Mulliken-Hush (GMH) scheme, and the FCD approach. We studied the sensitivity of FCD and GMH couplings to the donor-acceptor energy gap and found both schemes to be quite robust; they are applicable also in cases where donor and acceptor states are off resonance. In the application to π-stacks of DNA, we demonstrated for the Watson-Crick pair dimer [(GC),(GC)] how structural changes considerably affect the coupling strength of electron hole transfer. For models of three Watson-Crick pairs, we showed that the two-state model significantly overestimates the hole transfer coupling whereas simultaneous treatment of several states leads to satisfactory results.

Solar wind ion composition and charge states

NASA Technical Reports Server (NTRS)

vonSteiger, R.

1995-01-01

The solar wind, a highly tenuous plasma streaming from the Sun into interplanetary space at supersonic speed, is roughly composed of 95% hydrogen and 5% helium by number. All other, heavy elements contribute less than 0.1% by number and thus are truly test particles Nevertheless, these particles provide valuable information not present in the main components. We first discuss the importance of the heavy ions as tracers for processes in the solar atmosphere. Specifically, their relative abundances are found to be different in the solar wind as compared to the photosphere. This fractionation, which is best organized as a function of the first ionization time (FIT) of the elements under solar surface conditions, provides information on the structure of the chromosphere. where it is imparted on the partially ionized material by an atom-ion separation mechanism. Moreover, the charge states of the heavy ions can be used to infer the coronal temperature, since they are frozen-in near the altitude where the expansion time scale overcomes the ionization/recombination time scales. Next, we review the published values of ion abundances in the solar wind, concentrating on the recent results of the SWICS instrument on Ulysses. About 8 elements and more than 20 charge states can be routinely analyzed by this sensor. There is clear evidence that both the composition and the charge state distribution is significantly different in the fast solar wind from the south polar coronal hole, traversed by Ulysses in 1993/94, as compared to the solar wind normally encountered near the ecliptic plane. The fractionation between low- and high-FIT elements is reduced, and the charge states indicate a lower, more uniform coronal temperature in the hole. Finally, we discuss these results in the framework of existing theoretical models of the chromosphere and corona, attempting to identify differences between the low- and high-latitude regions of the solar atmosphere.

Photoinduced electron transfer in fixed distance chlorophyll-quinone donor-acceptor molecules

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

Wasielewski, M.R.; Johnson, D.G.; Svec, W.A.

1987-01-01

A series of fixed distance chlorophyll-quinone donor-acceptor molecules have been prepared. The donor consists of either methyl pyropheophorbide a or methyl pyrochlorophyllide a, while the acceptor is either benzoquinone or naphthoquinone. The acceptors are fused to a triptycene spacer group, which in turn is attached to the donors at their vinyl groups. Picosecond transient absorption measurements have been used to identify electron transfer from the lowest excited singlet state of the donor to the acceptor as the mechanism of fluorescence quenching in these molecules. The charge separation rate constants increase from 2 x 10/sup 10/ s/sup -1/ to 4 xmore » 10/sup 11/ s/sup -1/ as the free energy of charge separation increases, while the radical pair recombination rate constants decrease from 1.2 x 10/sup 11/ s/sup -1/ to 2 x 10/sup 9/ s/sup -1/ as the free energy of recombination increases. The resulting total reorganization energy lambda = 0.9 eV.« less

Separation of heat and charge currents for boosted thermoelectric conversion

NASA Astrophysics Data System (ADS)

Mazza, Francesco; Valentini, Stefano; Bosisio, Riccardo; Benenti, Giuliano; Giovannetti, Vittorio; Fazio, Rosario; Taddei, Fabio

2015-06-01

In a multiterminal device the (electronic) heat and charge currents can follow different paths. In this paper we introduce and analyze a class of multiterminal devices where this property is pushed to its extreme limits, with charge and heat currents flowing in different reservoirs. After introducing the main characteristics of this heat-charge current separation regime, we show how to realize it in a multiterminal device with normal and superconducting leads. We demonstrate that this regime allows us to control independently heat and charge flows and to greatly enhance thermoelectric performances at low temperatures. We analyze in detail a three-terminal setup involving a superconducting lead, a normal lead, and a voltage probe. For a generic scattering region we show that in the regime of heat-charge current separation both the power factor and the figure of merit Z T are highly increased with respect to a standard two-terminal system. These results are confirmed for the specific case of a system consisting of three coupled quantum dots.

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

NASA Astrophysics Data System (ADS)

Pavlovich, V. S.

2014-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

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.

Rapid preparative separation of monoclonal antibody charge variants using laterally-fed membrane chromatography.

PubMed

Sadavarte, Rahul; Madadkar, Pedram; Filipe, Carlos Dm; Ghosh, Raja

2018-01-15

Monoclonal antibodies undergo various forms of chemical transformation which have been shown to cause loss in efficacy and alteration in pharmacokinetic properties of these molecules. Such modified antibody molecules are known as variants. They also display physical properties such as charge that are different from intact antibody molecules. However, the difference in charge is very subtle and separation based on it is quite challenging. Charge variants are usually separated using ion-exchange column chromatography or isoelectric focusing. In this paper, we report a rapid and scalable method for fractionating monoclonal antibody charge variants, based on the use of cation exchange laterally-fed membrane chromatography (LFMC). Starting with a sample of monoclonal antibody hIgG1-CD4, three well-resolved fractions were obtained using either pH or salt gradient. These fractions were identified as acidic, neutral and basic variants. Each of these fractions contained intact heavy and light chains and so antibody fragmentation had no role in variant generation. The separation was comparable to that using column chromatography but was an order of magnitude faster. Copyright © 2017 Elsevier B.V. All rights reserved.

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

Charge-based separation of particles and cells with similar sizes via the wall-induced electrical lift.

PubMed

Thomas, Cory; Lu, Xinyu; Todd, Andrew; Raval, Yash; Tzeng, Tzuen-Rong; Song, Yongxin; Wang, Junsheng; Li, Dongqing; Xuan, Xiangchun

2017-01-01

The separation of particles and cells in a uniform mixture has been extensively studied as a necessity in many chemical and biomedical engineering and research fields. This work demonstrates a continuous charge-based separation of fluorescent and plain spherical polystyrene particles with comparable sizes in a ψ-shaped microchannel via the wall-induced electrical lift. The effects of both the direct current electric field in the main-branch and the electric field ratio in between the inlet branches for sheath fluid and particle mixture are investigated on this electrokinetic particle separation. A Lagrangian tracking method based theoretical model is also developed to understand the particle transport in the microchannel and simulate the parametric effects on particle separation. Moreover, the demonstrated charge-based separation is applied to a mixture of yeast cells and polystyrene particles with similar sizes. Good separation efficiency and purity are achieved for both the cells and the particles. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Non-aqueous capillary electrophoretic separation of cholesterol and 25-hydroxycholesterol after derivatization with Girard P reagent.

PubMed

Gregus, Michal; Roberg-Larsen, Hanne; Lundanes, Elsa; Foret, Frantisek; Kuban, Petr; Wilson, Steven Ray

2017-10-01

Capillary electrophoresis (CE) can provide high separation efficiency with very simple instrumentation, but has yet to be explored regarding oxysterols/cholesterol. Cholesterol and 25-hydroxycholesterol (both are 4-ene-3-ketosteroids) were quantitatively transformed into hydrazones using Girard P reagent after enzymatic oxidation by cholesterol oxidase. Separation was achieved using non-aqueous capillary electrophoresis with UV detection at 280nm; the "charge-tagging" Girard P reagent ensured both charge and chromophore (which are requirements for CE-UV). Excess reagent was also separated from the two analytes, eliminating the need for removal prior to the analysis. The compounds were separated in less than 5min with excellent separation efficiency, using separation electrolytes fully compatible with mass spectrometry. The CE-UV method was used to optimize steps for charge-tagging, revealing that the procedure is affected by the analyte/reagent ratio and reaction time, but also the analyte structure. Copyright © 2017 Elsevier B.V. All rights reserved.

Method development of enantiomer separations by affinity capillary electrophoresis, cyclodextrin electrokinetic chromatography and capillary electrophoresis-mass spectrometry.

PubMed

Tanaka, Yoshihide

2002-07-01

Capillary electrophoresis (CE) has become a powerful tool for enantiomer separations during the last decade. Since 1993, the author has investigated enantiomer separations by affinity capillary electrophoresis (affinity CE) with some proteins and by cyclodextrin electrokinetic chromatography (CDEKC) with some charged cyclodextrins (CDs). Many successful enantiomer separations are demonstrated from our study in this review article. In the enantiomer separations by affinity CE, the deterioration of detection sensitivity was observed under high concentration of the protein in running solutions. The partial filling technique was practically useful to solve the serious problem. It allowed operation at high protein concentrations, such as 500 mumol/L, without the detection problem. Charged CDs had several advantages for the enantiomer separations over neutral ones. Strong electrostatic interactions between a charged CD and oppositely charged analytes should be effective for the formation of the complex. A large difference in electrophoretic mobility between the free analyte and the inclusion complex should also enhance the enantiomeric resolution. In CE-mass spectrometry (CE-MS), the partial filling technique was applied to avoid the introduction of nonvolatile chiral selectors into the CE-MS interface. By replacing the nonvolatile electrolytes in the running buffer by volatile ones, the separation conditions employed in CE with the UV detection method could be transferred to CE-MS.

Role of coherence and delocalization in photo-induced electron transfer at organic interfaces

NASA Astrophysics Data System (ADS)

Abramavicius, V.; Pranculis, V.; Melianas, A.; Inganäs, O.; Gulbinas, V.; Abramavicius, D.

2016-09-01

Photo-induced charge transfer at molecular heterojunctions has gained particular interest due to the development of organic solar cells (OSC) based on blends of electron donating and accepting materials. While charge transfer between donor and acceptor molecules can be described by Marcus theory, additional carrier delocalization and coherent propagation might play the dominant role. Here, we describe ultrafast charge separation at the interface of a conjugated polymer and an aggregate of the fullerene derivative PCBM using the stochastic Schrödinger equation (SSE) and reveal the complex time evolution of electron transfer, mediated by electronic coherence and delocalization. By fitting the model to ultrafast charge separation experiments, we estimate the extent of electron delocalization and establish the transition from coherent electron propagation to incoherent hopping. Our results indicate that even a relatively weak coupling between PCBM molecules is sufficient to facilitate electron delocalization and efficient charge separation at organic interfaces.

Controlling Gas-Phase Reactions for Efficient Charge Reduction Electrospray Mass Spectrometry of Intact Proteins

PubMed Central

Frey, Brian L.; Lin, Yuan; Westphall, Michael S.; Smith, Lloyd M.

2006-01-01

Charge reduction electrospray mass spectrometry (CREMS) reduces the charge states of electrospray-generated ions, which concentrates the ions from a protein into fewer peaks spread over a larger m/z range, thereby increasing peak separation and decreasing spectral congestion. An optimized design for a CREMS source is described that provides an order-of-magnitude increase in sensitivity compared to previous designs and provides control over the extent of charge reduction. Either a corona discharge or an α-particle source was employed to generate anions that abstract protons from electrosprayed protein cations. These desired ion/ion proton transfer reactions predominated, but some oxidation and ion-attachment reactions also occurred leading to new peaks or mass-shifted broader peaks while decreasing signal intensity. The species producing these deleterious side-reactions were identified, and conditions were found that prevented their formation. Spectrometer m/z biases were examined because of their effect upon the signal intensity of higher m/z charge-reduced protein ions. The utility of this atmospheric pressure CREMS was demonstrated using a cell lysate fraction from E. coli. The spectral simplification afforded by CREMS reveals more proteins than are observed without charge reduction. PMID:16198118

Eliminating Overerase Behavior by Designing Energy Band in High-Speed Charge-Trap Memory Based on WSe2.

PubMed

Liu, Chunsen; Yan, Xiao; Wang, Jianlu; Ding, Shijin; Zhou, Peng; Zhang, David Wei

2017-05-01

Atomic crystal charge trap memory, as a new concept of nonvolatile memory, possesses an atomic level flatness interface, which makes them promising candidates for replacing conventional FLASH memory in the future. Here, a 2D material WSe 2 and a 3D Al 2 O 3 /HfO 2 /Al 2 O 3 charge-trap stack are combined to form a charge-trap memory device with a separation of control gate and memory stack. In this device, the charges are erased/written by built-in electric field, which significantly enhances the write speed to 1 µs. More importantly, owing to the elaborate design of the energy band structure, the memory only captures electrons with a large electron memory window over 20 V and trap selectivity about 13, both of them are the state-of-the-art values ever reported in FLASH memory based on 2D materials. Therefore, it is demonstrated that high-performance charge trap memory based on WSe 2 without the fatal overerase issue in conventional FLASH memory can be realized to practical application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Photoinduced Charge Transfer and Electrochemical Properties of Triphenylamine Ih-Sc3N@C80 Donor-Acceptor Conjugates

PubMed Central

Pinzón, Julio R.; Gasca, Diana C.; Shankara, Gayathri. S; Bottari, Giovanni; Torres, Tomás; Guldi, Dirk M.; Echegoyen, Luis

2009-01-01

Two isomeric [5,6]-pyrrolidine-Ih-Sc3N@C80 electron donor acceptor conjugates containing triphenylamine (TPA) as the donor system were synthesized. Electrochemical and photophysical studies of the novel conjugates were made and compared with those of their C60 analogues, in order to determine i) the effect of the linkage position (N-substituted versus 2-substituted pyrrolidine) of the donor system in the formation of photoinduced charge separated states, ii) the thermal stability towards the retro-cycloaddition reaction and iii) the effect of changing C60 for Ih-Sc3N@C80 as the electron acceptor. It was found that when the donor is connected to the pyrrolidine nitrogen atom, the resulting dyad produces a significantly longer lived radical pair than the corresponding 2-substituted isomer for both the C60 and Ih-Sc3N@C80 dyads. In addition to that, the N-substituted TPA-Ih-Sc3N@C80 dyad has much better thermal stability than the 2-subtituted one. Finally, the Ih-Sc3N@C80 dyads have considerably longer lived charge separated states than their C60 analogues, thus approving the advantage of using Ih-Sc3N@C80 instead of C60 as the acceptor for the construction of fullerene based donor acceptor conjugates. These findings are important for the design and future application of Ih-Sc3N@C80 dyads as materials for the construction of plastic organic solar cells. PMID:19445462

Self-assembled photosynthesis-inspired light harvesting material and solar cells containing the same

DOEpatents

Lindsey, Jonathan S [Raleigh, NC; Chinnasamy, Muthiah [Raleigh, NC; Fan, Dazhong [Raleigh, NC

2009-12-15

A solar cell is described that comprises: (a) a semiconductor charge separation material; (b) at least one electrode connected to the charge separation material; and (c) a light-harvesting film on the charge separation material, the light-harvesting film comprising non-covalently coupled, self-assembled units of porphyrinic macrocycles. The porphyrinic macrocycles preferably comprise: (i) an intramolecularly coordinated metal; (ii) a first coordinating substituent; and (iii) a second coordinating substituent opposite the first coordinating substituent. The porphyrinic macrocycles can be assembled by repeating intermolecular coordination complexes of the metal, the first coordinating substituent and the second coordinating substituent.

CHARGE BOTTLE FOR A MASS SEPARATOR

DOEpatents

Davidson, P.H.

1959-07-01

Improved mass separator charge bottles are described for containing a dense charge of a chemical compound of copper, nickel, lead or other useful substance which is to be vaporized, and to the method of utilizing such improvcd charge bottles so that the chemical compound is vaporized from the under surface of the charge and thus permits the non-volatile portion thereof to fall to the bottom of the charge bottle where it does not form an obstacle to further evaporation. The charge bottle comprises a vertically disposed cylindrical portion, an inner re-entrant cylindrical portion extending axially and downwardly into the same from the upper end thereof, and evaporative source material in the form of a chemical compound compacted within the upper annular pontion of the charge bottle formed by the re-entrant cylindrical portion, whereby vapor from the chemical compound will pass outwardly from the charge bottle through an apertured closure.

Continuous-Time Monitoring of Landau-Zener Interference in a Cooper-Pair Box

NASA Astrophysics Data System (ADS)

Sillanpää, Mika; Lehtinen, Teijo; Paila, Antti; Makhlin, Yuriy; Hakonen, Pertti

2006-05-01

Landau-Zener (LZ) tunneling can occur with a certain probability when crossing energy levels of a quantum two-level system are swept across the minimum energy separation. Here we present experimental evidence of quantum interference effects in solid-state LZ tunneling. We used a Cooper-pair box qubit where the LZ tunneling occurs at the charge degeneracy. By employing a weak nondemolition monitoring, we observe interference between consecutive LZ-tunneling events; we find that the average level occupancies depend on the dynamical phase. The system’s unusually strong linear response is explained by interband relaxation. Our interferometer can be used as a high-resolution Mach-Zehnder type detector for phase and charge.

Continuous-time monitoring of Landau-Zener interference in a cooper-pair box.

PubMed

Sillanpää, Mika; Lehtinen, Teijo; Paila, Antti; Makhlin, Yuriy; Hakonen, Pertti

2006-05-12

Landau-Zener (LZ) tunneling can occur with a certain probability when crossing energy levels of a quantum two-level system are swept across the minimum energy separation. Here we present experimental evidence of quantum interference effects in solid-state LZ tunneling. We used a Cooper-pair box qubit where the LZ tunneling occurs at the charge degeneracy. By employing a weak nondemolition monitoring, we observe interference between consecutive LZ-tunneling events; we find that the average level occupancies depend on the dynamical phase. The system's unusually strong linear response is explained by interband relaxation. Our interferometer can be used as a high-resolution Mach-Zehnder-type detector for phase and charge.

Tight-binding model of the photosystem II reaction center: application to two-dimensional electronic spectroscopy

NASA Astrophysics Data System (ADS)

Gelzinis, Andrius; Valkunas, Leonas; Fuller, Franklin D.; Ogilvie, Jennifer P.; Mukamel, Shaul; Abramavicius, Darius

2013-07-01

We propose an optimized tight-binding electron-hole model of the photosystem II (PSII) reaction center (RC). Our model incorporates two charge separation pathways and spatial correlations of both static disorder and fast fluctuations of energy levels. It captures the main experimental features observed in time-resolved two-dimensional (2D) optical spectra at 77 K: peak pattern, lineshapes and time traces. Analysis of 2D spectra kinetics reveals that specific regions of the 2D spectra of the PSII RC are sensitive to the charge transfer states. We find that the energy disorder of two peripheral chlorophylls is four times larger than the other RC pigments.

Up-Conversion Intersystem Crossing Rates in Organic Emitters for Thermally Activated Delayed Fluorescence: Impact of the Nature of Singlet vs Triplet Excited States.

PubMed

Samanta, Pralok K; Kim, Dongwook; Coropceanu, Veaceslav; Brédas, Jean-Luc

2017-03-22

The rates for up-conversion intersystem crossing (UISC) from the T 1 state to the S 1 state are calculated for a series of organic emitters with an emphasis on thermally activated delayed fluorescence (TADF) materials. Both the spin-orbit coupling and the energy difference between the S 1 and T 1 states (ΔE ST ) are evaluated, at the density functional theory (DFT) and time-dependent DFT levels. The calculated UISC rates and ΔE ST values are found to be in good agreement with available experimental data. Our results underline that small ΔE ST values and sizable spin-orbit coupling matrix elements have to be simultaneously realized in order to facilitate UISC and ultimately TADF. Importantly, the spatial separation of the highest occupied and lowest unoccupied molecular orbitals of the emitter, a widely accepted strategy for the design of TADF molecules, does not necessarily lead to a sufficient reduction in ΔE ST ; in fact, either a significant charge-transfer (CT) contribution to the T 1 state or a minimal energy difference between the local-excitation and charge-transfer triplet states is required to achieve a small ΔE ST . Also, having S 1 and T 1 states of a different nature is found to strongly enhance spin-orbit coupling, which is consistent with the El-Sayed rule for ISC rates. Overall, our results indicate that having either similar energies for the local-excitation and charge-transfer triplet states or the right balance between a substantial CT contribution to T 1 and somewhat different natures of the S 1 and T 1 states, paves the way toward UISC enhancement and thus TADF efficiency improvement.

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

PubMed

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

2011-10-27

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

Femtosecond-picosecond laser photolysis studies on the dynamics of excited charge-transfer complexes: Aromatic hydrocarbon-acid anhydride, -tetracyanoethylene, and -tetracyanoquinodimethane systems in acetonitrile solutions

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

Asahi, Tsuyoshi; Mataga, Noboru

1991-03-07

Formation processes of contact ion pairs (CIP) from the excited Franck-Condon (FC) state of charge-transfer (CT) complexes of aromatic hydrocarbons with acid anhydride as well as cyano compound acceptors in acetonitrile solution and charge recombination (CR) rates (k{sub CR}{sup CIP}) of produced CIP states have been investigated by femtosecond and picosecond laser phototlysis and time-resolved absorption spectral measurements covering a wide range of free energy gap-{Delta}G{degree}{sub ip} between the ion pair and the ground state. It has been confirmed that the CIP formation becomes faster and k{sub CR}{sup CIP} of the produced CIP increases with increase of the strengths ofmore » the electron donor (D) and acceptor (A) in the complex, i.e., with decrease of the {minus}{Delta}G{degree}{sub ip} value. This peculiar energy gap dependence of k{sub CR}{sup CIP}, quite different from the bell-shaped one observed in the case of the solvent-separated ion pairs (SSIP) or loose ion pairs (LIP) formed by encounter between fluorescer and quencher in the fluoresence quenching reaction, has been interpreted by assuming the change of electronic and geometrical structures of CIP depending on the strengths of D and A.« less

Flexible solid-state symmetric supercapacitors based on MnO2 nanofilms with high rate capability and long cyclability

NASA Astrophysics Data System (ADS)

Wu, Lingxia; Li, Ruizhi; Guo, Junling; Zhou, Cheng; Zhang, Wenpei; Wang, Chong; Huang, Yu; Li, Yuanyuan; Liu, Jinping

2013-08-01

Flexible solid-state symmetric supercapacitor was fabricated using MnO2 nanofilms growing directly on carbon cloth as the electrodes and PVA/H3PO4 gel as the electrolyte/separator. The device can be operated at a stable cell-voltage up to 1.4 V, obviously larger than that of conventional solid-state symmetric supercapacitors (≤1 V). It exhibited excellent rate capability with a scan rate as high as 20 V s-1 and a long cyclability (˜60000 cycles) even under severe mechanical deformation. The charge storage mechanism at different scan rates was also quantitatively analyzed.

Spin dynamics of light-induced charge separation in composites of semiconducting polymers and PC60BM revealed using Q-band pulse EPR.

PubMed

Lukina, E A; Suturina, E; Reijerse, E; Lubitz, W; Kulik, L V

2017-08-23

Light-induced processes in composites of semiconducting polymers and fullerene derivatives have been widely studied due to their usage as active layers of organic solar cells. However the process of charge separation under light illumination - the key process of an organic solar cell is not well understood yet. Here we report a Q-band pulse electron paramagnetic resonance study of composites of the fullerene derivative PC 60 BM ([6,6]-phenyl-C 61 -butyric acid methyl ester) with different p-type semiconducting polymers regioregular and regiorandom P3HT (poly(3-hexylthiophene-2,5-diyl), MEH-PPV (poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]), PCDTBT (poly[N-9'-heptadecanyl-2,7-carbazole-alt-5,5-(4',7'-di-2-thienyl-2',1',3'-benzothiadiazole)]), PTB7 (poly({4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl}{3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}))), resulting in a detailed description of the in-phase laser flash-induced electron spin echo (ESE) signal. We found that in organic donor-acceptor composites the laser flash simultaneously induces species of two types: a polymer˙ + /fullerene˙ - spin-correlated polaron pair (SCPP) with an initial singlet spin state and (nearly) free polymer˙ + and fullerene˙ - species with non-equilibrium spin polarization. Species of the first type (SCPP) are well-known for polymer/fullerene blends and are usually associated with a charge-separated state. Also, spin polarization of long-living free species (polarons in deep traps) is affected by the laser flash, which is the third contribution to the flash-induced ESE signal. A protocol for extracting the in-phase ESE signal of the SCPP based on the dependence of the microwave nutation frequency on the strength of the spin coupling within the polaron pair was developed. Nutation experiments revealed an unusual pattern of the SCPP in RR-P3HT/PC 60 BM composites, from which the strength of the exchange interaction between the polymer˙ + and fullerene˙ - was extracted. In composites with low-efficient polymers the contribution of the SCPP to the in-phase ESE signal is high, while in composites with high-efficient polymers it is low. This finding can be used as a selection criterion of charge separation efficiency in the polymer/fullerene composites.

Ion species stratification within strong shocks in two-ion plasmas

DOE PAGES

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.; ...

2018-03-01

We report strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likelymore » contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Lastly, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M 4 for M»1.« less

Ion species stratification within strong shocks in two-ion plasmas

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

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.

We report strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likelymore » contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Lastly, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M 4 for M»1.« less

Ion species stratification within strong shocks in two-ion plasmas

NASA Astrophysics Data System (ADS)

Keenan, Brett D.; Simakov, Andrei N.; Taitano, William T.; Chacón, Luis

2018-03-01

Strong collisional shocks in multi-ion plasmas are featured in many environments, with Inertial Confinement Fusion (ICF) experiments being one prominent example. Recent work [Keenan et al., Phys. Rev. E 96, 053203 (2017)] answered in detail a number of outstanding questions concerning the kinetic structure of steady-state, planar plasma shocks, e.g., the shock width scaling by the Mach number, M. However, it did not discuss shock-driven ion-species stratification (e.g., relative concentration modification and temperature separation). These are important effects since many recent ICF experiments have evaded explanation by standard, single-fluid, radiation-hydrodynamic (rad-hydro) numerical simulations, and shock-driven fuel stratification likely contributes to this discrepancy. Employing the state-of-the-art Vlasov-Fokker-Planck code, iFP, along with multi-ion hydro simulations and semi-analytics, we quantify the ion stratification by planar shocks with the arbitrary Mach number and the relative species concentration for two-ion plasmas in terms of ion mass and charge ratios. In particular, for strong shocks, we find that the structure of the ion temperature separation has a nearly universal character across ion mass and charge ratios. Additionally, we find that the shock fronts are enriched with the lighter ion species and the enrichment scales as M4 for M ≫ 1.

Surface-Micromachined Microfluidic Devices

DOEpatents

Galambos, Paul C.; Okandan, Murat; Montague, Stephen; Smith, James H.; Paul, Phillip H.; Krygowski, Thomas W.; Allen, James J.; Nichols, Christopher A.; Jakubczak, II, Jerome F.

2004-09-28

Microfluidic devices are disclosed which can be manufactured using surface-micromachining. These devices utilize an electroosmotic force or an electromagnetic field to generate a flow of a fluid in a microchannel that is lined, at least in part, with silicon nitride. Additional electrodes can be provided within or about the microchannel for separating particular constituents in the fluid during the flow based on charge state or magnetic moment. The fluid can also be pressurized in the channel. The present invention has many different applications including electrokinetic pumping, chemical and biochemical analysis (e.g. based on electrophoresis or chromatography), conducting chemical reactions on a microscopic scale, and forming hydraulic actuators. Microfluidic devices are disclosed which can be manufactured using surface-micromachining. These devices utilize an electroosmotic force or an electromagnetic field to generate a flow of a fluid in a microchannel that is lined, at least in part, with silicon nitride. Additional electrodes can be provided within or about the microchannel for separating particular constituents in the fluid during the flow based on charge state or magnetic moment. The fluid can also be pressurized in the channel. The present invention has many different applications including electrokinetic pumping, chemical and biochemical analysis (e.g. based on electrophoresis or chromatography), conducting chemical reactions on a microscopic scale, and forming hydraulic actuators.

Supramolecular control of the spin-dependent dynamics of long-lived charge-separated states at the micellar interface as studied by magnetic field effect.

PubMed

Miura, Tomoaki

2013-05-30

Spin selectivity in long-lived charge separation at the micellar interface is studied using the magnetic field effect (MFE). An amphiphilic viologen is complexed with a nonionic surfactant to form a supramolecular acceptor cage, of which the size is controlled by the acceptor concentration, as confirmed by dynamic light scattering measurement. Photoinduced electron transfer (ET) from a guest polyaromatic molecule to the viologen moiety is observed spin-dependently with time-resolved fluorescence (trFL) and transient absorption (TA). A negative MFE on the radical yield is successfully observed, which indicates generation of singlet-born long-lived radical pair that is realized by supramolecular control of the donor-acceptor (D-A) distances. The dominance of the singlet-precursor MFE is sensitive to the acceptor concentration, which presumably affects the D-A distance as well as the cage size. However, theoretical analysis of the MFE gives large recombination rates of ca. 10(8) s(-1), which indicate the contribution of spin-allowed recombination of the pseudocontact radical pair generated by still active in-cage diffusion. Dependence of the viologen concentration and alkyl chain length on the recombination and escape dynamics is discussed in terms of precursor spin states and the microenvironments in the cage.

Charge Weld Effects on High Cycle Fatigue Behavior of a Hollow Extruded AA6082 Profile

NASA Astrophysics Data System (ADS)

Nanninga, N.; White, C.; Dickson, R.

2011-10-01

Fatigue properties of specimens taken from different locations along the length of a hollow AA6082 extrusion, where charge weld (interface between successive billets in multi-billet extrusions) properties and the degree of coring (accumulation of highly sheared billet surface material at back end of billet) are expected to vary, have been evaluated. The fatigue strength of transverse specimens containing charge welds is lower near the front of the extrusion where the charge weld separation is relatively large. The relationship between fatigue failure and charge weld separation appears to be directly related to charge weld properties. The lower fatigue properties of the specimens are likely associated with early overload fatigue failure along the charge weld interface. Coring does not appear to have significantly affected fatigue behavior.

Particle separation

NASA Technical Reports Server (NTRS)

Arnott, W. Patrick (Inventor); Chakrabarty, Rajan K. (Inventor); Moosmuller, Hans (Inventor)

2011-01-01

Embodiments of a method for selecting particles, such as based on their morphology, is disclosed. In a particular example, the particles are charged and acquire different amounts of charge, or have different charge distributions, based on their morphology. The particles are then sorted based on their flow properties. In a specific example, the particles are sorted using a differential mobility analyzer, which sorts particles, at least in part, based on their electrical mobility. Given a population of particles with similar electrical mobilities, the disclosed process can be used to sort particles based on the net charge carried by the particle, and thus, given the relationship between charge and morphology, separate the particles based on their morphology.

Particle separation

DOEpatents

Moosmuller, Hans [Reno, NV; Chakrabarty, Rajan K [Reno, NV; Arnott, W Patrick [Reno, NV

2011-04-26

Embodiments of a method for selecting particles, such as based on their morphology, is disclosed. In a particular example, the particles are charged and acquire different amounts of charge, or have different charge distributions, based on their morphology. The particles are then sorted based on their flow properties. In a specific example, the particles are sorted using a differential mobility analyzer, which sorts particles, at least in part, based on their electrical mobility. Given a population of particles with similar electrical mobilities, the disclosed process can be used to sort particles based on the net charge carried by the particle, and thus, given the relationship between charge and morphology, separate the particles based on their morphology.

The effect of cosmic rays on thunderstorm electricity

NASA Technical Reports Server (NTRS)

Bragin, Y. A.

1975-01-01

The inflow of charges of small ions, formed by cosmic rays, into thunderstorm cells is estimated on the basis of rocket measurements of ionic concentrations below 90 km. Out of the two processes that form the thunderstorm charge (generation and separation of charges), the former is supposed to be caused by cosmic rays, and the nature of separation is assumed to be the same as in other thunderstorm theories.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids

NASA Astrophysics Data System (ADS)

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K. G.

2009-05-01

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids.

PubMed

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K G

2009-05-28

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Electrochromic optical switching device

DOEpatents

Lampert, C.M.; Visco, S.J.

1992-08-25

An electrochromic cell is disclosed which comprises an electrochromic layer, a polymerizable organo-sulfur layer which comprises the counter electrode of the structure, and an ionically conductive electronically insulating material which comprises the separator between the electrodes. In a preferred embodiment, both the separator and the organo-sulfur electrode (in both its charged and uncharged states) are transparent either to visible light or to the entire solar spectrum. An electrochromic device is disclosed which comprises such electrodes and separator encased in glass plates on the inner surface of each of which is formed a transparent electrically conductive film in respective electrical contact with the electrodes which facilitates formation of an external electrical connection or contact to the electrodes of the device to permit electrical connection of the device to an external potential source. 3 figs.

Electrochromic optical switching device

DOEpatents

Lampert, Carl M.; Visco, Steven J.

1992-01-01

An electrochromic cell is disclosed which comprises an electrochromic layer, a polymerizable organo-sulfur layer which comprises the counter electrode of the structure, and an ionically conductive electronically insulating material which comprises the separator between the electrodes. In a preferred embodiment, both the separator and the organo-sulfur electrode (in both its charged and uncharged states) are transparent either to visible light or to the entire solar spectrum. An electrochromic device is disclosed which comprises such electrodes and separator encased in glass plates on the inner surface of each of which is formed a transparent electrically conductive film in respective electrical contact with the electrodes which facilitates formation of an external electrical connection or contact to the electrodes of the device to permit electrical connection of the device to an external potential source.

Impacts of side chain and excess energy on the charge photogeneration dynamics of low-bandgap copolymer-fullerene blends

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

Huo, Ming-Ming, E-mail: hithuomm@163.com; Zhang, Jian-Ping, E-mail: jpzhang@chem.ruc.edu.cn, E-mail: hjhzlz@iccas.ac.cn; Department of Chemistry, Renmin University of China, Beijing 100872

2014-02-28

Primary charge photogeneration dynamics in neat and fullerene-blended films of a pair of alternating benzo[1,2-b:4,5-b{sup ′}]dithiophene (BDT) and thieno[3,4-b]thiophene (TT) copolymers are comparatively studied by using near-infrared, time-resolved absorption (TA) spectroscopy under low excitation photon fluence. PBDTTT-E and PBDTTT-C, differed merely in the respective TT-substituents of ester (-E) and carbonyl (-C), show distinctly different charge photogeneration dynamics. The pair of neat PBDTTT films show exciton lifetimes of ∼0.1 ns and fluorescence quantum yields below 0.2%, as well as prominent excess-energy enhanced exciton dissociation. In addition, PBDTTT-C gives rise to >50% higher P{sup •+} yield than PBDTTT-E does irrespective to themore » excitation photon energy. Both PBDTTT-E:PC{sub 61}BM and PBDTTT-C:PC{sub 61}BM blends show subpicosecond exciton lifetimes and nearly unitary fluorescence quenching efficiency and, with respect to the former blend, the latter one shows substantially higher branching ratio of charge separated (CS) state over interfacial charge transfer (ICT) state, and hence more efficient exciton-to-CS conversion. For PBDTTT-C:PC{sub 61}BM, the ultrafast charge dynamics clearly show the processes of ICT-CS interconversion and P{sup •+} migration, which are possibly influenced by the ICT excess energy. However, such processes are relatively indistinctive in the case of PBDTTT-E:PC{sub 61}BM. The results strongly prove the importance of ICT dissociation in yielding free charges, and are discussed in terms of the film morphology and the precursory solution-phase macromolecular conformation.« less

Hierarchical FeTiO3-TiO2 hollow spheres for efficient simulated sunlight-driven water oxidation.

PubMed

Han, Taoran; Chen, Yajie; Tian, Guohui; Wang, Jian-Qiang; Ren, Zhiyu; Zhou, Wei; Fu, Honggang

2015-10-14

Oxygen generation is the key step for the photocatalytic overall water splitting and considered to be kinetically more challenging than hydrogen generation. Here, an effective water oxidation catalyst of hierarchical FeTiO3-TiO2 hollow spheres are prepared via a two-step sequential solvothermal processes and followed by thermal treatment. The existence of an effective heterointerface and built-in electric field in the surface space charge region in FeTiO3-TiO2 hollow spheres plays a positive role in promoting the separation of photoinduced electron-hole pairs. Surface photovoltage, transient-state photovoltage, fluorescence and electrochemical characterization are used to investigate the transfer process of photoinduced charge carriers. The photogenerated charge carriers in the hierarchical FeTiO3-TiO2 hollow spheres with a proper molar ratio display much higher separation efficiency and longer lifetime than those in the FeTiO3 alone. Moreover, it is suggested that the hierarchical porous hollow structure can contribute to the enhancement of light utilization, surface active sites and material transportation through the framework walls. This specific synergy significantly contributes to the remarkable improvement of the photocatalytic water oxidation activity of the hierarchical FeTiO3-TiO2 hollow spheres under simulated sunlight (AM1.5).

A Decaheme Cytochrome as a Molecular Electron Conduit in Dye-Sensitized Photoanodes

PubMed Central

Hwang, Ee Taek; Sheikh, Khizar; Orchard, Katherine L; Hojo, Daisuke; Radu, Valentin; Lee, Chong-Yong; Ainsworth, Emma; Lockwood, Colin; Gross, Manuela A; Adschiri, Tadafumi; Reisner, Erwin; Butt, Julea N; Jeuken, Lars J C

2015-01-01

In nature, charge recombination in light-harvesting reaction centers is minimized by efficient charge separation. Here, it is aimed to mimic this by coupling dye-sensitized TiO2 nanocrystals to a decaheme protein, MtrC from Shewanella oneidensis MR-1, where the 10 hemes of MtrC form a ≈7-nm-long molecular wire between the TiO2 and the underlying electrode. The system is assembled by forming a densely packed MtrC film on an ultra-flat gold electrode, followed by the adsorption of approximately 7 nm TiO2 nanocrystals that are modified with a phosphonated bipyridine Ru(II) dye (RuP). The step-by-step construction of the MtrC/TiO2 system is monitored with (photo)electrochemistry, quartz-crystal microbalance with dissipation (QCM-D), and atomic force microscopy (AFM). Photocurrents are dependent on the redox state of the MtrC, confirming that electrons are transferred from the TiO2 nanocrystals to the surface via the MtrC conduit. In other words, in these TiO2/MtrC hybrid photodiodes, MtrC traps the conduction-band electrons from TiO2 before transferring them to the electrode, creating a photobioelectrochemical system in which a redox protein is used to mimic the efficient charge separation found in biological photosystems. PMID:26180522

High open-circuit voltage small-molecule p-DTS(FBTTh 2 ) 2.ICBA bulk heterojunction solar cells – morphology, excited-state dynamics, and photovoltaic performance

DOE PAGES

Ko Kyaw, Aung Ko; Gehrig, Dominik; Zhang, Jie; ...

2014-11-27

The photovoltaic performance of bulk heterojunction solar cells using the solution-processable small molecule donor 7,7'-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b']dithiophene-2,6-diyl)bis(6-fluoro-4-(5'-hexyl-[2,2'-bithiophene]-5-yl)benzo[c][1,2,5]thiadiazole) (p-DTS(FBTTh 2) 2 in combination with indene-C60 bis-adduct (ICBA) as an acceptor is systematically optimized by altering the processing conditions. A high open-circuit voltage of 1 V, more than 0.2 V higher than that of a p-DTS(FBTTh 2) 2:PC 70BM blend, is achieved. However, the power conversion efficiency remains around 5% and thus is lower than ~8% previously reported for p-DTS(FBTTh 2) 2:PC 70BM. Transient absorption (TA) pump–probe spectroscopy over a wide spectral (Vis-NIR) and dynamic (fs to μs) range in combination with multivariate curvemore » resolution analysis of the TA data reveals that generation of free charges is more efficient in the blend with PC 70BM as an acceptor. In contrast, blends with ICBA create more coulombically bound interfacial charge transfer (CT) states, which recombine on the sub-nanosecond timescale by geminate recombination. Furthermore, the ns to μs charge carrier dynamics in p-DTS(FBTTh 2) 2:ICBA blends are only weakly intensity dependent implying a significant contribution of recombination from long-lived CT states and trapped charges, while those in p-DTS(FBTTh 2) 2:PC 70BM decay via an intensity-dependent recombination mechanism indicating that spatially separated (free) charge carriers are observed, which can be extracted as photocurrent from the device.« less

In vivo determination of steric and electrostatic exclusion of albumin in rat skin and skeletal muscle

PubMed Central

Gyenge, Christina C; Tenstad, Olav; Wiig, Helge

2003-01-01

In order to estimate the magnitude of electrostatic exclusion provided by the fixed negative charges of the skin and muscle interstitia of rat in vivo we measured the distribution volumes of two differently charged albumin probes within these tissues. An implanted osmotic pump was used to reach and maintain a steady-state extracellular concentration of a mixture containing two iodine-labelled probes: a charged-modified human serum albumin, cHSA (i.e. a positive probe, isoelectirc point (pI) = 7.6) and a native human serum albumin, HSA (i.e. a normally charged, negative probe, pI = 5.0). Steady-state tissue concentrations were achieved after intravenous infusion of probes for 5–7 days. At the end of this period the animals were nephrectomized and a bolus of 51Cr-EDTA was administered for estimating the extracellular volume. Plasma volumes were measured as 5-min distribution volume of 125I-HSA in separate experiments. The steady-state interstitial fluid concentrations of all probes were determined using nylon wicks implanted postmortem. Calculations of labelled probes were made for interstitial fluid volumes (Vi), extravascular albumin distribution volumes (Vav,a) and relative interstitial excluded volume fractions (Vex,a/Vi). We found that the positive probe is excluded from a significantly smaller fraction of the interstitium. Specifically, the average relative albumin exclusion fractions obtained were: 16% and 26% in skeletal muscle and 30% and 40% in skin, for cHSA and HSA, respectively. On average, the fixed negative charges of the interstitium are responsible for about 40% of the total albumin exclusion in skeletal muscle and 25% in the whole skin tissue and thus, contribute significantly to volume exclusion in these tissues. PMID:12937287

In vivo determination of steric and electrostatic exclusion of albumin in rat skin and skeletal muscle.

PubMed

Gyenge, Christina C; Tenstad, Olav; Wiig, Helge

2003-11-01

In order to estimate the magnitude of electrostatic exclusion provided by the fixed negative charges of the skin and muscle interstitia of rat in vivo we measured the distribution volumes of two differently charged albumin probes within these tissues. An implanted osmotic pump was used to reach and maintain a steady-state extracellular concentration of a mixture containing two iodine-labelled probes: a charged-modified human serum albumin, cHSA (i.e. a positive probe, isoelectirc point (pI) = 7.6) and a native human serum albumin, HSA (i.e. a normally charged, negative probe, pI = 5.0). Steady-state tissue concentrations were achieved after intravenous infusion of probes for 5-7 days. At the end of this period the animals were nephrectomized and a bolus of 51Cr-EDTA was administered for estimating the extracellular volume. Plasma volumes were measured as 5-min distribution volume of 125I-HSA in separate experiments. The steady-state interstitial fluid concentrations of all probes were determined using nylon wicks implanted postmortem. Calculations of labelled probes were made for interstitial fluid volumes (Vi), extravascular albumin distribution volumes (Vav,a) and relative interstitial excluded volume fractions (Vex,a/Vi). We found that the positive probe is excluded from a significantly smaller fraction of the interstitium. Specifically, the average relative albumin exclusion fractions obtained were: 16% and 26% in skeletal muscle and 30% and 40% in skin, for cHSA and HSA, respectively. On average, the fixed negative charges of the interstitium are responsible for about 40% of the total albumin exclusion in skeletal muscle and 25% in the whole skin tissue and thus, contribute significantly to volume exclusion in these tissues.

Search for Charged Higgs Bosons Produced via Vector Boson Fusion and Decaying into a Pair of W and Z Bosons Using p p Collisions at s = 13 TeV

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

Sirunyan, A. M.; Tumasyan, A.; Adam, W.

A search for charged Higgs bosons produced via vector boson fusion and decaying into W and Z bosons using proton-proton collisions at √s=13 TeV is presented. The data sample corresponds to an integrated luminosity of 15.2 fb -1 collected with the CMS detector in 2015 and 2016. The event selection requires three leptons (electrons or muons), two jets with large pseudorapidity separation and high dijet mass, and missing transverse momentum. Furthermore, the observation agrees with the standard model prediction. Limits on the vector boson fusion production cross section times branching fraction for new charged physical states are reported as amore » function of mass from 200 to 2000 GeV and interpreted in the context of Higgs triplet models.« less

Search for Charged Higgs Bosons Produced via Vector Boson Fusion and Decaying into a Pair of W and Z Bosons Using p p Collisions at s = 13 TeV

DOE PAGES

Sirunyan, A. M.; Tumasyan, A.; Adam, W.; ...

2017-10-04

A search for charged Higgs bosons produced via vector boson fusion and decaying into W and Z bosons using proton-proton collisions at √s=13 TeV is presented. The data sample corresponds to an integrated luminosity of 15.2 fb -1 collected with the CMS detector in 2015 and 2016. The event selection requires three leptons (electrons or muons), two jets with large pseudorapidity separation and high dijet mass, and missing transverse momentum. Furthermore, the observation agrees with the standard model prediction. Limits on the vector boson fusion production cross section times branching fraction for new charged physical states are reported as amore » function of mass from 200 to 2000 GeV and interpreted in the context of Higgs triplet models.« less

Oligomeric ferrocene rings

NASA Astrophysics Data System (ADS)

Inkpen, Michael S.; Scheerer, Stefan; Linseis, Michael; White, Andrew J. P.; Winter, Rainer F.; Albrecht, Tim; Long, Nicholas J.

2016-09-01

Cyclic oligomers comprising strongly interacting redox-active monomer units represent an unknown, yet highly desirable class of nanoscale materials. Here we describe the synthesis and properties of the first family of molecules belonging to this compound category—differently sized rings comprising only 1,1‧-disubstituted ferrocene units (cyclo[n], n = 5-7, 9). Due to the close proximity and connectivity of centres (covalent Cp-Cp linkages; Cp = cyclopentadienyl) solution voltammograms exhibit well-resolved, separated 1e- waves. Theoretical interrogations into correlations based on ring size and charge state are facilitated using values of the equilibrium potentials of these transitions, as well as their relative spacing. As the interaction free energies between the redox centres scale linearly with overall ring charge and in conjunction with fast intramolecular electron transfer (˜107 s-1), these molecules can be considered as uniformly charged nanorings (diameter ˜1-2 nm).

Search for Charged Higgs Bosons Produced via Vector Boson Fusion and Decaying into a Pair of W and Z Bosons Using p p Collisions at √{s }=13 TeV

NASA Astrophysics Data System (ADS)

Sirunyan, A. M.; Tumasyan, A.; Adam, W.; Asilar, E.; Bergauer, T.; Brandstetter, J.; Brondolin, E.; Dragicevic, M.; Erö, J.; Flechl, M.; Friedl, M.; Frühwirth, R.; Ghete, V. M.; Hartl, C.; Hörmann, N.; Hrubec, J.; Jeitler, M.; König, A.; Krätschmer, I.; Liko, D.; Matsushita, T.; Mikulec, I.; Rabady, D.; Rad, N.; Rahbaran, B.; Rohringer, H.; Schieck, J.; Strauss, J.; Waltenberger, W.; Wulz, C.-E.; Dvornikov, O.; Makarenko, V.; Mossolov, V.; Suarez Gonzalez, J.; Zykunov, V.; Shumeiko, N.; Alderweireldt, S.; De Wolf, E. A.; Janssen, X.; Lauwers, J.; Van De Klundert, M.; Van Haevermaet, H.; Van Mechelen, P.; Van Remortel, N.; Van Spilbeeck, A.; Abu Zeid, S.; Blekman, F.; D'Hondt, J.; Daci, N.; De Bruyn, I.; Deroover, K.; Lowette, S.; Moortgat, S.; Moreels, L.; Olbrechts, A.; Python, Q.; Skovpen, K.; Tavernier, S.; Van Doninck, W.; Van Mulders, P.; Van Parijs, I.; Brun, H.; Clerbaux, B.; De Lentdecker, G.; Delannoy, H.; Fasanella, G.; Favart, L.; Goldouzian, R.; Grebenyuk, A.; Karapostoli, G.; Lenzi, T.; Léonard, A.; Luetic, J.; Maerschalk, T.; Marinov, A.; Randle-conde, A.; Seva, T.; Vander Velde, C.; Vanlaer, P.; Vannerom, D.; Yonamine, R.; Zenoni, F.; Zhang, F.; Cornelis, T.; Dobur, D.; Fagot, A.; Gul, M.; Khvastunov, I.; Poyraz, D.; Salva, S.; Schöfbeck, R.; Tytgat, M.; Van Driessche, W.; Verbeke, W.; Zaganidis, N.; Bakhshiansohi, H.; Bondu, O.; Brochet, S.; Bruno, G.; Caudron, A.; De Visscher, S.; Delaere, C.; Delcourt, M.; Francois, B.; Giammanco, A.; Jafari, A.; Komm, M.; Krintiras, G.; Lemaitre, V.; Magitteri, A.; Mertens, A.; Musich, M.; Piotrzkowski, K.; Quertenmont, L.; Vidal Marono, M.; Wertz, S.; Beliy, N.; Aldá Júnior, W. L.; Alves, F. L.; Alves, G. A.; Brito, L.; Hensel, C.; Moraes, A.; Pol, M. E.; Rebello Teles, P.; Belchior Batista Das Chagas, E.; Carvalho, W.; Chinellato, J.; Custódio, A.; Da Costa, E. M.; Da Silveira, G. G.; De Jesus Damiao, D.; De Oliveira Martins, C.; Fonseca De Souza, S.; Huertas Guativa, L. M.; Malbouisson, H.; Matos Figueiredo, D.; Mora Herrera, C.; Mundim, L.; Nogima, H.; Prado Da Silva, W. L.; Santoro, A.; Sznajder, A.; Tonelli Manganote, E. J.; Torres Da Silva De Araujo, F.; Vilela Pereira, A.; Ahuja, S.; Bernardes, C. A.; Dogra, S.; Fernandez Perez Tomei, T. R.; Gregores, E. M.; Mercadante, P. G.; Moon, C. S.; Novaes, S. F.; Padula, Sandra S.; Romero Abad, D.; Ruiz Vargas, J. C.; Aleksandrov, A.; Hadjiiska, R.; Iaydjiev, P.; Rodozov, M.; Stoykova, S.; Sultanov, G.; Vutova, M.; Dimitrov, A.; Glushkov, I.; Litov, L.; Pavlov, B.; Petkov, P.; Fang, W.; Gao, X.; Ahmad, M.; Bian, J. G.; Chen, G. M.; Chen, H. S.; Chen, M.; Chen, Y.; Cheng, T.; Jiang, C. H.; Leggat, D.; Liu, Z.; Romeo, F.; Ruan, M.; Shaheen, S. M.; Spiezia, A.; Tao, J.; Wang, C.; Wang, Z.; Yazgan, E.; Zhang, H.; Zhao, J.; Ban, Y.; Chen, G.; Li, Q.; Liu, S.; Mao, Y.; Qian, S. J.; Wang, D.; Xu, Z.; Avila, C.; Cabrera, A.; Chaparro Sierra, L. F.; Florez, C.; Gomez, J. P.; González Hernández, C. F.; Ruiz Alvarez, J. D.; Sanabria, J. C.; Godinovic, N.; Lelas, D.; Puljak, I.; Ribeiro Cipriano, P. M.; Sculac, T.; Antunovic, Z.; Kovac, M.; Brigljevic, V.; Ferencek, D.; Kadija, K.; Mesic, B.; Susa, T.; Ather, M. W.; Attikis, A.; Mavromanolakis, G.; Mousa, J.; Nicolaou, C.; Ptochos, F.; Razis, P. A.; Rykaczewski, H.; Finger, M.; Finger, M.; Carrera Jarrin, E.; Abdelalim, A. A.; Mohammed, Y.; Salama, E.; Kadastik, M.; Perrini, L.; Raidal, M.; Tiko, A.; Veelken, C.; Eerola, P.; Pekkanen, J.; Voutilainen, M.; Härkönen, J.; Järvinen, T.; Karimäki, V.; Kinnunen, R.; Lampén, T.; Lassila-Perini, K.; Lehti, S.; Lindén, T.; Luukka, P.; Tuominiemi, J.; Tuovinen, E.; Wendland, L.; Talvitie, J.; Tuuva, T.; Besancon, M.; Couderc, F.; Dejardin, M.; Denegri, D.; Fabbro, B.; Faure, J. L.; Favaro, C.; Ferri, F.; Ganjour, S.; Ghosh, S.; Givernaud, A.; Gras, P.; Hamel de Monchenault, G.; Jarry, P.; Kucher, I.; Locci, E.; Machet, M.; Malcles, J.; Rander, J.; Rosowsky, A.; Titov, M.; Abdulsalam, A.; Antropov, I.; Baffioni, S.; Beaudette, F.; Busson, P.; Cadamuro, L.; Chapon, E.; Charlot, C.; Davignon, O.; Granier de Cassagnac, R.; Jo, M.; Lisniak, S.; Lobanov, A.; Miné, P.; Nguyen, M.; Ochando, C.; Ortona, G.; Paganini, P.; Pigard, P.; Regnard, S.; Salerno, R.; Sirois, Y.; Stahl Leiton, A. G.; Strebler, T.; Yilmaz, Y.; Zabi, A.; Zghiche, A.; Agram, J.-L.; Andrea, J.; Bloch, D.; Brom, J.-M.; Buttignol, M.; Chabert, E. C.; Chanon, N.; Collard, C.; Conte, E.; Coubez, X.; Fontaine, J.-C.; Gelé, D.; Goerlach, U.; Le Bihan, A.-C.; Van Hove, P.; Gadrat, S.; Beauceron, S.; Bernet, C.; Boudoul, G.; Carrillo Montoya, C. A.; Chierici, R.; Contardo, D.; Courbon, B.; Depasse, P.; El Mamouni, H.; Fay, J.; Finco, L.; Gascon, S.; Gouzevitch, M.; Grenier, G.; Ille, B.; Lagarde, F.; Laktineh, I. B.; Lethuillier, M.; Mirabito, L.; Pequegnot, A. L.; Perries, S.; Popov, A.; Sordini, V.; Vander Donckt, M.; Verdier, P.; Viret, S.; Khvedelidze, A.; Tsamalaidze, Z.; Autermann, C.; Beranek, S.; Feld, L.; Kiesel, M. K.; Klein, K.; Lipinski, M.; Preuten, M.; Schomakers, C.; Schulz, J.; Verlage, T.; Albert, A.; Brodski, M.; Dietz-Laursonn, E.; Duchardt, D.; Endres, M.; Erdmann, M.; Erdweg, S.; Esch, T.; Fischer, R.; Güth, A.; Hamer, M.; Hebbeker, T.; Heidemann, C.; Hoepfner, K.; Knutzen, S.; Merschmeyer, M.; Meyer, A.; Millet, P.; Mukherjee, S.; Olschewski, M.; Padeken, K.; Pook, T.; Radziej, M.; Reithler, H.; Rieger, M.; Scheuch, F.; Sonnenschein, L.; Teyssier, D.; Thüer, S.; Cherepanov, V.; Flügge, G.; Kargoll, B.; Kress, T.; Künsken, A.; Lingemann, J.; Müller, T.; Nehrkorn, A.; Nowack, A.; Pistone, C.; Pooth, O.; Stahl, A.; Aldaya Martin, M.; Arndt, T.; Asawatangtrakuldee, C.; Beernaert, K.; Behnke, O.; Behrens, U.; Bin Anuar, A. A.; Borras, K.; Campbell, A.; Connor, P.; Contreras-Campana, C.; Costanza, F.; Diez Pardos, C.; Dolinska, G.; Eckerlin, G.; Eckstein, D.; Eichhorn, T.; Eren, E.; Gallo, E.; Garay Garcia, J.; Geiser, A.; Gizhko, A.; Grados Luyando, J. M.; Grohsjean, A.; Gunnellini, P.; Harb, A.; Hauk, J.; Hempel, M.; Jung, H.; Kalogeropoulos, A.; Karacheban, O.; Kasemann, M.; Keaveney, J.; Kleinwort, C.; Korol, I.; Krücker, D.; Lange, W.; Lelek, A.; Lenz, T.; Leonard, J.; Lipka, K.; Lohmann, W.; Mankel, R.; Melzer-Pellmann, I.-A.; Meyer, A. B.; Mittag, G.; Mnich, J.; Mussgiller, A.; Ntomari, E.; Pitzl, D.; Placakyte, R.; Raspereza, A.; Roland, B.; Sahin, M. Ö.; Saxena, P.; Schoerner-Sadenius, T.; Spannagel, S.; Stefaniuk, N.; Van Onsem, G. P.; Walsh, R.; Wissing, C.; Blobel, V.; Centis Vignali, M.; Draeger, A. R.; Dreyer, T.; Garutti, E.; Gonzalez, D.; Haller, J.; Hoffmann, M.; Junkes, A.; Klanner, R.; Kogler, R.; Kovalchuk, N.; Kurz, S.; Lapsien, T.; Marchesini, I.; Marconi, D.; Meyer, M.; Niedziela, M.; Nowatschin, D.; Pantaleo, F.; Peiffer, T.; Perieanu, A.; Scharf, C.; Schleper, P.; Schmidt, A.; Schumann, S.; Schwandt, J.; Sonneveld, J.; Stadie, H.; Steinbrück, G.; Stober, F. M.; Stöver, M.; Tholen, H.; Troendle, D.; Usai, E.; Vanelderen, L.; Vanhoefer, A.; Vormwald, B.; Akbiyik, M.; Barth, C.; Baur, S.; Baus, C.; Berger, J.; Butz, E.; Caspart, R.; Chwalek, T.; Colombo, F.; De Boer, W.; Dierlamm, A.; Fink, S.; Freund, B.; Friese, R.; Giffels, M.; Gilbert, A.; Goldenzweig, P.; Haitz, D.; Hartmann, F.; Heindl, S. M.; Husemann, U.; Kassel, F.; Katkov, I.; Kudella, S.; Mildner, H.; Mozer, M. U.; Müller, Th.; Plagge, M.; Quast, G.; Rabbertz, K.; Röcker, S.; Roscher, F.; Schröder, M.; Shvetsov, I.; Sieber, G.; Simonis, H. J.; Ulrich, R.; Wayand, S.; Weber, M.; Weiler, T.; Williamson, S.; Wöhrmann, C.; Wolf, R.; Anagnostou, G.; Daskalakis, G.; Geralis, T.; Giakoumopoulou, V. A.; Kyriakis, A.; Loukas, D.; Topsis-Giotis, I.; Kesisoglou, S.; Panagiotou, A.; Saoulidou, N.; Tziaferi, E.; Kousouris, K.; Evangelou, I.; Flouris, G.; Foudas, C.; Kokkas, P.; Loukas, N.; Manthos, N.; Papadopoulos, I.; Paradas, E.; Triantis, F. A.; Filipovic, N.; Pasztor, G.; Bencze, G.; Hajdu, C.; Horvath, D.; Sikler, F.; Veszpremi, V.; Vesztergombi, G.; Zsigmond, A. J.; Beni, N.; Czellar, S.; Karancsi, J.; Makovec, A.; Molnar, J.; Szillasi, Z.; Bartók, M.; Raics, P.; Trocsanyi, Z. L.; Ujvari, B.; Choudhury, S.; Komaragiri, J. R.; Bahinipati, S.; Bhowmik, S.; Mal, P.; Mandal, K.; Nayak, A.; Sahoo, D. K.; Sahoo, N.; Swain, S. K.; Bansal, S.; Beri, S. B.; Bhatnagar, V.; Chawla, R.; Bhawandeep, U.; Kalsi, A. K.; Kaur, A.; Kaur, M.; Kumar, R.; Kumari, P.; Mehta, A.; Mittal, M.; Singh, J. B.; Walia, G.; Kumar, Ashok; Bhardwaj, A.; Choudhary, B. C.; Garg, R. B.; Keshri, S.; Kumar, A.; Malhotra, S.; Naimuddin, M.; Ranjan, K.; Sharma, R.; Sharma, V.; Bhattacharya, R.; Bhattacharya, S.; Chatterjee, K.; Dey, S.; Dutt, S.; Dutta, S.; Ghosh, S.; Majumdar, N.; Modak, A.; Mondal, K.; Mukhopadhyay, S.; Nandan, S.; Purohit, A.; Roy, A.; Roy, D.; Roy Chowdhury, S.; Sarkar, S.; Sharan, M.; Thakur, S.; Behera, P. K.; Chudasama, R.; Dutta, D.; Jha, V.; Kumar, V.; Mohanty, A. K.; Netrakanti, P. K.; Pant, L. M.; Shukla, P.; Topkar, A.; Aziz, T.; Dugad, S.; Kole, G.; Mahakud, B.; Mitra, S.; Mohanty, G. B.; Parida, B.; Sur, N.; Sutar, B.; Banerjee, S.; Dewanjee, R. K.; Ganguly, S.; Guchait, M.; Jain, Sa.; Kumar, S.; Maity, M.; Majumder, G.; Mazumdar, K.; Sarkar, T.; Wickramage, N.; Chauhan, S.; Dube, S.; Hegde, V.; Kapoor, A.; Kothekar, K.; Pandey, S.; Rane, A.; Sharma, S.; Chenarani, S.; Eskandari Tadavani, E.; Etesami, S. M.; Khakzad, M.; Mohammadi Najafabadi, M.; Naseri, M.; Paktinat Mehdiabadi, S.; Rezaei Hosseinabadi, F.; Safarzadeh, B.; Zeinali, M.; Felcini, M.; Grunewald, M.; Abbrescia, M.; Calabria, C.; Caputo, C.; Colaleo, A.; Creanza, D.; Cristella, L.; De Filippis, N.; De Palma, M.; Fiore, L.; Iaselli, G.; Maggi, G.; Maggi, M.; Miniello, G.; My, S.; Nuzzo, S.; Pompili, A.; Pugliese, G.; Radogna, R.; Ranieri, A.; Selvaggi, G.; Sharma, A.; Silvestris, L.; Venditti, R.; Verwilligen, P.; Abbiendi, G.; Battilana, C.; Bonacorsi, D.; Braibant-Giacomelli, S.; Brigliadori, L.; Campanini, R.; Capiluppi, P.; Castro, A.; Cavallo, F. R.; Chhibra, S. S.; Codispoti, G.; Cuffiani, M.; Dallavalle, G. M.; Fabbri, F.; Fanfani, A.; Fasanella, D.; Giacomelli, P.; Grandi, C.; Guiducci, L.; Marcellini, S.; Masetti, G.; Montanari, A.; Navarria, F. L.; Perrotta, A.; Rossi, A. M.; Rovelli, T.; Siroli, G. 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C.; Kubota, Y.; Lesko, Z.; Mans, J.; Nourbakhsh, S.; Ruckstuhl, N.; Rusack, R.; Tambe, N.; Turkewitz, J.; Acosta, J. G.; Oliveros, S.; Avdeeva, E.; Bloom, K.; Claes, D. R.; Fangmeier, C.; Gonzalez Suarez, R.; Kamalieddin, R.; Kravchenko, I.; Malta Rodrigues, A.; Monroy, J.; Siado, J. E.; Snow, G. R.; Stieger, B.; Alyari, M.; Dolen, J.; Godshalk, A.; Harrington, C.; Iashvili, I.; Nguyen, D.; Parker, A.; Rappoccio, S.; Roozbahani, B.; Alverson, G.; Barberis, E.; Hortiangtham, A.; Massironi, A.; Morse, D. M.; Nash, D.; Orimoto, T.; Teixeira De Lima, R.; Trocino, D.; Wang, R.-J.; Wood, D.; Bhattacharya, S.; Charaf, O.; Hahn, K. A.; Mucia, N.; Odell, N.; Pollack, B.; Schmitt, M. H.; Sung, K.; Trovato, M.; Velasco, M.; Dev, N.; Hildreth, M.; Hurtado Anampa, K.; Jessop, C.; Karmgard, D. 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R.; Faulkner, J.; Gurpinar, E.; Kunori, S.; Lamichhane, K.; Lee, S. W.; Libeiro, T.; Peltola, T.; Undleeb, S.; Volobouev, I.; Wang, Z.; Greene, S.; Gurrola, A.; Janjam, R.; Johns, W.; Maguire, C.; Melo, A.; Ni, H.; Sheldon, P.; Tuo, S.; Velkovska, J.; Xu, Q.; Arenton, M. W.; Barria, P.; Cox, B.; Hirosky, R.; Ledovskoy, A.; Li, H.; Neu, C.; Sinthuprasith, T.; Sun, X.; Wang, Y.; Wolfe, E.; Xia, F.; Clarke, C.; Harr, R.; Karchin, P. E.; Sturdy, J.; Zaleski, S.; Belknap, D. A.; Buchanan, J.; Caillol, C.; Dasu, S.; Dodd, L.; Duric, S.; Gomber, B.; Grothe, M.; Herndon, M.; Hervé, A.; Hussain, U.; Klabbers, P.; Lanaro, A.; Levine, A.; Long, K.; Loveless, R.; Pierro, G. A.; Polese, G.; Ruggles, T.; Savin, A.; Smith, N.; Smith, W. H.; Taylor, D.; Woods, N.; CMS Collaboration

2017-10-01

A search for charged Higgs bosons produced via vector boson fusion and decaying into W and Z bosons using proton-proton collisions at √{s }=13 TeV is presented. The data sample corresponds to an integrated luminosity of 15.2 fb-1 collected with the CMS detector in 2015 and 2016. The event selection requires three leptons (electrons or muons), two jets with large pseudorapidity separation and high dijet mass, and missing transverse momentum. The observation agrees with the standard model prediction. Limits on the vector boson fusion production cross section times branching fraction for new charged physical states are reported as a function of mass from 200 to 2000 GeV and interpreted in the context of Higgs triplet models.

Search for Charged Higgs Bosons Produced via Vector Boson Fusion and Decaying into a Pair of W and Z Bosons Using pp Collisions at sqrt[s]=13  TeV.

PubMed

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Cali, I A; D'Alfonso, M; Demiragli, Z; Gomez Ceballos, G; Goncharov, M; Hsu, D; Iiyama, Y; Innocenti, G M; Klute, M; Kovalskyi, D; Krajczar, K; Lai, Y S; Lee, Y-J; Levin, A; Luckey, P D; Maier, B; Marini, A C; Mcginn, C; Mironov, C; Narayanan, S; Niu, X; Paus, C; Roland, C; Roland, G; Salfeld-Nebgen, J; Stephans, G S F; Tatar, K; Velicanu, D; Wang, J; Wang, T W; Wyslouch, B; Benvenuti, A C; Chatterjee, R M; Evans, A; Hansen, P; Kalafut, S; Kao, S C; Kubota, Y; Lesko, Z; Mans, J; Nourbakhsh, S; Ruckstuhl, N; Rusack, R; Tambe, N; Turkewitz, J; Acosta, J G; Oliveros, S; Avdeeva, E; Bloom, K; Claes, D R; Fangmeier, C; Gonzalez Suarez, R; Kamalieddin, R; Kravchenko, I; Malta Rodrigues, A; Monroy, J; Siado, J E; Snow, G R; Stieger, B; Alyari, M; Dolen, J; Godshalk, A; Harrington, C; Iashvili, I; Nguyen, D; Parker, A; Rappoccio, S; Roozbahani, B; Alverson, G; Barberis, E; Hortiangtham, A; Massironi, A; Morse, D M; Nash, D; Orimoto, T; Teixeira De Lima, R; Trocino, D; Wang, R-J; Wood, D; Bhattacharya, S; Charaf, O; Hahn, K A; Mucia, N; Odell, N; Pollack, B; Schmitt, M H; Sung, K; Trovato, M; Velasco, M; Dev, N; Hildreth, M; Hurtado Anampa, K; Jessop, C; Karmgard, D J; Kellams, N; Lannon, K; Marinelli, N; Meng, F; Mueller, C; Musienko, Y; Planer, M; Reinsvold, A; Ruchti, R; Rupprecht, N; Smith, G; Taroni, S; Wayne, M; Wolf, M; Woodard, A; Alimena, J; Antonelli, L; Bylsma, B; Durkin, L S; Flowers, S; Francis, B; Hart, A; Hill, C; Ji, W; Liu, B; Luo, W; Puigh, D; Winer, B L; Wulsin, H W; Cooperstein, S; Driga, O; Elmer, P; Hardenbrook, J; Hebda, P; Lange, D; Luo, J; Marlow, D; Medvedeva, T; Mei, K; Ojalvo, I; Olsen, J; Palmer, C; Piroué, P; Stickland, D; Svyatkovskiy, A; Tully, C; Malik, S; Barker, A; Barnes, V E; Folgueras, S; Gutay, L; Jha, M K; Jones, M; Jung, A W; Khatiwada, A; Miller, D H; Neumeister, N; Schulte, J F; Sun, J; Wang, F; Xie, W; Parashar, N; Stupak, J; Adair, A; Akgun, B; Chen, Z; Ecklund, K M; Geurts, F J M; Guilbaud, M; Li, W; Michlin, B; Northup, M; Padley, B P; Roberts, J; Rorie, J; Tu, Z; Zabel, J; Betchart, B; Bodek, A; de Barbaro, P; Demina, R; Duh, Y T; Ferbel, T; Galanti, M; Garcia-Bellido, A; Han, J; Hindrichs, O; Khukhunaishvili, A; Lo, K H; Tan, P; Verzetti, M; Agapitos, A; Chou, J P; Gershtein, Y; Gómez Espinosa, T A; Halkiadakis, E; Heindl, M; Hughes, E; Kaplan, S; Kunnawalkam Elayavalli, R; Kyriacou, S; Lath, A; Montalvo, R; Nash, K; Osherson, M; Saka, H; Salur, S; Schnetzer, S; Sheffield, D; Somalwar, S; Stone, R; Thomas, S; Thomassen, P; Walker, M; Delannoy, A G; Foerster, M; Heideman, J; Riley, G; Rose, K; Spanier, S; Thapa, K; Bouhali, O; Celik, A; Dalchenko, M; De Mattia, M; Delgado, A; Dildick, S; Eusebi, R; Gilmore, J; Huang, T; Juska, E; Kamon, T; Mueller, R; Pakhotin, Y; Patel, R; Perloff, A; Perniè, L; Rathjens, D; Safonov, A; Tatarinov, A; Ulmer, K A; Akchurin, N; Damgov, J; De Guio, F; Dragoiu, C; Dudero, P R; Faulkner, J; Gurpinar, E; Kunori, S; Lamichhane, K; Lee, S W; Libeiro, T; Peltola, T; Undleeb, S; Volobouev, I; Wang, Z; Greene, S; Gurrola, A; Janjam, R; Johns, W; Maguire, C; Melo, A; Ni, H; Sheldon, P; Tuo, S; Velkovska, J; Xu, Q; Arenton, M W; Barria, P; Cox, B; Hirosky, R; Ledovskoy, A; Li, H; Neu, C; Sinthuprasith, T; Sun, X; Wang, Y; Wolfe, E; Xia, F; Clarke, C; Harr, R; Karchin, P E; Sturdy, J; Zaleski, S; Belknap, D A; Buchanan, J; Caillol, C; Dasu, S; Dodd, L; Duric, S; Gomber, B; Grothe, M; Herndon, M; Hervé, A; Hussain, U; Klabbers, P; Lanaro, A; Levine, A; Long, K; Loveless, R; Pierro, G A; Polese, G; Ruggles, T; Savin, A; Smith, N; Smith, W H; Taylor, D; Woods, N

2017-10-06

A search for charged Higgs bosons produced via vector boson fusion and decaying into W and Z bosons using proton-proton collisions at sqrt[s]=13  TeV is presented. The data sample corresponds to an integrated luminosity of 15.2  fb^{-1} collected with the CMS detector in 2015 and 2016. The event selection requires three leptons (electrons or muons), two jets with large pseudorapidity separation and high dijet mass, and missing transverse momentum. The observation agrees with the standard model prediction. Limits on the vector boson fusion production cross section times branching fraction for new charged physical states are reported as a function of mass from 200 to 2000 GeV and interpreted in the context of Higgs triplet models.

Modular Homogeneous Chromophore–Catalyst Assemblies

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

Mulfort, Karen L.; Utschig, Lisa M.

2016-05-17

Photosynthetic reaction center (RC) proteins convert incident solar energy to chemical energy through a network of molecular cofactors which have been evolutionarily tuned to couple efficient light-harvesting, directional electron transfer, and long-lived charge separation with secondary reaction sequences. These molecular cofactors are embedded within a complex protein environment which precisely positions each cofactor in optimal geometries along efficient electron transfer pathways with localized protein environments facilitating sequential and accumulative charge transfer. By contrast, it is difficult to approach a similar level of structural complexity in synthetic architectures for solar energy conversion. However, by using appropriate self-assembly strategies, we anticipate thatmore » molecular modules, which are independently synthesized and optimized for either light-harvesting or redox catalysis, can be organized into spatial arrangements that functionally mimic natural photosynthesis. In this Account, we describe a modular approach to new structural designs for artificial photosynthesis which is largely inspired by photosynthetic RC proteins. We focus on recent work from our lab which uses molecular modules for light-harvesting or proton reduction catalysis in different coordination geometries and different platforms, spanning from discrete supramolecular assemblies to molecule–nanoparticle hybrids to protein-based biohybrids. Molecular modules are particularly amenable to high-resolution characterization of the ground and excited state of each module using a variety of physical techniques; such spectroscopic interrogation helps our understanding of primary artificial photosynthetic mechanisms. In particular, we discuss the use of transient optical spectroscopy, EPR, and X-ray scattering techniques to elucidate dynamic structural behavior and light-induced kinetics and the impact on photocatalytic mechanism. Two different coordination geometries of supramolecular photocatalyst based on the [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) light-harvesting module with cobaloxime-based catalyst module are compared, with progress in stabilizing photoinduced charge separation identified. These same modules embedded in the small electron transfer protein ferredoxin exhibit much longer charge-separation, enabled by stepwise electron transfer through the native [2Fe-2S] cofactor. We anticipate that the use of interchangeable, molecular modules which can interact in different coordination geometries or within entirely different structural platforms will provide important fundamental insights into the effect of environment on parameters such as electron transfer and charge separation, and ultimately drive more efficient designs for artificial photosynthesis.« less

Do diabetes group visits lead to lower medical care charges?

PubMed

Clancy, Dawn E; Dismuke, Clara E; Magruder, Kathryn Marley; Simpson, Kit N; Bradford, David

2008-01-01

To evaluate whether attending diabetes group visits (GVs) leads to lower medical care charges for inadequately insured patients with type 2 diabetes mellitus (DM). Randomized controlled clinical trial. Data were abstracted from financial records for 186 patients with uncontrolled type 2 DM randomized to receive care in GVs or usual care for 12 months. Mann-Whitney tests for differences of means for outpatient visits (primary and specialty care), emergency department (ED) visits, and inpatient stays were performed. Separate charge models were developed for primary and specialty outpatient visits. Because GV adherence is potentially dependent on unobserved patient characteristics, treatment effect models of outpatient charges and specialty care visits were estimated using maximum likelihood methods. Mann-Whitney test results indicated that GV patients had reduced ED and total charges but more outpatient charges than usual care patients. Ordinary least squares estimations confirmed that GVs increased outpatient visit charges; however, controlling for endogeneity by estimating a treatment effect model of outpatient visit charges showed that GVs statistically significantly reduced outpatient charges (P <.001). Estimation of a separate treatment effect model of specialty care visits confirmed that GV effects on outpatient visit charges occurred via a reduction in specialty care visits. After controlling for endogeneity via estimation of a treatment effect model, GVs statistically significantly reduced outpatient visit charges. Estimation of a separate treatment effect model of specialty care visits indicated that GVs likely substitute for more expensive specialty care visits.

Constructions of secure entanglement channels assisted by quantum dots inside single-sided optical cavities

NASA Astrophysics Data System (ADS)

Heo, Jino; Kang, Min-Sung; Hong, Chang-Ho; Choi, Seong-Gon; Hong, Jong-Phil

2017-08-01

We propose quantum information processing schemes to generate and swap entangled states based on the interactions between flying photons and quantum dots (QDs) confined within optical cavities for quantum communication. To produce and distribute entangled states (Bell and Greenberger-Horne-Zeilinger [GHZ] states) between the photonic qubits of flying photons of consumers (Alice and Bob) and electron-spin qubits of a provider (trust center, or TC), the TC employs the interactions of the QD-cavity system, which is composed of a charged QD (negatively charged exciton) inside a single-sided cavity. Subsequently, the TC constructs an entanglement channel (Bell state and 4-qubit GHZ state) to link one consumer with another through entanglement swapping, which can be realized to exploit a probe photon with interactions of the QD-cavity systems and single-qubit measurements without Bell state measurement, for quantum communication between consumers. Consequently, the TC, which has quantum nodes (QD-cavity systems), can accomplish constructing the entanglement channel (authenticated channel) between two separated consumers from the distributions of entangled states and entanglement swapping. Furthermore, our schemes using QD-cavity systems, which are feasible with a certain probability of success and high fidelity, can be experimentally implemented with technology currently in use.

Trap and transfer. two-step hole injection across the Sb2S3/CuSCN interface in solid-state solar cells.

PubMed

Christians, Jeffrey A; Kamat, Prashant V

2013-09-24

In solid-state semiconductor-sensitized solar cells, commonly known as extremely thin absorber (ETA) or solid-state quantum-dot-sensitized solar cells (QDSCs), transfer of photogenerated holes from the absorber species to the p-type hole conductor plays a critical role in the charge separation process. Using Sb2S3 (absorber) and CuSCN (hole conductor), we have constructed ETA solar cells exhibiting a power conversion efficiency of 3.3%. The hole transfer from excited Sb2S3 into CuSCN, which limits the overall power conversion efficiency of these solar cells, is now independently studied using transient absorption spectroscopy. In the Sb2S3 absorber layer, photogenerated holes are rapidly localized on the sulfur atoms of the crystal lattice, forming a sulfide radical (S(-•)) species. This trapped hole is transferred from the Sb2S3 absorber to the CuSCN hole conductor with an exponential time constant of 1680 ps. This process was monitored through the spectroscopic signal seen for the S(-•) species in Sb2S3, providing direct evidence for the hole transfer dynamics in ETA solar cells. Elucidation of the hole transfer mechanism from Sb2S3 to CuSCN represents a significant step toward understanding charge separation in Sb2S3 solar cells and provides insight into the design of new architectures for higher efficiency devices.

The financial impact of robotic technology for partial and radical nephrectomy.

PubMed

Kates, Max; Ball, Mark W; Patel, Hiten D; Gorin, Michael A; Pierorazio, Phillip M; Allaf, Mohamad E

2015-03-01

We sought to evaluate the financial impact of robotic technology for partial nephrectomy (PN) and radical nephrectomy (RN) in the state of Maryland. The Maryland Health Services Cost Review Commission (HSCRC) documents all acute care hospital charges data. This database was queried for patients who underwent laparoscopic or robot-assisted RN and PN from 2008 to 2012. Total hospital charge, subcharge, and length of stay (LOS) were analyzed separately for RN and PN. Overall, 2834 patients were identified. Of those, 282 were laparoscopic PN (LPN), 1078 robot-assisted PN (RPN), 1098 laparoscopic RN (LRN), and 376 robot-assisted RN (RRN). For PN, the total hospital charge was $19,062 for LPN and $18,255 for RPN (P=0.138), with a charge savings of $807 per case in favor of robotics. For RN, the total hospital charge was $23,391 for RRN and $18,280 for LRN (P=0.004), with a charge premium of $5111 for robotic cases. LOS was shorter for RPN compared with LPN (2.51 vs 2.99 days, P<0.0001) and for RRN compared with LRN (3.52 vs 3.98, P=0.0498). RPN is associated with lower hospital charges than LPN, while RRN is associated with higher hospital charges than LRN. Savings for RPN are driven by decreased room and board charge, while the premium for RRN is driven by higher operating room and supply charges. Because RRN use is increasing, the financial implications of RRN use for routine cases warrants further study.

Simulations to Predict the Phase Behavior and Structure of Multipolar Colloidal Particles

NASA Astrophysics Data System (ADS)

Rutkowski, David Matthew

Colloidal particles with anisotropic charge distributions can assemble into a number of interesting structures including chains, lattices and micelles that could be useful in biotechnology, optics and electronics. The goal of this work is to understand how the properties of the colloidal particles, such as their charge distribution or shape, affect the selfassembly and phase behavior of collections of such particles. The specific aim of this work is to understand how the separation between a pair of oppositely signed charges affects the phase behavior and structure of assemblies of colloidal particles. To examine these particles, we have used both discontinuous molecular dynamics (DMD) and Monte Carlo (MC) simulation techniques. In our first study of colloidal particles with finite charge separation, we simulate systems of 2-D colloidal rods with four possible charge separations. Our simulations show that the charge separation does indeed have a large effect on the phase behavior as can be seen in the phase diagrams we construct for these four systems in the area fraction-reduced temperature plane. The phase diagrams delineate the boundaries between isotropic fluid, string-fluid and percolated fluid for all systems considered. In particular, we find that coarse gel-like structures tend to form at large charge separations while denser aggregates form at small charge separations, suggesting a route to forming low volume gels by focusing on systems with large charge separations. Next we examine systems of circular particles with four embedded charges of alternating sign fixed to a triangular lattice. This system is found to form a limit periodic structure, a theoretical structure with an infinite number of phase transitions, under specific conditions. The limit-periodic structure only forms when the rotation of the particles in the system is restricted to increments of pi/3. When the rotation is restricted to increments of th/6 or the rotation is continuous, related structures form including a striped phase and a phase with nematic order. Neither the distance from the point charges to the center of the particle nor the angle between the charges influences whether the system forms a limit-periodic structure, suggesting that point quadrupoles may also be able to form limit-periodic structures. Results from these simulations will likely aid in the quest to find an experimental realization of a limit-periodic structure. Next we examine the effect of charge separation on the self-assembly of systems of 2-D colloidal particles with off-center extended dipoles. We simulate systems with both small and large charge separations for a set of displacements of the dipole from the particle center. Upon cooling, these particles self-assemble into closed, cyclic structures at large displacements including dimers, triangular shapes and square shapes, and chain-like structures at small displacements. At extremely low temperatures, the cyclic structures form interesting lattices with particles of similar chirality grouped together. Results from this work could aid in the experimental construction of open lattice-like structures that could find use in photonic applications. Finally, we present work in collaboration with Drs. Bhuvnesh Bharti and Orlin Velev in which we investigate how the surface coverage affects the self-assembly of systems of Janus particles coated with both an iron oxide and fatty acid chain layer. We model these particles by decorating a sphere with evenly dispersed points that interact with points on other spheres through square-well interactions. The interactions are designed to mimic specific coverage values for the iron oxide/fatty acid chain layer. Structures similar to those found in experiment form readily in the simulations. The number of clusters formed as a function of surface coverage agrees well with experiment. The aggregation behavior of these novel particles can therefore, be described by a relatively simple model.

Cherenkov and scintillation light separation on the CheSS experiment

NASA Astrophysics Data System (ADS)

Caravaca, Javier; Land, Benjamin; Descamps, Freija; Orebi Gann, Gabriel D.

2016-09-01

Separation of the scintillation and Cherenkov light produced in liquid scintillators enables outstanding capabilities for future particle detectors, the most relevant being: particle directionality information in a low energy threshold detector and improved particle identification. The CheSS experiment uses an array of small, fast photomultipliers (PMTs) and state-of-the-art electronics to demonstrate the reconstruction of a Cherenkov ring in liquid scintillator using two techniques: based on the photon density and using the photon hit time information. A charged particle ionizing a scintillation medium produces a prompt Cherenkov cone and late isotropic scintillation light, typically delayed by several ns. The fast response of our PMTs and DAQ provides a precision well below the ns level, making possible the time separation. Furthermore, the usage of the new developed water-based liquid scintillators (WbLS) enhances the separation since it allows tuning of the Cherenkov/Scintillation ratio. Latest results on the separation for pure liquid scintillators and WbLS will be presented.

Elemental and charge state composition of the fast solar wind observed with SMS instruments on WIND

NASA Technical Reports Server (NTRS)

Gloeckler, G.; Galvin, A. B.; Ipavich, F. M.; Hamilton, D. C.; Bochsler, P.; Geiss, J.; Fisk, L. A.; Wilken, B.

1995-01-01

The elemental composition and charge state distributions of heavy ions of the solar wind provide essential information about: (1) atom-ion separation processes in the solar atmosphere leading to the 'FIP effect' (the overabundance of low First Ionization potential (FIP) elements in the solar wind compared to the photosphere); and (2) coronal temperature profiles, as well as mechanisms which heat the corona and accelerate the solar wind. This information is required for solar wind acceleration models. The SWICS instrument on Ulysses measures for all solar wind flow conditions the relative abundance of about 8 elements and 20 charge states of the solar wind. Furthermore, the Ulysses high-latitude orbit provides an unprecedented look at the solar wind from the polar coronal holes near solar minimum conditions. The MASS instrument on the WIND spacecraft is a high-mass resolution solar wind ion mass spectrometer that will provide routinely not only the abundances and charge state of all elements easily measured with SWICS, but also of N, Mg, S. The MASS sensor was fully operational at the end of 1994 and has sampled the in-ecliptic solar wind composition in both the slow and the corotating fast streams. This unique combination of SWICS on Ulysses and MASS on WIND allows us to view for the first time the solar wind from two regions of the large coronal hole. Observations with SWICS in the coronal hole wind: (1) indicate that the FIP effect is small; and (2) allow us determine the altitude of the maximum in the electron temperature profile, and indicate a maximum temperature of approximately 1.5 MK. New results from the SMS instruments on Wind will be compared with results from SWICS on Ulysses.

Microscopic dynamics of charge separation at the aqueous electrochemical interface.

PubMed

Kattirtzi, John A; Limmer, David T; Willard, Adam P

2017-12-19

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water-metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali-halide pair, Na + I - , or classical ions, and the products of water autoionization, H 3 O + OH - , or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water's collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface.

Microscopic dynamics of charge separation at the aqueous electrochemical interface

PubMed Central

Kattirtzi, John A.; Limmer, David T.; Willard, Adam P.

2017-01-01

We have used molecular simulation and methods of importance sampling to study the thermodynamics and kinetics of ionic charge separation at a liquid water–metal interface. We have considered this process using canonical examples of two different classes of ions: a simple alkali–halide pair, Na+I−, or classical ions, and the products of water autoionization, H3O+OH−, or water ions. We find that for both ion classes, the microscopic mechanism of charge separation, including water’s collective role in the process, is conserved between the bulk liquid and the electrode interface. However, the thermodynamic and kinetic details of the process differ between these two environments in a way that depends on ion type. In the case of the classical ion pairs, a higher free-energy barrier to charge separation and a smaller flux over that barrier at the interface result in a rate of dissociation that is 40 times slower relative to the bulk. For water ions, a slightly higher free-energy barrier is offset by a higher flux over the barrier from longer lived hydrogen-bonding patterns at the interface, resulting in a rate of association that is similar both at and away from the interface. We find that these differences in rates and stabilities of charge separation are due to the altered ability of water to solvate and reorganize in the vicinity of the metal interface. PMID:28698368

Comparison of rhenium–porphyrin dyads for CO2 photoreduction: photocatalytic studies and charge separation dynamics studied by time-resolved IR spectroscopy† †Electronic supplementary information (ESI) available: NMR spectra, cyclic voltammograms, crystallographic data, fluorescence data, spectra from photoreactions and photocatalytic data. CCDC 1406000 and 1406001. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc02099a

PubMed Central

Windle, Christopher D.; Summers, Peter A.; Sun, Xue Zhong; Whitwood, Adrian C.

2015-01-01

We report a study of the photocatalytic reduction of CO2 to CO by zinc porphyrins covalently linked to [ReI(2,2′-bipyridine)(CO)3L]+/0 moieties with visible light of wavelength >520 nm. Dyad 1 contains an amide C6H4NHC(O) link from porphyrin to bipyridine (Bpy), Dyad 2 contains an additional methoxybenzamide within the bridge C6H4NHC(O)C6H3(OMe)NHC(O), while Dyad 3 has a saturated bridge C6H4NHC(O)CH2; each dyad is studied with either L = Br or 3-picoline. The syntheses, spectroscopic characterisation and cyclic voltammetry of Dyad 3 Br and [Dyad 3 pic]OTf are described. The photocatalytic performance of [Dyad 3 pic]OTf in DMF/triethanolamine (5 : 1) is approximately an order of magnitude better than [Dyad 1 pic]PF6 or [Dyad 2 pic]OTf in turnover frequency and turnover number, reaching a turnover number of 360. The performance of the dyads with Re–Br units is very similar to that of the dyads with [Re–pic]+ units in spite of the adverse free energy of electron transfer. The dyads undergo reactions during photocatalysis: hydrogenation of the porphyrin to form chlorin and isobacteriochlorin units is detected by visible absorption spectroscopy, while IR spectroscopy reveals replacement of the axial ligand by a triethanolaminato group and insertion of CO2 into the latter to form a carbonate. Time-resolved IR spectra of [Dyad 2 pic]OTf and [Dyad 3 pic]OTf (560 nm excitation in CH2Cl2) demonstrated electron transfer from porphyrin to Re(Bpy) units resulting in a shift of ν(CO) bands to low wavenumbers. The rise time of the charge-separated species for [Dyad 3 pic]OTf is longest at 8 (±1) ps and its lifetime is also the longest at 320 (±15) ps. The TRIR spectra of Dyad 1 Br and Dyad 2 Br are quite different showing a mixture of 3MLCT, IL and charge-separated excited states. In the case of Dyad 3 Br, the charge-separated state is absent altogether. The TRIR spectra emphasize the very different excited states of the bromide complexes and the picoline complexes. Thus, the similarity of the photocatalytic data for bromide and picoline dyads suggests that they share common intermediates. Most likely, these involve hydrogenation of the porphyrin and substitution of the axial ligand at rhenium. PMID:29861927

Electrochemical cell assembled in discharged state

DOEpatents

Yao, Neng-Ping; Walsh, William J.

1976-01-01

A secondary, electrochemical cell is assembled in a completely discharged state within a sealed containment. As assembled, the cell includes a positive electrode separated from a negative electrode by a molten salt electrolyte. The positive electrode is contained within a porous structure, permitting passage of molten electrolyte, and includes one or more layers of a metallic mesh, e.g. iron, impregnated with an intimate mixture of lithium sulfide and the electrolyte. The negative electrode is a porous plaque of aluminum metal. Prior to using the cell, an electrical charge forms lithium-aluminum alloy within the negative electrode and metal sulfide within the positive electrode.

A SONOS device with a separated charge trapping layer for improvement of charge injection

NASA Astrophysics Data System (ADS)

Ahn, Jae-Hyuk; Moon, Dong-Il; Ko, Seung-Won; Kim, Chang-Hoon; Kim, Jee-Yeon; Kim, Moon-Seok; Seol, Myeong-Lok; Moon, Joon-Bae; Choi, Ji-Min; Oh, Jae-Sub; Choi, Sung-Jin; Choi, Yang-Kyu

2017-03-01

A charge trapping layer that is separated from the primary gate dielectric is implemented on a FinFET SONOS structure. By virtue of the reduced effective oxide thickness of the primary gate dielectric, a strong gate-to-channel coupling is obtained and thus short-channel effects in the proposed device are effectively suppressed. Moreover, a high program/erase speed and a large shift in the threshold voltage are achieved due to the improved charge injection by the reduced effective oxide thickness. The proposed structure has potential for use in high speed flash memory.

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 technological design and development. Time dependent perturbation theory, employed by non-equilibrium Green's function formalism, is utilized to study the effect of quantum coherences on electron transport and the effect of symmetry breaking on the electronic spectra of model molecular junctions. The fourth part of this thesis presents the design of a physical chemistry course based on a pedagogical approach called Writing-to-Teach. The nature of inaccuracies expressed in student-generated explanations of quantum chemistry topics, and the ability of a peer review process to engage these inaccuracies, is explored within this context.

On the role of local charge carrier mobility in the charge separation mechanism of organic photovoltaics.

PubMed

Yoshikawa, Saya; Saeki, Akinori; Saito, Masahiko; Osaka, Itaru; Seki, Shu

2015-07-21

Although the charge separation (CS) and transport processes that compete with geminate and non-geminate recombination are commonly regarded as the governing factors of organic photovoltaic (OPV) efficiency, the details of the CS mechanism remain largely unexplored. Here we provide a systematic investigation on the role of local charge carrier mobility in bulk heterojunction films of ten different low-bandgap polymers and polythiophene analogues blended with methanofullerene (PCBM). By correlating with the OPV performances, we demonstrated that the local mobility of the blend measured by time-resolved microwave conductivity is more important for the OPV output than those of the pure polymers. Furthermore, the results revealed two separate trends for crystalline and semi-crystalline polymers. This work offers guidance in the design of high-performance organic solar cells.

Hydrodynamics with chiral anomaly and charge separation in relativistic heavy ion collisions

DOE PAGES

Yin, Yi; Liao, Jinfeng

2016-03-03

Matter with chiral fermions is microscopically described by theory with quantum anomaly and macroscopically described (at low energy) by anomalous hydrodynamics. For such systems in the presence of external magnetic field and chirality imbalance, a charge current is generated along the magnetic field direction ₋ a phenomenon known as the Chiral Magnetic Effect (CME). The quark- gluon plasma created in relativistic heavy ion collisions provides an (approximate) example, for which the CME predicts a charge separation perpendicular to the collisional reaction plane. Charge correlation measurements designed for the search of such signal have been done at RHIC and the LHCmore » for which the interpretations, however, remain unclear due to contamination by background effects that are collective flow driven, theoretically poorly constrained, and experimentally hard to separate. Using anomalous (and viscous) hydrodynamic simulations, we make a first attempt at quantifying contributions to observed charge correlations from both CME and background effects in one and same framework. We discuss the implications for the search of CME.« less

The nature of the lower excited state of the special pair of bacterial photosynthetic reaction center of Rhodobacter Sphaeroides and the dynamics of primary charge separation

NASA Astrophysics Data System (ADS)

Ivashin, N. V.; Shchupak, E. E.

2016-08-01

Quantum-chemical calculations of the structure in the ground and lower singlet excited states and the vibrations (in the ground state) of special pair P of photosynthetic reaction center of purple bacteria (RCPb) Rhodobacter Sphaeroides, consisting of two bacteriochlorophyll molecules PA and PB, have been carried out. It is shown that excitation of the special pair is followed by fast relaxation dynamics, accompanied by the transformation of the initial P* state into the P A δ+ P B δ- state (δ ~ 0.5) with charge separation. This behavior is due to the presence of several nonplanar vibrations with participation of the acetyl group of macrocycle PB in the nuclear wave packet on the potential surface of the P* state; these vibrations facilitate destabilization of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the macrocycle PA and formation of the P A δ+ P B δ- state. The structural transformations in the P* state are due to its linking character in the contact region of the acetyl group-containing pyrrole rings of PA and PB. The transition from the P* state to specifically the P A δ+ P B δ- state is related to the fact that the acetyl group PA is involved in the intermolecular hydrogen bond with amino acid residue HisL168; for this reason, this group and the pyrrole ring linked with it can hardly participate in structural transformations. The electronic matrix element H12 of the electron transfer from the special pair in the P A δ+ P B δ- state to a molecule of accessory bacteriochlorophyll BA greatly exceeds that for the transfer to BB. This circumstance and the fact that the P A δ+ P B δ- state is energetically more favorable than the P* state facilitate the preferred directionality of the electron transfer in RCPb Rhodobacter Sphaeroides with participation of the cofactors located in its subunit L.

Photoinduced charge separation at polymer-fullerene interfaces of BHJ solar cells (Conference Presentation)

NASA Astrophysics Data System (ADS)

Poluektov, Oleg G.; Niklas, Jens; Mardis, Kristy

2016-09-01

While photovoltaic cells are highly promising man-made devices for direct solar energy utilization, a number of fundamental questions about how the organic bulk heterojunction cell enables efficient long-lived and long-range charge separation remain unanswered. These questions were address by employing an advanced suite of EPR spectroscopy in combination with DFT calculations to study mechanism of charge separation at the polymer-fullerene interfaces of photo-active BHJ. Observed charge delocalization in BHJ upon photoinduced ET is analogous to that in organic donor-acceptor material. This is an efficient mechanism of charge stabilization in photosynthetic assemblies. Time-resolved EPR spectra show a strong polarization pattern for all polymer-fullerene blends under study, which is caused by non-Boltzmann population of the electron spin energy levels in the radical pairs. The first observation of this phenomenon was reported in natural and artificial photosynthetic assemblies, and comparison with these systems allows us to better understand charge separation processes in OPVs. The spectral analysis presented here, in combination with DFT calculations, shows that CS processes in OPV materials are similar to that in organic photosynthetic systems. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences, under Contract DE-AC02-06CH11357 at Argonne National Laboratory.

Computational Investigation of In-Flight Temperature in Shaped Charge Jets and Explosively Formed Penetrators

NASA Astrophysics Data System (ADS)

Sable, Peter; Helminiak, Nathaniel; Harstad, Eric; Gullerud, Arne; Hollenshead, Jeromy; Hertel, Eugene; Sandia National Laboratories Collaboration; Marquette University Collaboration

2017-06-01

With the increasing use of hydrocodes in modeling and system design, experimental benchmarking of software has never been more important. While this has been a large area of focus since the inception of computational design, comparisons with temperature data are sparse due to experimental limitations. A novel temperature measurement technique, magnetic diffusion analysis, has enabled the acquisition of in-flight temperature measurements of hyper velocity projectiles. Using this, an AC-14 bare shaped charge and an LX-14 EFP, both with copper linings, were simulated using CTH to benchmark temperature against experimental results. Particular attention was given to the slug temperature profiles after separation, and the effect of varying equation-of-state and strength models. Simulations are in agreement with experimental, attaining better than 2% error between observed shaped charge temperatures. This varied notably depending on the strength model used. Similar observations were made simulating the EFP case, with a minimum 4% deviation. Jet structures compare well with radiographic images and are consistent with ALEGRA simulations previously conducted. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Synthesis of Nb doped TiO2 nanotube/reduced graphene oxide heterostructure photocatalyst with high visible light photocatalytic activity

NASA Astrophysics Data System (ADS)

Niu, Xiaoyou; Yan, Weijing; Zhao, Hongli; Yang, Jingkai

2018-05-01

Limited by the narrowed photoresponse range and unsatisfactory recombination of photoinduced electron-hole pairs, the photocatalytic efficiency of TiO2 is still far below what is expected. Here, we initially doped TiO2 nanotubes (TNTS) by transition metal ion Nb, then it is coupled with reduced graphene oxide (rGO) to construct a heterostructure photocatalyst. The defect state presented in TiO2 leading to the formation of localized midgap states (MS) in the bandgap, which regulating the band structure of TiO2 and extending the optical absorption to visible light region. The internal charge transport and transfer behavior analyzed by electrochemical impedance spectroscopy (EIS) reveal that the coupling of rGO with TNTS results in the formation of electron transport channel in the heterostructure, which makes a great contribution to the photoinduced charge separation. As expected, the Nb-TNTS/rGO exhibits a stable and remarkably enhanced photocatalytic activity in the visible-light irradiation degradation of methylene blue (MB), up to ∼5 times with respect to TNTS, which is attributed to the effective inhibition of charge recombination, the reduction of bandgap and higher redox potential, as well as the great adsorptivity.

Mutation-Induced Changes in the Protein Environment and Site Energies in the (M)L214G Mutant of the Rhodobacter sphaeroides Bacterial Reaction Center.

PubMed

Jankowiak, Ryszard; Rancova, Olga; Chen, Jinhai; Kell, Adam; Saer, Rafael G; Beatty, J Thomas; Abramavicius, Darius

2016-08-18

This work focuses on the low-temperature (5 K) photochemical (transient) hole-burned (HB) spectra within the P870 absorption band, and their theoretical analysis, for the (M)L214G mutant of the photosynthetic Rhodobacter sphaeroides bacterial reaction center (bRC). To provide insight into system-bath interactions of the bacteriochlorophyll a (BChl a) special pair, i.e., P870, in the mutated bRC, the optical line shape function for the P870 band is calculated numerically. On the basis of the modeling studies, we demonstrate that (M)L214G mutation leads to a heterogeneous population of bRCs with modified (increased) total electron-phonon coupling strength of the special pair BChl a and larger inhomogeneous broadening. Specifically, we show that after mutation in the (M)L214G bRC a large fraction (∼50%) of the bacteriopheophytin (HA) chromophores shifts red and the 800 nm absorption band broadens, while the remaining fraction of HA cofactors retains nearly the same site energy as HA in the wild-type bRC. Modeling using these two subpopulations allowed for fits of the absorption and nonresonant (transient) HB spectra of the mutant bRC in the charge neutral, oxidized, and charge-separated states using the Frenkel exciton Hamiltonian, providing new insight into the mutant's complex electronic structure. Although the average (M)L214G mutant quantum efficiency of P(+)QA(-) state formation seems to be altered in comparison with the wild-type bRC, the average electron transfer time (measured via resonant transient HB spectra within the P870 band) was not affected. Thus, mutation in the vicinity of the electron acceptor (HA) does not tune the charge separation dynamics. Finally, quenching of the (M)L214G mutant excited states by P(+) is addressed by persistent HB spectra burned within the B band in chemically oxidized samples.

Tetra- and Heptametallic Ru(II),Rh(III) Supramolecular Hydrogen Production Photocatalysts

DOE PAGES

Manbeck, Gerald F.; Fujita, Etsuko; Brewer, Karen J.

2017-06-01

Supramolecular mixed metal complexes combining the trimetallic chromophore [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 6+ (Ru 3) with [Rh(bpy)Cl 2] + or [RhCl 2] + catalytic fragments to form [{(bpy) 2Ru(dpp)} 2Ru(dpp)RhCl 2(bpy)](PF 6) 7 (Ru 3Rh) or [{(bpy) 2Ru(dpp)} 2Ru(dpp)] 2RhCl 2(PF 6) 13 (Ru 3RhRu 3) (bpy = 2,2'-bipyridine and dpp = 2,3-bis(2-pyridyl)pyrazine) catalyze the photochemical reduction of protons to H 2. This first example of a heptametallic Ru,Rh photocatalyst produces over 300 turnovers of H 2 upon photolysis of a solution of acetonitrile, water, triflic acid, and N,N-dimethylaniline as an electron donor. Conversely, the tetrametallic Ru 3Rh produces only 40more » turnovers of H 2 due to differences in the excited state properties and nature of the catalysts upon reduction as ascertained from electrochemical data, transient absorption spectroscopy, and flash-quench experiments. And while the lowest unoccupied molecular orbital of Ru 3Rh is localized on a bridging ligand, it is Rh-centered in Ru 3RhRu 3 facilitating electron collection at Rh in the excited state and reductively quenched state. The Ru → Rh charge separated state of Ru 3RhRu 3 is endergonic with respect to the emissive Ru → dpp 3MLCT excited and cannot be formed by static electron transfer quenching of the 3MLCT state. Instead, a mechanism of subnanosecond charge separation from high lying states is proposed. Multiple reductions of Ru 3 and Ru 3Rh using sodium amalgam were carried out to compare UV–vis absorption spectra of reduced species and to evaluate the stability of highly reduced complexes. Furthermore, the Ru 3 and Ru 3Rh can be reduced by 10 and 13 electrons, respectively, to final states with all bridging ligands doubly reduced and all bpy ligands singly reduced.« less

Ultrafast Photoinduced Electron Transfer in a π-Conjugated Oligomer/Porphyrin Complex.

PubMed

Aly, Shawkat M; Goswami, Subhadip; Alsulami, Qana A; Schanze, Kirk S; Mohammed, Omar F

2014-10-02

Controlling charge transfer (CT), charge separation (CS), and charge recombination (CR) at the donor-acceptor interface is extremely important to optimize the conversion efficiency in solar cell devices. In general, ultrafast CT and slow CR are desirable for optimal device performance. In this Letter, the ultrafast excited-state CT between platinum oligomer (DPP-Pt(acac)) as a new electron donor and porphyrin as an electron acceptor is monitored for the first time using femtosecond (fs) transient absorption (TA) spectroscopy with broad-band capability and 120 fs temporal resolution. Turning the CT on/off has been shown to be possible either by switching from an organometallic oligomer to a metal-free oligomer or by controlling the charge density on the nitrogen atom of the porphyrin meso unit. Our time-resolved data show that the CT and CS between DPP-Pt(acac) and cationic porphyrin are ultrafast (approximately 1.5 ps), and the CR is slow (ns time scale), as inferred from the formation and the decay of the cationic and anionic species. We also found that the metallic center in the DPP-Pt(acac) oligomer and the positive charge on the porphyrin are the keys to switching on/off the ultrafast CT process.

Molecular Photovoltaics in Nanoscale Dimension

PubMed Central

Burtman, Vladimir; Zelichonok, Alexander; Pakoulev, Andrei V.

2011-01-01

This review focuses on the intrinsic charge transport in organic photovoltaic (PVC) devices and field-effect transistors (SAM-OFETs) fabricated by vapor phase molecular self-assembly (VP-SAM) method. The dynamics of charge transport are determined and used to clarify a transport mechanism. The 1,4,5,8-naphthalene-tetracarboxylic diphenylimide (NTCDI) SAM devices provide a useful tool to study the fundamentals of polaronic transport at organic surfaces and to discuss the performance of organic photovoltaic devices in nanoscale. Time-resolved photovoltaic studies allow us to separate the charge annihilation kinetics in the conductive NTCDI channel from the overall charge kinetic in a SAM-OFET device. It has been demonstrated that tuning of the type of conductivity in NTCDI SAM-OFET devices is possible by changing Si substrate doping. Our study of the polaron charge transfer in organic materials proposes that a cation-radical exchange (redox) mechanism is the major transport mechanism in the studied SAM-PVC devices. The role and contribution of the transport through delocalized states of redox active surface molecular aggregates of NTCDI are exposed and investigated. This example of technological development is used to highlight the significance of future technological development of nanotechnologies and to appreciate a structure-property paradigm in organic nanostructures. PMID:21339983

Generalized Mulliken-Hush analysis of electronic coupling interactions in compressed pi-stacked porphyrin-bridge-quinone systems.

PubMed

Zheng, Jieru; Kang, Youn K; Therien, Michael J; Beratan, David N

2005-08-17

Donor-acceptor interactions were investigated in a series of unusually rigid, cofacially compressed pi-stacked porphyrin-bridge-quinone systems. The two-state generalized Mulliken-Hush (GMH) approach was used to compute the coupling matrix elements. The theoretical coupling values evaluated with the GMH method were obtained from configuration interaction calculations using the INDO/S method. The results of this analysis are consistent with the comparatively soft distance dependences observed for both the charge separation and charge recombination reactions. Theoretical studies of model structures indicate that the phenyl units dominate the mediation of the donor-acceptor coupling and that the relatively weak exponential decay of rate with distance arises from the compression of this pi-electron stack.

Modeling of the charge-state separation at ITEP experimental facility for material science based on a Bernas ion source.

PubMed

Barminova, H Y; Saratovskyh, M S

2016-02-01

The experiment automation system is supposed to be developed for experimental facility for material science at ITEP, based on a Bernas ion source. The program CAMFT is assumed to be involved into the program of the experiment automation. CAMFT is developed to simulate the intense charged particle bunch motion in the external magnetic fields with arbitrary geometry by means of the accurate solution of the particle motion equation. Program allows the consideration of the bunch intensity up to 10(10) ppb. Preliminary calculations are performed at ITEP supercomputer. The results of the simulation of the beam pre-acceleration and following turn in magnetic field are presented for different initial conditions.

Exploring Low Internal Reorganization Energies for Silicene Nanoclusters

NASA Astrophysics Data System (ADS)

Pablo-Pedro, Ricardo; Lopez-Rios, Hector; Mendoza-Cortes, Jose-L.; Kong, Jing; Fomine, Serguei; Van Voorhis, Troy; Dresselhaus, Mildred S.

2018-05-01

This paper is a contribution to the Physical Review Applied collection in memory of Mildred S. Dresselhaus. High-performance materials rely on small reorganization energies to facilitate both charge separation and charge transport. Here, we perform density-functional-theory calculations to predict small reorganization energies of rectangular silicene nanoclusters with hydrogen-passivated edges denoted by H-SiNC. We observe that across all geometries, H-SiNCs feature large electron affinities and highly stabilized anionic states, indicating their potential as n -type materials. Our findings suggest that fine-tuning the size of H-SiNCs along the "zigzag" and "armchair" directions may permit the design of novel n -type electronic materials and spintronics devices that incorporate both high electron affinities and very low internal reorganization energies.

Modeling of the charge-state separation at ITEP experimental facility for material science based on a Bernas ion source

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

Barminova, H. Y., E-mail: barminova@bk.ru; Saratovskyh, M. S.

2016-02-15

The experiment automation system is supposed to be developed for experimental facility for material science at ITEP, based on a Bernas ion source. The program CAMFT is assumed to be involved into the program of the experiment automation. CAMFT is developed to simulate the intense charged particle bunch motion in the external magnetic fields with arbitrary geometry by means of the accurate solution of the particle motion equation. Program allows the consideration of the bunch intensity up to 10{sup 10} ppb. Preliminary calculations are performed at ITEP supercomputer. The results of the simulation of the beam pre-acceleration and following turnmore » in magnetic field are presented for different initial conditions.« less

Reduced graphene oxide and porphyrin. An interactive affair in 2-D.

PubMed

Wojcik, Aleksandra; Kamat, Prashant V

2010-11-23

Photoexcited cationic 5,10,15,20-tetrakis(1-methyl-4-pyridinio)porphyrin tetra(p-toluenesulfonate) (TMPyP) undergoes charge-transfer interaction with chemically reduced graphene oxide (RGO). Formation of the ground-state TMPyP-RGO complex in solution is marked by the red-shift of the porphyrin absorption band. This complexation was analyzed by Benesi-Hildebrand plot. Porphyrin fluorescence lifetime reduced from 5 to 1 ns upon complexation with RGO, indicating excited-state interaction between singlet excited porphyrin and RGO. Femtosecond transient absorption measurements carried out with TMPyP adsorbed on RGO film revealed fast decay of the singlet excited state, followed by the formation of a longer-living product with an absorption maximum around 515 nm indicating the formation of a porphyrin radical cation. The ability of TMPyP-RGO to undergo photoinduced charge separation was further confirmed from the photoelectrochemical measurements. TMPyP-RGO coated conducting glass electrodes are capable of generating photocurrent under visible excitation. These results are indicative of the electron transfer between photoexcited porphyrin and RGO. The role of graphene in accepting and shuttling electrons in light-harvesting assemblies is discussed.

A theory of X and Z multiquark resonances

NASA Astrophysics Data System (ADS)

Maiani, Luciano; Polosa, Antonio D.; Riquer, Veronica

2018-03-01

We introduce the hypothesis that diquarks and antidiquarks in tetraquarks are separated by a potential barrier. We show that this notion can answer satisfactorily long standing questions challenging the diquark-antidiquark model of exotic resonances. The tetraquark description of X and Z resonances is shown to be compatible with present limits on the non-observation of charged partners X±, of the X (3872) and the absence of a hyperfine splitting between two different neutral states. In the same picture, Zc and Zb particles are expected to form complete isospin triplets plus singlets. It is also explained why the decay rate into final states including quarkonia are suppressed with respect to those having open charm/beauty states.

A DIM model for sodium cluster-ions interacting with a charged conducting sphere

NASA Astrophysics Data System (ADS)

Kuntz, P. J.

A diatomics-in-molecules (DIM) model for the energy, shape and charge distribution of metal cluster ions in the presence of a charged insulated conducting sphere is presented. The electrostatic interaction between the sphere and the cluster-ion is introduced in a self-consistent manner which allows the sphere to be polarized by the ion and the ion by the sphere. This interaction appears in the diagonal elements of the model Hamiltonian matrix in such a way that the lowest eigenvalue includes the correct electrostatic energy for the charge distribution in the ground state. The model is applied to the calculation of fusion barriers for Na+2 and Na+3 ions. When both the charge distribution and the geometric configuration of the cluster-ion are allowed to relax freely, the energy as a function of distance from the sphere is nearly the same as that calculated from the electrostatic energy alone, which implies that details of the molecular structure of the cluster-ion can be neglected in calculating fusion barriers from charge polarization alone. That the fusion barriers lie sufficiently far away from the sphere so that the molecule does not dissociate under the influence of the Coulomb interaction confirms that it is meaningful to speak of two separate entities at the barrier position.

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.

Separation of lymphocytes by electrophoresis under terrestrial conditions and at zero gravity

NASA Technical Reports Server (NTRS)

Rubin, A. L.

1977-01-01

Electrophoretic mobility (EPM) of human peripheral lymphocytes were examined with the following objectives: To determine differences in EPM of lymphocytes under immuno-stimulated and immuno-suppressed states. To define the conditions necessary for the separation of lymphocyte sub-populations in normal and pathological conditions; To investigate immunological active, charged chemical groups on lymphocyte surfaces; and to investigate pathophysiological mechanisms of immune responsiveness, as reflected by alterations in EPM. To evaluate the potential of lymphocyte electrophoresis as: (1) a means of monitoring the immune status of kidney transplant recipients, (2) in predicting the outcome of kidney transplants, and (3) as a method for separation of lymphocyte sub-populations, the EPM was studied for unfractionated human peripheral lymphocytes and of populations enriched with T and "B" cells from normal adults, hemodialysis patients and kidney transplant recipients.

High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

PubMed

Swearingen, Kristian E; Moritz, Robert L

2012-10-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

Phthalimide Copolymer Solar Cells

NASA Astrophysics Data System (ADS)

Xin, Hao; Guo, Xugang; Ren, Guoqiang; Kim, Felix; Watson, Mark; Jenekhe, Samson

2010-03-01

Photovoltaic properties of bulk heterojunction solar cells based on phthalimide donor-acceptor copolymers have been investigated. Due to the strong π-π stacking of the polymers, the state-of-the-art thermal annealing approach resulted in micro-scale phase separation and thus negligible photocurrent. To achieve ideal bicontinuous morphology, different strategies including quickly film drying and mixed solvent for film processing have been explored. In these films, nano-sale phase separation was achieved and a power conversion efficiency of 3.0% was obtained. Absorption and space-charge limited current mobility measurements reveal similar light harvesting and hole mobilities in all the films, indicating that the morphology is the dominant factor determining the photovoltaic performance. Our results demonstrate that for highly crystalline and/or low-solubility polymers, finding a way to prevent polymer aggregation and large scale phase separation is critical to realizing high performance solar cells.

Parafermionic zero modes in gapless edge states

NASA Astrophysics Data System (ADS)

Clarke, David

It has been recently demonstrated1 that Majorana zero modes may occur in the gapless edge of Abelian quantum Hall states at a boundary between different edge phases bordering the same bulk. Such a zero mode is guaranteed to occur when an edge phase that supports fermionic excitations borders one that does not. Here we generalize to the non-charge conserving case such as may occur when a superconductor abuts the quantum Hall edge. We find that not only Majorana zero modes, but their ℤN generalizations (known as parafermionic zero modes) may occur at boundaries between edge phases in a fractional quantum Hall state. In particular, we find thst the ν = 1 / 3 fractional quantum Hall state supports topologically distinct edge phases separated by ℤ3 parafermionic zero modes when charge conservation is broken. Paradoxically, an arrangement of phases can be made such that only an odd number of localized parafermionic zero modes occur around the edge of a quantum Hall droplet. Such an arrangement is not allowed in a gapped system, but here the paradox is resolved due to an extended zero mode in the edge spectrum. LPS-MPO-CMTC, JQI-NSF-PFC, Microsoft Station Q.

Poisson-Boltzmann theory of the charge-induced adsorption of semi-flexible polyelectrolytes.

PubMed

Ubbink, Job; Khokhlov, Alexei R

2004-03-15

A model is suggested for the structure of an adsorbed layer of a highly charged semi-flexible polyelectrolyte on a weakly charged surface of opposite charge sign. The adsorbed phase is thin, owing to the effective reversal of the charge sign of the surface upon adsorption, and ordered, owing to the high surface density of polyelectrolyte strands caused by the generally strong binding between polyelectrolyte and surface. The Poisson-Boltzmann equation for the electrostatic interaction between the array of adsorbed polyelectrolytes and the charged surface is solved for a cylindrical geometry, both numerically, using a finite element method, and analytically within the weak curvature limit under the assumption of excess monovalent salt. For small separations, repulsive surface polarization and counterion osmotic pressure effects dominate over the electrostatic attraction and the resulting electrostatic interaction curve shows a minimum at nonzero separations on the Angstrom scale. The equilibrium density of the adsorbed phase is obtained by minimizing the total free energy under the condition of equality of chemical potential and osmotic pressure of the polyelectrolyte in solution and in the adsorbed phase. For a wide range of ionic conditions and charge densities of the charged surface, the interstrand separation as predicted by the Poisson-Boltzmann model and the analytical theory closely agree. For low to moderate charge densities of the adsorbing surface, the interstrand spacing decreases as a function of the charge density of the charged surface. Above about 0.1 M excess monovalent salt, it is only weakly dependent on the ionic strength. At high charge densities of the adsorbing surface, the interstrand spacing increases with increasing ionic strength, in line with the experiments by Fang and Yang [J. Phys. Chem. B 101, 441 (1997)]. (c) 2004 American Institute of Physics.

Boundary conditions and formation of pure spin currents in magnetic field

NASA Astrophysics Data System (ADS)

Eliashvili, Merab; Tsitsishvili, George

2017-09-01

Schrödinger equation for an electron confined to a two-dimensional strip is considered in the presence of homogeneous orthogonal magnetic field. Since the system has edges, the eigenvalue problem is supplied by the boundary conditions (BC) aimed in preventing the leakage of matter away across the edges. In the case of spinless electrons the Dirichlet and Neumann BC are considered. The Dirichlet BC result in the existence of charge carrying edge states. For the Neumann BC each separate edge comprises two counterflow sub-currents which precisely cancel out each other provided the system is populated by electrons up to certain Fermi level. Cancelation of electric current is a good starting point for developing the spin-effects. In this scope we reconsider the problem for a spinning electron with Rashba coupling. The Neumann BC are replaced by Robin BC. Again, the two counterflow electric sub-currents cancel out each other for a separate edge, while the spin current survives thus modeling what is known as pure spin current - spin flow without charge flow.

Probing interfacial energetics and charge transfer kinetics in semiconductor nanocomposites: New insights into heterostructured TiO 2/BiVO 4 photoanodes

DOE PAGES

Hess, Lucas H.; Cooper, Jason K.; Loiudice, Anna; ...

2017-02-28

Heterostructured nanocomposites offer promise for creating systems exhibiting functional properties that exceed those of the isolated components. For solar energy conversion, such combinations of semiconducting nanomaterials can be used to direct charge transfer along pathways that reduce recombination and promote efficient charge extraction. However, interfacial energetics and associated kinetic pathways often differ significantly from predictions derived from the characteristics of pure component materials, particularly at the nanoscale. Here, the emergent properties of TiO 2/BiVO 4 nanocomposite photoanodes are explored using a combination of X-ray and optical spectroscopies, together with photoelectrochemical (PEC) characterization. Application of these methods to both the puremore » components and the fully assembled nanocomposites reveals unpredicted interfacial energetic alignment, which promotes ultrafast injection of electrons from BiVO 4 into TiO 2. Physical charge separation yields extremely long-lived photoexcited states and correspondingly enhanced photoelectrochemical functionality. This work highlights the importance of probing emergent interfacial energetic alignment and kinetic processes for understanding mechanisms of solar energy conversion in complex nanocomposites.« less

Triphenylamine-Based Push–Pull Molecule for Photovoltaic Applications: From Synthesis to Ultrafast Device Photophysics

PubMed Central

2017-01-01

Small push–pull molecules attract much attention as prospective donor materials for organic solar cells (OSCs). By chemical engineering, it is possible to combine a number of attractive properties such as broad absorption, efficient charge separation, and vacuum and solution processabilities in a single molecule. Here we report the synthesis and early time photophysics of such a molecule, TPA-2T-DCV-Me, based on the triphenylamine (TPA) donor core and dicyanovinyl (DCV) acceptor end group connected by a thiophene bridge. Using time-resolved photoinduced absorption and photoluminescence, we demonstrate that in blends with [70]PCBM the molecule works both as an electron donor and hole acceptor, thereby allowing for two independent channels of charge generation. The charge-generation process is followed by the recombination of interfacial charge transfer states that takes place on the subnanosecond time scale as revealed by time-resolved photoluminescence and nongeminate recombination as follows from the OSC performance. Our findings demonstrate the potential of TPA-DCV-based molecules as donor materials for both solution-processed and vacuum-deposited OSCs. PMID:28413568

Transient and modulated charge separation at CuInSe2/C60 and CuInSe2/ZnPc hybrid interfaces

NASA Astrophysics Data System (ADS)

von Morzé, Natascha; Dittrich, Thomas; Calvet, Wolfram; Lauermann, Iver; Rusu, Marin

2017-02-01

Spectral dependent charge transfer and exciton dissociation have been investigated at hybrid interfaces between inorganic polycrystalline CuInSe2 (untreated and Na-conditioned) thin films and organic C60 as well as zinc phthalocyanine (ZnPc) layers by transient and modulated surface photovoltage measurements. The stoichiometry and electronic properties of the bare CuInSe2 surface were characterized by photoelectron spectroscopy which revealed a Cu-poor phase with n-type features. After the deposition of the C60 layer, a strong band bending at the CuInSe2 surface was observed. Evidence for dissociation of excitons followed by charge separation was found at the CuInSe2/ZnPc interface. The Cu-poor layer at the CuInSe2 surface was found to be crucial for transient and modulated charge separation at CuInSe2/organic hybrid interfaces.

Tracking the coherent generation of polaron pairs in conjugated polymers

NASA Astrophysics Data System (ADS)

de Sio, Antonietta; Troiani, Filippo; Maiuri, Margherita; Réhault, Julien; Sommer, Ephraim; Lim, James; Huelga, Susana F.; Plenio, Martin B.; Rozzi, Carlo Andrea; Cerullo, Giulio; Molinari, Elisa; Lienau, Christoph

2016-12-01

The optical excitation of organic semiconductors not only generates charge-neutral electron-hole pairs (excitons), but also charge-separated polaron pairs with high yield. The microscopic mechanisms underlying this charge separation have been debated for many years. Here we use ultrafast two-dimensional electronic spectroscopy to study the dynamics of polaron pair formation in a prototypical polymer thin film on a sub-20-fs time scale. We observe multi-period peak oscillations persisting for up to about 1 ps as distinct signatures of vibronic quantum coherence at room temperature. The measured two-dimensional spectra show pronounced peak splittings revealing that the elementary optical excitations of this polymer are hybridized exciton-polaron-pairs, strongly coupled to a dominant underdamped vibrational mode. Coherent vibronic coupling induces ultrafast polaron pair formation, accelerates the charge separation dynamics and makes it insensitive to disorder. These findings open up new perspectives for tailoring light-to-current conversion in organic materials.

AlInAsSb separate absorption, charge, and multiplication avalanche photodiodes

NASA Astrophysics Data System (ADS)

Ren, Min; Maddox, Scott J.; Woodson, Madison E.; Chen, Yaojia; Bank, Seth R.; Campbell, Joe C.

2016-05-01

We report AlxIn1-xAsySb1-y separate absorption, charge, and multiplication avalanche photodiodes (APDs) that operate in the short-wavelength infrared spectrum. They exhibit excess noise factor less or equal to that of Si and the low dark currents typical of III-V compound APDs.

Charge and energy dynamics in photo-excited poly(para-phenylenevinylene) systems

NASA Astrophysics Data System (ADS)

Gisslén, L.; Johansson, A.˚.; Stafström, S.

2004-07-01

We report results from simulations of charge and energy dynamics in poly(para-phenylenevinylene) (PPV) and PPV interacting with C60. The simulations were performed by solving the time-dependent Schrödinger equation and the lattice equation of motion simultaneously and nonadiabatically. The electronic system and the coupling of the electrons to the lattice were described by an extended three-dimensional version of the Su-Schrieffer-Heeger model, which also included an external electric field. Electron and lattice dynamics following electronic excitations at different energies have been simulated. The effect of additional lattice energy was also included in the simulations. Our results show that both exciton diffusion and transitions from high to lower lying excitations are stimulated by increasing the lattice energy. Also field induced charge separation occurs faster if the lattice energy is increased. This separation process is highly nonadiabatic and involves a significant rearrangement of the electron distribution. In the case of PPV coupled to C60, we observe a spontaneous charge separation. The separation time is in this case limited by the local concentration of C60 molecules close to the PPV chain.

Bidirectional Photoinduced Electron Transfer in Ruthenium(II)-Tris-bipyridyl-Modified PpcA, a Multi-heme c -Type Cytochrome from Geobacter sulfurreducens

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

Kokhan, Oleksandr; Ponomarenko, Nina S.; Pokkuluri, P. Raj

PpcA, a tri-heme cytochrome c7 from Geobacter sulfurreducens was investigated as a model for photosensitizer-initiated electron transfer within a multi-heme "molecular wire" protein architecture. E. coli expression of PpcA was found to be tolerant of cysteine site-directed mutagenesis, demonstrated by the successful expression of natively folded proteins bearing cysteine mutations at a series of sites selected to vary characteristically with respect to the three -CXXCH- heme binding domains. A preliminary survey of 5 selected mutants found that the introduced cysteines can be readily covalently linked to a Ru(II)-(2,2'-bpy)2(4-bromomethyl-4’-methyl-2,2'-bpy) photosensitizer (where bpy = bipyridine), and that the linked constructs support bothmore » photo-oxidative and photo-reductive quenching of the photosensitizer excited-state, depending upon the initial heme redox state. For photo-oxidative electron transfer, apparent heme reduction risetimes were found to vary from 7 x 10-12 s to 5 x 10-8 s, depending upon the site of photosensitizer linking. The excited-state electron transfers are about 103-fold faster than any previously reported photosensitizer-redox protein covalently linked construct. Preliminary conformational analysis using molecular dynamics simulations shows that rates for electron transfer track both the distance and pathways for electron transfer. Two mutants with the fastest charge transfer rates, A23C and K29C, showed a significant role of specific paths for electron transfer. While K29C labeled mutant was expected to have approximately 0.8Å greater donor-acceptor distance, it showed 20-fold faster charge separation rate. Clear evidence for inter-heme electron transfer within the multi-heme protein is not detected within the lifetimes of the charge separated states. These results demonstrate an opportunity to develop multi-heme c-cytochromes for investigation of electron transfer in protein "molecular wires" and to serve as frameworks for metalloprotein designs that support multiple electron transfer redox chemistry.« less

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO 2 reduction

DOE PAGES

Hoch, Laura B.; Szymanski, Paul; Ghuman, Kulbir Kaur; ...

2016-11-28

In 2O 3-x(OH) y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO 2 to CO via the reverse water–gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In 2O 3-x(OH) y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play amore » significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO 2 reduction.« less

Carrier dynamics and the role of surface defects: Designing a photocatalyst for gas-phase CO 2 reduction

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

Hoch, Laura B.; Szymanski, Paul; Ghuman, Kulbir Kaur

In 2O 3-x(OH) y nanoparticles have been shown to function as an effective gas-phase photocatalyst for the reduction of CO 2 to CO via the reverse water–gas shift reaction. Their photocatalytic activity is strongly correlated to the number of oxygen vacancy and hydroxide defects present in the system. To better understand how such defects interact with photogenerated electrons and holes in these materials, we have studied the relaxation dynamics of In 2O 3-x(OH) y nanoparticles with varying concentration of defects using two different excitation energies corresponding to above-band-gap (318-nm) and near-band-gap (405-nm) excitations. Our results demonstrate that defects play amore » significant role in the excited-state, charge relaxation pathways. Higher defect concentrations result in longer excited-state lifetimes, which are attributed to improved charge separation. This correlates well with the observed trends in the photocatalytic activity. These results are further supported by density-functional theory calculations, which confirm the positions of oxygen vacancy and hydroxide defect states within the optical band gap of indium oxide. This enhanced understanding of the role these defects play in determining the optoelectronic properties and charge carrier dynamics can provide valuable insight toward the rational development of more efficient photocatalytic materials for CO 2 reduction.« less

Improved visible-light photocatalytic activity of TiO2 co-doped with copper and iodine

NASA Astrophysics Data System (ADS)

Dorraj, Masoumeh; Goh, Boon Tong; Sairi, Nor Asrina; Woi, Pei Meng; Basirun, Wan Jefrey

2018-05-01

Cu-I-co-doped TiO2 photocatalysts active to visible light absorption were prepared by hydrothermal method and calcined at various temperatures (350 °C, 450 °C, and 550 °C). The co-doped powders at 350 °C displayed the highest experimental Brunauer-Emmett-Teller surface area and lowest photoluminescence intensity, which demonstrated that a decrease in electron-hole recombination process. The synthesis of co-doped TiO2 was performed at this optimized temperature. In the co-doped sample, the Cu2+ doped TiO2 lattice created a major "red-shift" in the absorption edge due to the presence of the 3d Cu states, whereas the amount of red-shift from the I5+ doping in the TiO2 lattice was minor. Interestingly, the presence of Cu2+ species also boosted the reduction of I5+ ions to the lower multi-valance state I- in the TiO2 lattice by trapping the photogenerated electrons, which resulted in effective separation of the photogenerated charges. The Cu-I-co-doped TiO2 was able to degrade methyl orange dye under visible-light irradiation with improved photocatalytic activity compared with the single metal-doped TiO2 and pure TiO2 because of the strong visible light absorption and effective separation of photogenerated charges caused by the synergistic effects of Cu and I co-dopants.

Gradient Self-Doped CuBi2O4 with Highly Improved Charge Separation Efficiency.

PubMed

Wang, Fuxian; Septina, Wilman; Chemseddine, Abdelkrim; Abdi, Fatwa F; Friedrich, Dennis; Bogdanoff, Peter; van de Krol, Roel; Tilley, S David; Berglund, Sean P

2017-10-25

A new strategy of using forward gradient self-doping to improve the charge separation efficiency in metal oxide photoelectrodes is proposed. Gradient self-doped CuBi 2 O 4 photocathodes are prepared with forward and reverse gradients in copper vacancies using a two-step, diffusion-assisted spray pyrolysis process. Decreasing the Cu/Bi ratio of the CuBi 2 O 4 photocathodes introduces Cu vacancies that increase the carrier (hole) concentration and lowers the Fermi level, as evidenced by a shift in the flat band toward more positive potentials. Thus, a gradient in Cu vacancies leads to an internal electric field within CuBi 2 O 4 , which can facilitate charge separation. Compared to homogeneous CuBi 2 O 4 photocathodes, CuBi 2 O 4 photocathodes with a forward gradient show highly improved charge separation efficiency and enhanced photoelectrochemical performance for reduction reactions, while CuBi 2 O 4 photocathodes with a reverse gradient show significantly reduced charge separation efficiency and photoelectrochemical performance. The CuBi 2 O 4 photocathodes with a forward gradient produce record AM 1.5 photocurrent densities for CuBi 2 O 4 up to -2.5 mA/cm 2 at 0.6 V vs RHE with H 2 O 2 as an electron scavenger, and they show a charge separation efficiency of 34% for 550 nm light. The gradient self-doping accomplishes this without the introduction of external dopants, and therefore the tetragonal crystal structure and carrier mobility of CuBi 2 O 4 are maintained. Lastly, forward gradient self-doped CuBi 2 O 4 photocathodes are protected with a CdS/TiO 2 heterojunction and coated with Pt as an electrocatalyst. These photocathodes demonstrate photocurrent densities on the order of -1.0 mA/cm 2 at 0.0 V vs RHE and evolve hydrogen with a faradaic efficiency of ∼91%.

Foam separation of Rhodamine-G and Evans Blue using a simple separatory bottle system.

PubMed

Dasarathy, Dhweeja; Ito, Yoichiro

2017-09-29

A simple separatory glass bottle was used to improve separation effectiveness and cost efficiency while simultaneously creating a simpler system for separating biological compounds. Additionally, it was important to develop a scalable separation method so this would be applicable to both analytical and preparative separations. Compared to conventional foam separation methods, this method easily forms stable dry foam which ensures high purity of yielded fractions. A negatively charged surfactant, sodium dodecyl sulfate (SDS), was used as the ligand to carry a positively charged Rhodamine-G, leaving a negatively charged Evans Blue in the bottle. The performance of the separatory bottle was tested for separating Rhodamine-G from Evans Blue with sample sizes ranged from 1 to 12mg in preparative separations and 1-20μg in analytical separations under optimum conditions. These conditions including N 2 gas pressure, spinning speed of contents with a magnetic stirrer, concentration of the ligand, volume of the solvent, and concentration of the sample, were all modified and optimized. Based on the calculations at their peak absorbances, Rhodamine-G and Evans Blue were efficiently separated in times ranging from 1h to 3h, depending on sample volume. Optimal conditions were found to be 60psi N 2 pressure and 2mM SDS for the affinity ligand. This novel separation method will allow for rapid separation of biological compounds while simultaneously being scalable and cost effective. Published by Elsevier B.V.

Plasmonic Photovoltaic Cells with Dual-Functional Gold, Silver, and Copper Half-Shell Arrays.

PubMed

Wu, Ling; Kim, Gyu Min; Nishi, Hiroyasu; Tatsuma, Tetsu

2017-09-12

Solid-state photovoltaic cells based on plasmon-induced charge separation (PICS) have attracted growing attention during the past decade. However, the power conversion efficiency (PCE) of the previously reported devices, which are generally loaded with dispersed metal nanoparticles as light absorbers, has not been sufficiently high. Here we report simpler plasmonic photovoltaic cells with interconnected Au, Ag, and Cu half-shell arrays deposited on SiO 2 @TiO 2 colloidal crystals, which serve both as a plasmonic light absorber and as a current collector. The well-controlled and easily prepared plasmonic structure allows precise comparison of the PICS efficiency between different plasmonic metal species. The cell with the Ag half-shell array has higher photovoltaic performance than the cells with Au and Cu half-shell arrays because of the high population of photogenerated energetic electrons, which gives a high electron injection efficiency and suppressed charge recombination probability, achieving the highest PCE among the solid-state PICS devices even without a hole transport layer.

Atomic and electronic structure of Lomer dislocations at CdTe bicrystal interface

PubMed Central

Sun, Ce; Paulauskas, Tadas; Sen, Fatih G.; Lian, Guoda; Wang, Jinguo; Buurma, Christopher; Chan, Maria K. Y.; Klie, Robert F.; Kim, Moon J.

2016-01-01

Extended defects are of considerable importance in determining the electronic properties of semiconductors, especially in photovoltaics (PVs), due to their effects on electron-hole recombination. We employ model systems to study the effects of dislocations in CdTe by constructing grain boundaries using wafer bonding. Atomic-resolution scanning transmission electron microscopy (STEM) of a [1–10]/(110) 4.8° tilt grain boundary reveals that the interface is composed of three distinct types of Lomer dislocations. Geometrical phase analysis is used to map strain fields, while STEM and density functional theory (DFT) modeling determine the atomic structure at the interface. The electronic structure of the dislocation cores calculated using DFT shows significant mid-gap states and different charge-channeling tendencies. Cl-doping is shown to reduce the midgap states, while maintaining the charge separation effects. This report offers novel avenues for exploring grain boundary effects in CdTe-based solar cells by fabricating controlled bicrystal interfaces and systematic atomic-scale analysis. PMID:27255415

Origin of Capacity Fading in Nano-Sized Co3O4 Electrodes: Electrochemical Impedance Spectroscopy Study

NASA Astrophysics Data System (ADS)

Kang, Jin-Gu; Ko, Young-Dae; Park, Jae-Gwan; Kim, Dong-Wan

2008-10-01

Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4 with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4 anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

[Quantum differences of ortho/para H2O2 spin-isomers as a factor of the femtosecond charge separation kinetics modulation in reaction centers of purple bacteria].

PubMed

Pishchal'nikov, R Iu; Pershin, S M; Bunkin, A F

2012-01-01

We have proposed the mechanism of coherent modulations of the P* state in the transient absorption spectra of the reaction center isolated from purple bacteria. Two water molecules, located between special pair, Ba, Bb chlorophylls and histidine L173 and M202, are supposed to be ortho-H2O and para-H2O isomers with different magnetic properties. The distinctive modulation frequencies were labeling as rotational resonances of ortho-H2O. According to our assumption, the interaction of rotational modes of water isomers with the charge-transfer states is a reason of coherent modulations of kinetics. We have modified a Hamiltonian system in order to take into account the rotational modes of ortho-H2O. Evolution of the density matrix was calculated in Liouville space. The Redfield relaxation theory for molecular aggregates was used to model kinetics up to 3 ps.

Atomic and electronic structure of Lomer dislocations at CdTe bicrystal interface

DOE PAGES

Sun, Ce; Paulauskas, Tadas; Sen, Fatih G.; ...

2016-06-03

Extended defects are of considerable importance in determining the electronic properties of semiconductors, especially in photovoltaics (PVs), due to their effects on electron-hole recombination. We employ model systems to study the effects of dislocations in CdTe by constructing grain boundaries using wafer bonding. Atomic-resolution scanning transmission electron microscopy (STEM) of a [1–10]/ (110) 4.8° tilt grain boundary reveals that the interface is composed of three distinct types of Lomer dislocations. Geometrical phase analysis is used to map strain fields, while STEM and density functional theory (DFT) modeling determine the atomic structure at the interface. The electronic structure of the dislocationmore » cores calculated using DFT shows significant mid-gap states and different charge-channeling tendencies. Cl-doping is shown to reduce the midgap states, while maintaining the charge separation effects. In conclusion, this report offers novel avenues for exploring grain boundary effects in CdTe-based solar cells by fabricating controlled bicrystal interfaces and systematic atomic-scale analysis.« less

Density-based Energy Decomposition Analysis for Intermolecular Interactions with Variationally Determined Intermediate State Energies

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

Wu, Q.; Ayers, P.W.; Zhang, Y.

2009-10-28

The first purely density-based energy decomposition analysis (EDA) for intermolecular binding is developed within the density functional theory. The most important feature of this scheme is to variationally determine the frozen density energy, based on a constrained search formalism and implemented with the Wu-Yang algorithm [Q. Wu and W. Yang, J. Chem. Phys. 118, 2498 (2003) ]. This variational process dispenses with the Heitler-London antisymmetrization of wave functions used in most previous methods and calculates the electrostatic and Pauli repulsion energies together without any distortion of the frozen density, an important fact that enables a clean separation of these twomore » terms from the relaxation (i.e., polarization and charge transfer) terms. The new EDA also employs the constrained density functional theory approach [Q. Wu and T. Van Voorhis, Phys. Rev. A 72, 24502 (2005)] to separate out charge transfer effects. Because the charge transfer energy is based on the density flow in real space, it has a small basis set dependence. Applications of this decomposition to hydrogen bonding in the water dimer and the formamide dimer show that the frozen density energy dominates the binding in these systems, consistent with the noncovalent nature of the interactions. A more detailed examination reveals how the interplay of electrostatics and the Pauli repulsion determines the distance and angular dependence of these hydrogen bonds.« less

Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

PubMed

Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

2014-03-11

Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

Lamellar cationic lipid-DNA complexes from lipids with a strong preference for planar geometry: A Minimal Electrostatic Model.

PubMed

Perico, Angelo; Manning, Gerald S

2014-11-01

We formulate and analyze a minimal model, based on condensation theory, of the lamellar cationic lipid (CL)-DNA complex of alternately charged lipid bilayers and DNA monolayers in a salt solution. Each lipid bilayer, composed by a random mixture of cationic and neutral lipids, is assumed to be a rigid uniformly charged plane. Each DNA monolayer, located between two lipid bilayers, is formed by the same number of parallel DNAs with a uniform separation distance. For the electrostatic calculation, the model lipoplex is collapsed to a single plane with charge density equal to the net lipid and DNA charge. The free energy difference between the lamellar lipoplex and a reference state of the same number of free lipid bilayers and free DNAs, is calculated as a function of the fraction of CLs, of the ratio of the number of CL charges to the number of negative charges of the DNA phosphates, and of the total number of planes. At the isoelectric point the free energy difference is minimal. The complex formation, already favoured by the decrease of the electrostatic charging free energy, is driven further by the free energy gain due to the release of counterions from the DNAs and from the lipid bilayers, if strongly charged. This minimal model compares well with experiment for lipids having a strong preference for planar geometry and with major features of more detailed models of the lipoplex. © 2014 Wiley Periodicals, Inc.

An Analytical Model of Tribocharging in Regolith

NASA Astrophysics Data System (ADS)

Carter, D. P.; Hartzell, C. M.

2015-12-01

Nongravitational forces, including electrostatic forces and cohesion, can drive the behavior of regolith in low gravity environments such as the Moon and asteroids. Regolith is the 'skin' of solid planetary bodies: it is the outer coating that is observed by orbiters and the first material contacted by landers. Triboelectric charging, the phenomenon by which electrical charge accumulates during the collision or rubbing of two surfaces, has been found to occur in initially electrically neutral granular mixtures. Although charge transfer is often attributed to chemical differences between the different materials, charge separation has also been found to occur in mixtures containing grains of a single material, but with a variety of grain sizes. In such cases, the charge always separates according to grain size; typically the smaller grains acquire a more negative charge than the larger grains. Triboelectric charging may occur in a variety of planetary phenomena (including mass wasting and dust storms) as well as during spacecraft-surface interactions (including sample collection and wheel motion). Interactions between charged grains or with the solar wind plasma could produce regolith motion. However, a validated, predictive model of triboelectric charging between dielectric grains has not yet been developed. A model for such size-dependent charge separation will be presented, demonstrating how random collisions between initially electrically neutral grains lead to net migration of electrons toward the smaller grains. The model is applicable to a wide range of single-material granular mixtures, including those with unusual or wildly varying size distributions, and suggests a possible mechanism for the reversal of the usual size-dependent charge polarity described above. This is a significant improvement over existing charge exchange models, which are restricted to two discrete grains sizes and provide severely limited estimates for charge magnitude. We will also discuss the design of an experiment planned to test the charging estimates provided by the model presented and the potential implications for our understanding of regolith behavior.

Analysis of heparin oligosaccharides by capillary electrophoresis-negative-ion electrospray ionization mass spectrometry.

PubMed

Lin, Lei; Liu, Xinyue; Zhang, Fuming; Chi, Lianli; Amster, I Jonathan; Leach, Franklyn E; Xia, Qiangwei; Linhardt, Robert J

2017-01-01

Most hyphenated analytical approaches that rely on liquid chromatography-MS require relatively long separation times, produce incomplete resolution of oligosaccharide mixtures, use eluents that are incompatible with electrospray ionization, or require oligosaccharide derivatization. Here we demonstrate the analysis of heparin oligosaccharides, including disaccharides, ultralow molecular weight heparin, and a low molecular weight heparin, using a novel electrokinetic pump-based CE-MS coupling eletrospray ion source. Reverse polarity CE separation and negative-mode electrospray ionization were optimized using a volatile methanolic ammonium acetate electrolyte and sheath fluid. The online CE hyphenated negative-ion electrospray ionization MS on an LTQ Orbitrap mass spectrometer was useful in disaccharide compositional analysis and bottom-up and top-down analysis of low molecular weight heparin. The application of this CE-MS method to ultralow molecular heparin suggests that a charge state distribution and the low level of sulfate group loss that is achieved make this method useful for online tandem MS analysis of heparins. Graphical abstract Most hyphenated analytical approaches that rely on liquid chromatography-MS require relatively long separation times, produce incomplete resolution of oligosaccharide mixtures, use eluents that are incompatible with electrospray ionization, or require oligosaccharide derivatization. Here we demonstrate the analysis of heparin oligosaccharides, including disaccharides, ultralow molecular weight heparin, and a low molecular weight heparin, using a novel electrokinetic pump-based CE-MS coupling eletrospray ion source. Reverse polarity CE separation and negative-mode electrospray ionization were optimized using a volatile methanolic ammonium acetate electrolyte and sheath fluid. The online CE hyphenated negative-ion electrospray ionization MS on an LTQ Orbitrap mass spectrometer was useful in disaccharide compositional analysis and bottom-up and top-down analysis of low molecular weight heparin. The application of this CE-MS method to ultralow molecular heparin suggests that a charge state distribution and the low level of sulfate group loss that is achieved make this method useful for online tandem MS analysis of heparins.

Final Report, DOE-BES grant DE-FG02-06ER46315

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

Clay, Rudolf Torsten; Mazumdar, Sumit

Determination of the mechanism of correlated-electron superconductivity (SC) has turned out to be the hardest problem in condensed matter physics. After nearly three decades of intense investigation of the high-T c cuprates it now appears that one key idea, viz., - weak doping of Mott-Hubbard semiconductors leads to SC -may not be correct, or is at least incomplete. This conclusion is arrived from recent experiments that have clearly indicated that the pseudogap state in the cuprates, separated by a thermodynamic phase transition from the undoped antiferromagnet, is significantly more complicated than thought before. Buried inside it there is a distinct charge-ordered (CO) state. Understanding the complete set of competing and coexisting phases in the pseudogap state is thus a formidable challenge. It follows that research on other correlated superconductors, which have also been known for a long time, may be able to give much needed fresh insight. It is with this motivation in this project we pursued theoretical research to understand the unconventional SC that is found in an apparently completely separate family of materials, the organic charge-transfer solids (CTS). A unique feature of the CTS is that SC there universally occurs at the carrier concentrationmore » $$\\rho$$ of 0.5 per organic molecule, rather than under carrier doping as in the cuprates. Our work in this project focused on the correlated physics of the organic CTS as well as other inorganic materials with the same carrier density, $$\\rho$$=0.5. This project resulted in several theoretical advances in understanding these materials.« less

Mimicking the photosynthetic triplet energy-transfer relay

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

Gust, D.; Moore, T.A.; Moore, A.L.

1993-06-30

In the reaction centers of photosynthetic organisms, chlorophyll triplet states are sometimes formed by recombination of charge-separated intermediates. These triplets are excellent sensitizers for singlet oxygen formation. Carotenoid polyenes can provide photoprotection from singlet oxygen generation by rapidly quenching chlorophyll triplet states via triplet-triplet energy transfer. Because in bacteria the reaction center carotenoid is not located adjacent to the bacteriochlorophyll special pair, which is the origin of the charge separation, it has been postulated that quenching may occur via a triplet relay involving an intermediate chlorophyll monomer. We now report the synthesis and spectroscopic study of a covalently linked carotenoidmore » (C)-porphyrin (P)-pyropheophorbide (Ppd) triad molecule which mimics this triplet relay. The pyropheophorbide singlet-state C-P-[sup 1]Ppd (generated by direct excitation or energy transfer from the attached porphyrin) undergoes intersystem crossing to the triplet C-P-[sup 3]Ppd. In oxygen-free solutions, this triplet decays to [sup 3]C-p-Ppd through a triplet-transfer relay involving an intermediate C-[sup 3]P-Ppd species. In aerated solutions, quenching of C-P-[sup 3]Ppd by the attached carotenoid competes with singlet oxygen sensitization and thus provides a degree of photoprotection. In a similar traid containing a zinc porphyrin moiety, triplet transfer is slow due to the higher energy of the C-[sup 3]P[sub Zn]-Ppd intermediate, and photoprotection via the relay is nonexistent. The triplet relay ceases to function at low temperatures in both the natural and biomimetic cases due to the endergonicity of the first step. 37 refs., 6 figs., 1 tab.« less

Strong field gravitational lensing by a charged Galileon black hole

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

Zhao, Shan-Shan; Xie, Yi, E-mail: clefairy035@163.com, E-mail: yixie@nju.edu.cn

Strong field gravitational lensings are dramatically disparate from those in the weak field by representing relativistic images due to light winds one to infinity loops around a lens before escaping. We study such a lensing caused by a charged Galileon black hole, which is expected to have possibility to evade no-hair theorem. We calculate the angular separations and time delays between different relativistic images of the charged Galileon black hole. All these observables can potentially be used to discriminate a charged Galileon black hole from others. We estimate the magnitudes of these observables for the closest supermassive black hole Sgrmore » A*. The strong field lensing observables of the charged Galileon black hole can be close to those of a tidal Reissner-Nordström black hole or those of a Reissner-Nordström black hole. It will be helpful to distinguish these black holes if we can separate the outermost relativistic images and determine their angular separation, brightness difference and time delay, although it requires techniques beyond the current limit.« less

Energy storage device with large charge separation

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

Holme, Timothy P.; Prinz, Friedrich B.; Iancu, Andrei T.

High density energy storage in semiconductor devices is provided. There are two main aspects of the present approach. The first aspect is to provide high density energy storage in semiconductor devices based on formation of a plasma in the semiconductor. The second aspect is to provide high density energy storage based on charge separation in a p-n junction.

Energy storage device with large charge separation

DOEpatents

Holme, Timothy P.; Prinz, Friedrich B.; Iancu, Andrei

2016-04-12

High density energy storage in semiconductor devices is provided. There are two main aspects of the present approach. The first aspect is to provide high density energy storage in semiconductor devices based on formation of a plasma in the semiconductor. The second aspect is to provide high density energy storage based on charge separation in a p-n junction.

Action spectra of photosystems II and I and quantum yield of photosynthesis in leaves in State 1.

PubMed

Laisk, Agu; Oja, Vello; Eichelmann, Hillar; Dall'Osto, Luca

2014-02-01

The spectral global quantum yield (YII, electrons/photons absorbed) of photosystem II (PSII) was measured in sunflower leaves in State 1 using monochromatic light. The global quantum yield of PSI (YI) was measured using low-intensity monochromatic light flashes and the associated transmittance change at 810nm. The 810-nm signal change was calibrated based on the number of electrons generated by PSII during the flash (4·O2 evolution) which arrived at the PSI donor side after a delay of 2ms. The intrinsic quantum yield of PSI (yI, electrons per photon absorbed by PSI) was measured at 712nm, where photon absorption by PSII was small. The results were used to resolve the individual spectra of the excitation partitioning coefficients between PSI (aI) and PSII (aII) in leaves. For comparison, pigment-protein complexes for PSII and PSI were isolated, separated by sucrose density ultracentrifugation, and their optical density was measured. A good correlation was obtained for the spectral excitation partitioning coefficients measured by these different methods. The intrinsic yield of PSI was high (yI=0.88), but it absorbed only about 1/3 of quanta; consequently, about 2/3 of quanta were absorbed by PSII, but processed with the low intrinsic yield yII=0.63. In PSII, the quantum yield of charge separation was 0.89 as detected by variable fluorescence Fv/Fm, but 29% of separated charges recombined (Laisk A, Eichelmann H and Oja V, Photosynth. Res. 113, 145-155). At wavelengths less than 580nm about 30% of excitation is absorbed by pigments poorly connected to either photosystem, most likely carotenoids bound in pigment-protein complexes. Copyright © 2013 Elsevier B.V. All rights reserved.

The project of the mass separator of atomic nuclei produced in heavy ion induced reactions

NASA Astrophysics Data System (ADS)

Oganessian, Yu. Ts.; Shchepunov, V. A.; Dmitriev, S. N.; Itkis, M. G.; Gulbekyan, G. G.; Khabarov, M. V.; Bekhterev, V. V.; Bogomolov, S. L.; Efremov, A. A.; Pashenko, S. V.; Stepantsov, S. V.; Yeremin, A. V.; Yavor, M. I.; Kalimov, A. G.

2003-05-01

A new separator and mass analyzer, named MASHA (mass analyzer of super heavy atoms), has been designed at the Flerov Laboratory JINR Dubna to separate and measure masses of nuclei and molecules with precision better than 10 -3. The set up can work in the wide mass range from A≈20 to A≈500, its mass acceptance is as large as ±2.8%. In particular, it allows unambiguous mass identification of super heavy nuclei with a resolution better than 1 amu at the level of 300 amu. Synthesized in nuclear reactions nuclides are emitted from an ECR ion source at energy E=40 kV and charge state Q=+1. Then they pass the following steps of separation and analysis: the first section of rough separation, the second section of separation and mass analysis and the final section of separation with a 90° electrostatic deflector. In the focal plane of the device, a focal plane detector determines positions (masses) of studied nuclei. Ion optics of the analyzer, optimized up to the second order, is considered. Description of its elements and subsystems is given.

The energetics of the primary proton transfer in bacteriorhodopsin revisited: it is a sequential light-induced charge separation after all.

PubMed

Braun-Sand, Sonja; Sharma, Pankaz K; Chu, Zhen T; Pisliakov, Andrei V; Warshel, Arieh

2008-05-01

The light-induced proton transport in bacteriorhodopsin has been considered as a model for other light-induced proton pumps. However, the exact nature of this process is still unclear. For example, it is not entirely clear what the driving force of the initial proton transfer is and, in particular, whether it reflects electrostatic forces or other effects. The present work simulates the primary proton transfer (PT) by a specialized combination of the EVB and the QCFF/PI methods. This combination allows us to obtain sufficient sampling and a quantitative free energy profile for the PT at different protein configurations. The calculated profiles provide new insight about energetics of the primary PT and its coupling to the protein conformational changes. Our finding confirms the tentative analysis of an earlier work (A. Warshel, Conversion of light energy to electrostatic energy in the proton pump of Halobacterium halobium, Photochem. Photobiol. 30 (1979) 285-290) and determines that the overall PT process is driven by the energetics of the charge separation between the Schiff base and its counterion Asp85. Apparently, the light-induced relaxation of the steric energy of the chromophore leads to an increase in the ion-pair distance, and this drives the PT process. Our use of the linear response approximation allows us to estimate the change in the protein conformational energy and provides the first computational description of the coupling between the protein structural changes and the PT process. It is also found that the PT is not driven by twist-modulated changes of the Schiff base's pKa, changes in the hydrogen bond directionality, or other non-electrostatic effects. Overall, based on a consistent use of structural information as the starting point for converging free energy calculations, we conclude that the primary event should be described as a light-induced formation of an unstable ground state, whose relaxation leads to charge separation and to the destabilization of the ion-pair state. This provides the driving force for the subsequent PT steps.

Capillary electrophoresis electrospray ionization mass spectrometry interface

DOEpatents

Smith, Richard D.; Severs, Joanne C.

1999-01-01

The present invention is an interface between a capillary electrophoresis separation capillary end and an electrospray ionization mass spectrometry emitter capillary end, for transporting an anolyte sample from a capillary electrophoresis separation capillary to a electrospray ionization mass spectrometry emitter capillary. The interface of the present invention has: (a) a charge transfer fitting enclosing both of the capillary electrophoresis capillary end and the electrospray ionization mass spectrometry emitter capillary end; (b) a reservoir containing an electrolyte surrounding the charge transfer fitting; and (c) an electrode immersed into the electrolyte, the electrode closing a capillary electrophoresis circuit and providing charge transfer across the charge transfer fitting while avoiding substantial bulk fluid transfer across the charge transfer fitting. Advantages of the present invention have been demonstrated as effective in providing high sensitivity and efficient analyses.

Radiative decay of neutron-unbound intruder states in 19O

NASA Astrophysics Data System (ADS)

Dungan, R.; Tabor, S. L.; Tripathi, Vandana; Volya, A.; Kravvaris, K.; Abromeit, B.; Caussyn, D. D.; Morrow, S.; Parker, J. J.; Tai, P.-L.; VonMoss, J. M.

2016-02-01

The 9Be(14C, α γ ) reaction at EL a b=30 and 35 MeV was used to study excited states of 19O. The Florida State University (FSU) γ detector array was used to detect γ radiation in coincidence with charged particles detected and identified with a silicon Δ E -E particle telescope. γ decays have been observed for the first time from six states ranging from 368 to 2147 keV above the neutron separation energy (Sn=3962 keV) in 19O. The γ -decaying states are interspersed among states previously observed to decay by neutron emission. The ability of electromagnetic decay to compete successfully with neutron decay is explained in terms of neutron angular momentum barriers and small spectroscopic factors implying higher spin and complex structure for these intruder states. These results illustrate the need for complementary experimental approaches to best illuminate the complete nuclear structure.

Phase separation of electrons strongly coupled with phonons in cuprates and manganites

NASA Astrophysics Data System (ADS)

Alexandrov, Sasha

2009-03-01

Recent advanced Monte Carlo simulations have not found superconductivity and phase separation in the Hubbard model with on-site repulsive electron-electron correlations. I argue that microscopic phase separations in cuprate superconductors and colossal magnetoresistance (CMR) manganites originate from a strong electron-phonon interaction (EPI) combined with unavoidable disorder. Attractive electron correlations, caused by an almost unretarded EPI, are sufficient to overcome the direct inter-site Coulomb repulsion in these charge-transfer Mott-Hubbard insulators, so that low energy physics is that of small polarons and small bipolarons. They form clusters localized by disorder below the mobility edge, but propagate as the Bloch states above the mobility edge. I identify the Froehlich EPI as the most essential for pairing and phase separation in superconducting layered cuprates. The pairing of oxygen holes into heavy bipolarons in the paramagnetic phase (current-carrier density collapse (CCDC)) explains also CMR and high and low-resistance phase coexistence near the ferromagnetic transition of doped manganites.

Transition-state optimization by the free energy gradient method: Application to aqueous-phase Menshutkin reaction between ammonia and methyl chloride

NASA Astrophysics Data System (ADS)

Hirao, Hajime; Nagae, Yukihiko; Nagaoka, Masataka

2001-11-01

The transition state (TS) for the Menshutkin reaction H 3N+CH 3Cl→H 3NCH 3++Cl - in aqueous solution was located on the free energy surface (FES) by the free energy gradient (FEG) method. The solute-solvent system was described by a hybrid quantum mechanical and molecular mechanical (QM/MM) method. The reaction path in water was found to deviate largely from that in the gas phase. It was concluded that, in such a reaction including charge separation, TS structure optimization on an FES is inevitable for obtaining valid information about a TS in solution.

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

Ultrafast exciton dynamics and light-driven H2 evolution in colloidal semiconductor nanorods and Pt-tipped nanorods.

PubMed

Wu, Kaifeng; Zhu, Haiming; Lian, Tianquan

2015-03-17

Colloidal quantum confined one-dimensional (1D) semiconductor nanorods (NRs) and related semiconductor-metal heterostructures are promising new materials for efficient solar-to-fuel conversion because of their unique physical and chemical properties. NRs can simultaneously exhibit quantum confinement effects in the radial direction and bulk like carrier transport in the axial direction. The former implies that concepts well-established in zero-dimensional quantum dots, such as size-tunable energetics and wave function engineering through band alignment in heterostructures, can also be applied to NRs; while the latter endows NRs with fast carrier transport to achieve long distance charge separation. Selective growth of catalytic metallic nanoparticles, such as Pt, at the tips of NRs provides convenient routes to multicomponent heterostructures with photocatalytic capabilities and controllable charge separation distances. The design and optimization of such materials for efficient solar-to-fuel conversion require the understanding of exciton and charge carrier dynamics. In this Account, we summarize our recent studies of ultrafast charge separation and recombination kinetics and their effects on steady-state photocatalytic efficiencies of colloidal CdS and CdSe/CdS NRs and related NR-Pt heterostructures. After a brief introduction of their electronic structure, we discuss exciton dynamics of CdS NRs. By transient absorption and time-resolved photoluminescence decay, it is shown that although the conduction band electrons are long-lived, photogenerated holes in CdS NRs are trapped on an ultrafast time scale (∼0.7 ps), which forms localized excitons due to strong Coulomb interaction in 1D NRs. In quasi-type II CdSe/CdS dot-in-rod NRs, a large valence band offset drives the ultrafast localization of holes to the CdSe core, and the competition between this process and ultrafast hole trapping on a CdS rod leads to three types of exciton species with distinct spatial distributions. The effect of the exciton dynamics on photoreduction reactions is illustrated using methyl viologen (MV(2+)) as a model electron acceptor. The steady-state MV(2+) photoreduction quantum yield of CdSe/CdS dot-in-rod NRs approaches unity under rod excitation, much larger than CdSe QDs and CdSe/CdS core/shell QDs. Detailed time-resolved studies show that in quasi-type II CdSe/CdS NRs and type II ZnSe/CdS NRs strong quantum confinement in the radial direction facilitates fast electron transfer and hole removal, whereas the fast carrier mobility along the axial direction enables long distance charge separation and slow charge recombination, which is essential for efficient MV(2+) photoreduction. The NR/MV(2+) relay system can be coupled to Pt nanoparticles in solution for light-driven H2 generation. Alternatively, Pt-tipped CdS and CdSe/CdS NRs provide fully integrated all inorganic systems for light-driven H2 generation. In CdS-Pt and CdSe/CdS-Pt hetero-NRs, ultrafast hole trapping on the CdS rod surface or in CdSe core enables efficient electron transfer from NRs to Pt tips by suppressing hole and energy transfer. It is shown that the quantum yields of photodriven H2 generation using these heterostructures correlate well with measured hole transfer rates from NRs to sacrificial donors, revealing that hole removal is the key efficiency-limiting step. These findings provide important insights for designing more efficient quantum confined NR and NR-Pt based systems for solar-to-fuel conversion.

Separation and Purification of Mineral Salts from Spacecraft Wastewater Processing via Electrostatic Beneficiation

NASA Technical Reports Server (NTRS)

Miles, John D., II; Lunn, Griffin

2013-01-01

Electrostatic separation is a class of material processing technologies commonly used for the sorting of coarse mixtures by means of electrical forces acting on charged or polarized particles. Most if not all of the existing tribo-electrostatic separators had been initially developed for mineral ores beneficiation. It is a well-known process that has been successfully used to separate coal from minerals. Potash (potassium) enrichment where underground salt mines containing large amounts of sodium is another use of this techno logy. Through modification this technology can be used for spacecraft wastewater brine beneficiation. This will add in closing the gap beeen traveling around Earth's Gravity well and long-term space explorations. Food has been brought on all man missions, which is why plant growth for food crops continues to be of interest to NASA. For long-term mission considerations food productions is one of the top priorities. Nutrient recovery is essential for surviving in or past low earth orbit. In our advance bio-regenerative process instead of nitrogen gas produced; soluble nitrate salts that can be recovered for plant fertilizer would be produced instead. The only part missing is the beneficiation of brine to separate the potassium from the sodium. The use of electrostatic beneficiation in this experiment utilizes the electrical charge differences between aluminum and dried brine by surface contact. The helixes within the aluminum tribocharger allows for more surface contact when being agitated. When two materials are in contact, the material with the highest affinity for electrons becomes negatively charged, while the other becomes positively charged. This contact exchange of charge may cause the particles to agglomerate depending on their residence time within the tribocharger, compromising the efficiency of separation. The aim of this experiment is to further the development in electrostatic beneficiation by optimizing the separation of ersatz and possibly real wastewater brine residues. In doing so, ideally it will yield a high potassium enrichment for use in spacecraft plant systems.

Multi-frequency inversion-charge pumping for charge separation and mobility analysis in high-k/InGaAs metal-oxide-semiconductor field-effect transistors

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

Djara, V.; Cherkaoui, K.; Negara, M. A.

2015-11-28

An alternative multi-frequency inversion-charge pumping (MFICP) technique was developed to directly separate the inversion charge density (N{sub inv}) from the trapped charge density in high-k/InGaAs metal-oxide-semiconductor field-effect transistors (MOSFETs). This approach relies on the fitting of the frequency response of border traps, obtained from inversion-charge pumping measurements performed over a wide range of frequencies at room temperature on a single MOSFET, using a modified charge trapping model. The obtained model yielded the capture time constant and density of border traps located at energy levels aligned with the InGaAs conduction band. Moreover, the combination of MFICP and pulsed I{sub d}-V{sub g}more » measurements enabled an accurate effective mobility vs N{sub inv} extraction and analysis. The data obtained using the MFICP approach are consistent with the most recent reports on high-k/InGaAs.« less

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.

Molecular orbital evaluation of charge flow dynamics in natural pigments based photosensitizers.

PubMed

Heera, Thekinneydath Rajan; Cindrella, Louis

2010-03-01

The relationship between structure and photo electrochemical property of ten natural pigments from plants, insects and microbes has been analyzed using density functional theory (DFT) at the B3LYP/6-31G(d) level. The essential parameters for their photoelectrochemical behaviour such as ground state geometries, electronic transition energies and oxidation potentials are computed. The attachment tendency of the anchoring groups, expressed as the deprotonation order, is determined by calculating the proton affinities at different sites of the molecules. A thorough analysis of the charge flow dynamics in the molecular orbitals (HOMO and LUMO) of these molecules has been carried out and presented to emphasize the role of these orbitals in effective charge separation, the important feature of photosensitizers for DSSC. This study highlights that the flexible spatial orientation provided by the bridging aliphatic unsaturation favours the oscillator strength and the hydroxyl anchor group attached to the ring of delocalized pi electron cloud acts as the effective anchor.

Inversion layer solar cell fabrication and evaluation

NASA Technical Reports Server (NTRS)

Call, R. L.

1972-01-01

Silicon solar cells with induced junctions were created by forming an inversion layer near the surface of the silicon by supplying a sheet of positive charge above the surface. This charged layer was supplied through three mechanisms: (1) supplying a positive potential to a transparent electrode separated from the silicon surface by a dielectric, (2) contaminating the oxide layer with positive ions, and (3) forming donor surface states that leave a positive charge on the surface. A movable semi-infinite shadow delineated the extent of sensitivity of the cell due to the inversion region. Measurements of the inversion layer cell response to light of different wavelengths indicated it to be more sensitive to the shorter wavelengths of the sun's spectrum than conventional cells. Theory of the conductance of the inversion layer vs. strength of the inversion layer was compared with experiment and found to match. Theoretical determinations of junction depth and inversion layer strength were made as a function of the surface potential for the transparent electrode cell.

Charged pion production in $$\

DOE PAGES

Eberly, B.; et al.

2015-11-23

Charged pion production via charged-current νμ interactions on plastic scintillator (CH) is studied using the MINERvA detector exposed to the NuMI wideband neutrino beam at Fermilab. Events with hadronic invariant mass W < 1.4 GeV and W < 1.8 GeV are selected in separate analyses: the lower W cut isolates single pion production, which is expected to occur primarily through the Δ(1232) resonance, while results from the higher cut include the effects of higher resonances. Cross sections as functions of pion angle and kinetic energy are compared to predictions from theoretical calculations and generator-based models for neutrinos ranging in energymore » from 1.5–10 GeV. The data are best described by calculations which include significant contributions from pion intranuclear rescattering. As a result, these measurements constrain the primary interaction rate and the role of final state interactions in pion production, both of which need to be well understood by neutrino oscillation experiments.« less

Inversion layer solar cell fabrication and evaluation. [measurement of response of inversion layer solar cell to light of different wavelengths

NASA Technical Reports Server (NTRS)

Call, R. L.

1973-01-01

Silicon solar cells operating with induced junctions rather than diffused junctions have been fabricated and tested. Induced junctions were created by forming an inversion layer near the surface of the silicon by supplying a sheet of positive charge above the surface. This charged layer was supplied through three mechanisms: (1) applying a positive potential to a transparent electrode separated from the silicon surface by a dielectric, (2) contaminating the oxide layer with positive ions, and (3) forming donor surface states that leave a positive charge on the surface. A movable semi-infinite shadow delineated the extent of sensitivity of the cell due to the inversion region. Measurements of the response of the inversion layer cell to light of different wavelengths indicated it to be more sensitive to the shorter wavelengths of the sun's spectrum than conventional cells. The greater sensitivity occurs because of the shallow junction and the strong electric field at the surface.